Transfer sheet for forming concavo-convex shape, method for manufacturing transfer sheet for forming concavo-convex shape, and method for forming concavo-convex shape

Abstract

A transfer sheet (10) for texturing formation includes: a water-soluble-resin layer (20) that is formed from a water-soluble resin in which the dissolving time in distilled water at 25°C is 0.2-1.0 s / µm and that has projections and recesses on a first surface thereof; and a water-insoluble resin layer (30) that is layered on the first surface.

Description

Technical Field

[0001] The present invention relates to a transfer sheet for forming an uneven shape suitable for forming a coating layer having unevenness on, for example, the surface of an aircraft fuselage or the surface of an automobile body, a method for manufacturing the transfer sheet for forming an uneven shape, and a method for forming an uneven shape.

Background Art

[0002] It is known that by forming an uneven shape on the surface of an aircraft fuselage or the surface of an automobile body, etc., the resistance of the fluid flowing on the surface can be reduced and the fuel consumption can be improved. Examples of such uneven shapes include sharkskin shapes and riblets. The inventors of the present invention have proposed a technique of directly attaching a transfer sheet laminated with a water-soluble resin layer and a coating material layer to the surface of an aircraft fuselage or the surface of an automobile body, etc., and washing the surface with water to expose an uneven shape made of the coating material layer on the surface (see Patent Document 1). With this technique, a desired uneven shape can be transferred to the transfer target without being affected by the shape of the transfer target.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] In the technique described in Patent Document 1, for example, when forming an uneven shape on the surface of an aircraft fuselage using such a transfer sheet, there is an advantage that a large device is not required and a precise shape can be formed with high accuracy even on a curved surface, but there is a demand for shortening the water washing operation time required for water washing.

[0005] In view of the above circumstances, an object of the present invention is to provide a transfer sheet for forming an uneven shape, which can shorten the water washing operation time in the step of forming an uneven water-insoluble resin layer on a transfer object, and further prevent cracking in the step of manufacturing the transfer sheet, a method for manufacturing such a transfer sheet for forming an uneven shape, and a method for forming an uneven shape.

Means for Solving the Problems

[0006] In order to achieve the above object, a transfer sheet for forming an uneven shape according to the present invention is made of a water-soluble resin having a dissolution time in distilled water at 25°C of 0.2 seconds / μm or more and 1.0 second / μm or less, and includes a water-soluble resin layer having unevenness on its first surface and a water-insoluble resin layer laminated on the first surface.

[0007] In the step of forming an uneven water-insoluble resin layer on a transfer object, after the transfer sheet is attached to the surface of the transfer object, the surface is washed with water to remove the water-soluble resin layer, and an uneven shape made of a water-insoluble resin layer is exposed on the surface. In the present invention, since the water-soluble resin layer has a dissolution time in distilled water at 25°C of 0.2 seconds / μm or more, the water washing operation time during the above water washing can be shortened. On the other hand, since the water-soluble resin has a dissolution time in distilled water at 25°C of 1.0 second / μm or less, cracking in the step of manufacturing the transfer sheet can be prevented.

[0008] In the transfer sheet for forming an uneven shape according to the present invention, the water-soluble resin preferably contains polyvinyl alcohol and polyvinylpyrrolidone, and the total mass of polyvinyl alcohol and polyvinylpyrrolidone is 40 mass percent or more and less than 100 mass percent based on the total amount of the water-soluble resin, more preferably 50 mass% or more and 98 mass% or less. This is because if it is less than 40 mass%, the film strength at normal temperature decreases and the uneven processing property decreases. If it is 100 mass%, the film strength during heating decreases. In the transfer sheet for forming the concavo-convex shape according to the present invention, it is preferable that the water-soluble resin has a degree of polymerization of polyvinyl alcohol of 250 or more and 1000 or less, and more preferably 300 or more and 800 or less. This is because if the degree of polymerization of polyvinyl alcohol is less than 250, the hygroscopicity at room temperature will increase. If the degree of polymerization of polyvinyl alcohol exceeds 1000, the solubility will decrease.

[0009] Also, in the transfer sheet for forming the concavo-convex shape according to the present invention, it is preferable that the water-soluble resin has a degree of polymerization of polyvinylpyrrolidone of 100 or more and 2000 or less, and more preferably 200 or more and 1000 or less. This is because if the degree of polymerization of polyvinylpyrrolidone is less than 100, the hygroscopicity at room temperature will increase. If the degree of polymerization of polyvinylpyrrolidone exceeds 2000, the solubility will decrease and the concavo-convex processability will decrease.

[0010] In the transfer sheet for forming the concavo-convex shape according to the present invention, it is preferable that the water-soluble resin has a mass ratio of polyvinyl alcohol to polyvinylpyrrolidone in the range of 80:20 to 20:80, and more preferably in the range of 70:30 to 30:70. This is because if the mass ratio of polyvinyl alcohol is high, the solubility will decrease. If the mass ratio of polyvinylpyrrolidone is high, the hygroscopicity will increase.

[0011] In the transfer sheet for forming the concavo-convex shape according to the present invention, it is preferable that the saponification degree of the polyvinyl alcohol in the water-soluble resin is 70% or more and 99% or less, and more preferably 80% or more and 90% or less. This is because if the saponification degree is lower than 70%, the strength of the film will be weak and the concavo-convex shape cannot be maintained. If the saponification degree exceeds 99%, the solubility is low, that is, it is difficult to dissolve.

[0012] In the transfer sheet for forming the concavo-convex shape according to the present invention, it is preferable that the water-soluble resin layer contains latex or a plasticizer.

[0013] When the water-soluble resin layer contains latex or a plasticizer, when forming an uneven shape on the first surface of the water-soluble resin layer typically using a heated embossing roller, the uneven shape can be accurately transferred.

[0014] In the transfer sheet for forming an uneven shape according to the present invention, it is preferable that the water-soluble resin layer contains 2 mass percent or more and 50 mass percent or less of latex, and more preferably contains 5 mass percent or more and 40 mass percent or less of latex. This is because when the latex content is less than 2 mass percent, the film strength decreases during heating. When the latex content exceeds 50 mass percent, the film strength at room temperature decreases and the embossing processability deteriorates.

[0015] The plasticizer contained in the water-soluble resin layer is typically a high-boiling alcohol and may be contained in a lower content than the latex. In the transfer sheet for forming an uneven shape according to the present invention, it is preferable that the water-soluble resin layer contains 2 mass percent or more and 10 mass percent or less of the plasticizer, and more preferably contains 3 mass percent or more and 8 mass percent or less of the plasticizer. This is because when the plasticizer content is less than 2 mass percent, the film strength decreases during heating. When the plasticizer content exceeds 10 mass percent, the film strength at room temperature decreases and the embossing processability deteriorates.

[0016] The transfer sheet for forming an uneven shape according to the present invention is preferably a long sheet wound in a roll shape. This reduces the bulk, making it easier to transport and store. Also, the exposed area of the transfer sheet for forming an uneven shape decreases, making it difficult for moisture to be absorbed from the sheet surface into the sheet interior.

[0017] The transfer sheet for forming an uneven shape according to the present invention includes a support layer laminated on the opposite surface of the first surface of the water-soluble resin layer, and it is preferable that the peel peel strength between the support layer and the water-soluble resin layer is 2 g / cm or more and 70 g / cm or less. When the peel peel strength is less than 2 g / cm, it will peel off during handling, and when the peel peel strength exceeds 70 g / cm, it cannot be easily removed before the water washing operation.

[0018] The transfer sheet for forming the concavo-convex shape according to the present invention preferably has a sliding layer on the surface opposite to the surface in contact with the water-insoluble resin layer of the support layer. By having the sliding layer, when the transfer sheet for forming the concavo-convex shape is attached to the object to be transferred, a spatula or a rubber spatula can be efficiently slid, and the generation of wrinkles and air pockets can be prevented.

[0019] The transfer sheet for forming the concavo-convex shape according to the present invention may include an adhesive layer laminated on the surface opposite to the surface facing the first surface of the water-soluble resin layer of the water-insoluble resin layer. Thereby, further working time can be shortened. In the transfer sheet for forming the concavo-convex shape according to the present invention, it is preferable that the water-insoluble resin layer is formed of a coating liquid dissolved in a solvent, typically a coating material. By using the coating liquid, it becomes easy to adjust the penetrability into the concavo-convexities on the first surface of the water-soluble resin according to the resin composition, viscosity, and coating method. In the transfer sheet for forming the concavo-convex shape according to the present invention, it is preferable that the water-insoluble resin layer is made of polyurethane or an acrylic resin. By using polyurethane or an acrylic resin, the strength and durability of the water-insoluble resin layer can be improved, and the cost can be reduced. In the transfer sheet for forming the concavo-convex shape according to the present invention, it is preferable that the water-insoluble resin layer is made of a resin obtained by curing an ultraviolet-curable resin composition. By using a resin obtained by curing an ultraviolet-curable resin composition, the viscosity can be easily adjusted, and the concavo-convex shape can be transferred with higher accuracy. Also, the strength of the concavo-convex shape can be ensured.

[0020] The method for manufacturing the transfer sheet for forming the concavo-convex shape according to the present invention includes a step of preparing a water-soluble resin layer made of a water-soluble resin having a dissolution time in distilled water at 25 ° C of 0.2 seconds / μm or more and 1.0 seconds / μm or less and having concavo-convexities on the first surface, and a step of forming a water-insoluble resin layer on the first surface. In the present invention, a water-insoluble resin layer may be formed on the object to be transferred, and then a water-insoluble resin layer may be formed on the first surface.

[0021] In the method for manufacturing a transfer sheet for forming a concavo-convex shape according to the present invention, the step of preparing a water-soluble resin layer having concavo-convexities on the first surface preferably includes a step of feeding a roll-shaped water-soluble resin sheet constituting the water-soluble resin layer, and a step of transferring the concavo-convexities to the first surface of the fed water-soluble resin sheet using a heated concavo-convex roller.

[0022] In the method for manufacturing a transfer sheet for forming a concavo-convex shape according to the present invention, after forming a water-insoluble resin layer on the first surface, it is preferable to further include a step of winding the transfer sheet for forming a concavo-convex shape into a roll shape.

[0023] In the method for manufacturing a transfer sheet for forming a concavo-convex shape according to the present invention, the water-insoluble resin layer is made of a coating material, and the step of forming the water-insoluble resin layer on the first surface may include a step of laminating a coating liquid of the coating material on the first surface, and a step of drying the coating liquid to form a coating material layer on the first surface of the water-soluble resin layer.

[0024] In the method for manufacturing a transfer sheet for forming a concavo-convex shape according to the present invention, the water-insoluble resin layer is made of a resin obtained by curing an ultraviolet-curable resin composition, and the step of forming the water-insoluble resin layer on the first surface may include a step of laminating a coating liquid of the ultraviolet resin composition on the first surface, and a step of curing the coating liquid to form a resin obtained by curing the ultraviolet-curable resin composition on the first surface of the water-soluble resin layer.

[0025] The method for forming a concavo-convex shape according to the present invention includes a step of attaching the water-insoluble resin layer side of any of the above transfer sheets for forming a concavo-convex shape to the surface of the object to be transferred, and a step of removing the water-soluble resin layer of the transfer sheet for forming a concavo-convex shape attached to the surface of the object to be transferred to leave the water-insoluble resin layer on the surface of the object to be transferred, and exposing the concavo-convex shape made of the water-insoluble resin layer on the surface of the object to be transferred.

Effects of the Invention

[0026] According to the present invention, it is possible to shorten the water washing operation time in the step of forming a water-insoluble resin layer with a concavo-convex shape on the object to be transferred, and further prevent cracking in the step of manufacturing the transfer sheet.

Brief Description of the Drawings

[0027]

Figure 1

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Figure 4

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Figure 9

Figure 10

Modes for Carrying Out the Invention

[0028] Hereinafter, embodiments of the present invention will be described with reference to the drawings.

[0029] <Configuration of the Transfer Sheet for Forming a Concavo-Convex Shape> FIG. 1 is a cross-sectional view of a transfer sheet for forming concavo-convex shapes according to an embodiment of the present invention.

[0030] As shown in FIG. 1, the transfer sheet 10 for forming concavo-convex shapes has a water-soluble resin layer 20 and a water-insoluble resin layer 30.

[0031] The transfer sheet 10 for forming concavo-convex shapes is used, for example, to form a water-insoluble resin layer 30 made of a coating material that functions as a riblet on the surface of an aircraft fuselage or an automobile body. However, the transfer sheet for forming concavo-convex shapes according to the present invention is not limited to riblet formation, and its use is not limited as long as it is for forming concavo-convex shapes. <<Water-soluble resin layer>> The water-soluble resin layer 20 is made of a water-soluble resin having a dissolution time in distilled water at 25°C of 0.2 seconds / μm or more and 1.0 second / μm or less, and has concavo-convexities 22 on the first surface 21. It is more preferable that the water-soluble resin has a dissolution time in distilled water at 25°C of 0.5 seconds / μm or more and 0.6 seconds / μm or less.

[0032] Here, the dissolution time is the dissolution time per unit film thickness of the water-soluble resin layer. After measuring the thickness of a 2 cm square water-soluble resin layer fixed to a jig, 800 ml of distilled water was placed in a 1 L beaker, and while maintaining a temperature of 25°C, the entire jig was immersed in the water stirred by a stirrer (600 rpm), and the time until dissolution was measured. Here, dissolution means a state where the particles become insoluble fine particles with a diameter of 1 mm or less. As the water-soluble resin, polyvinyl alcohol, polyvinyl pyrrolidone, and / or gelatin can be used. Among these, polyvinyl alcohol and polyvinyl pyrrolidone are preferable. Further, a combination of polyvinyl alcohol and polyvinyl pyrrolidone is particularly preferable in terms of dissolution time, concavo-convex processability, and film strength. The total mass of polyvinyl alcohol and polyvinyl pyrrolidone in the water-soluble resin is 40 mass percent or more and less than 100 mass percent. It is more preferable that the total mass of polyvinyl alcohol and polyvinyl pyrrolidone in the water-soluble resin is 50 mass percent or more and 98 mass percent or less.

[0033] The water-soluble resin has a degree of polymerization of polyvinyl alcohol of 250 or more and 1000 or less, and a degree of polymerization of polyvinylpyrrolidone of 100 or more and 2000 or less.

[0034] The water-soluble resin has a mass ratio of polyvinyl alcohol to polyvinylpyrrolidone in the range of 80:20 to 20:80. It is more preferable that the mass ratio of polyvinyl alcohol to polyvinylpyrrolidone in the water-soluble resin is in the range of 70:30 to 30:70.

[0035] In addition to the composition containing polyvinyl alcohol and polyvinylpyrrolidone, the water-soluble resin may contain latex (styrene-butadiene latex, acrylate latex), plasticizer (glycerin, diglycerin, trimethylolpropane, polyethylene glycol), other water-soluble polymers (unmodified PVA-based resin, modified PVA-based resin other than anionic group, sodium polyacrylate, polyethylene oxide, polyvinylpyrrolidone, dextrin, chitosan, chitin, methylcellulose, hydroxyethylcellulose, etc.), fragrance, rust inhibitor, colorant, extender, defoamer, ultraviolet absorber, etc.

[0036] The water-soluble resin layer 20 contains latex or plasticizer. Thereby, the occurrence of cracks during the uneven shape processing can be prevented. It is preferable that the water-soluble resin layer 20 contains 2% by mass or more and 50% by mass or less of latex, and it is preferable that the water-soluble resin layer 20 contains 5% by mass or more and 40% by mass or less of latex.

[0037] The water-soluble resin layer 20 may contain a plasticizer instead of latex. The plasticizer is typically a high-boiling alcohol and may have a lower content than latex. It is preferable that the water-soluble resin layer 20 contains 2% by mass or more and 10% by mass or less of the plasticizer, and it is preferable that the water-soluble resin layer 20 contains 3% by mass or more and 8% by mass or less of the plasticizer.

[0038] The water-soluble resin layer 20 is preferably thicker than the height of the peaks of the unevenness 22. Typically, the water-soluble resin layer 20 has a thickness of 50 μm or more and 250 μm or less, more preferably 80 μm or more and 200 μm or less. At this time, the height of the peaks of the unevenness 22 is 10 μm or more and 150 μm or less. If the thickness of the water-soluble resin layer is less than 50 μm, accurate recesses may not be formed. If it exceeds 200 μm, the time required to wash away the water-soluble resin sheet may become too long. <<Support for the water-soluble resin layer>> If necessary, a support layer 50 may be provided on the surface 23 opposite to the first surface 21 on which the water-insoluble resin layer 30 is laminated as shown in FIG. 2 in the water-soluble resin layer 20. As the support layer 50, a known resin film, paper, coated paper, or the like can be used. This can prevent dimensional deformation of the water-soluble resin and prevent damage. The thickness of the support layer 50 is preferably 20 μm or more and 200 μm or less.

[0039] Further, a surface treatment (not shown) for adjusting the adhesive force between the support layer 50 and the water-soluble resin layer 20 may be performed on the support layer 50. As the surface treatment, corona treatment, primer treatment, adhesion treatment, anchor treatment, or the like can be used. The peel-off force between the support layer and the water-soluble resin layer is 2 g / cmm or more and 70 g / cm or less, more preferably 20 g / cmm or more and 50 g / cm or less.

[0040] <<Sliding layer of the support for the water-soluble resin layer>> Furthermore, when the support layer 50 is a resin film, a layer (not shown) for improving slipperiness may be provided on the surface opposite to the surface facing the water-soluble resin layer 20 of the support layer 50, if necessary. The layer may be formed by applying a coating solution such as an acrylic polymer containing fine particles or the like with a thickness of 2 to 30 μm, or by attaching paper or coated paper.

[0041] <<Water-insoluble resin layer>> The water-insoluble resin layer 30 is laminated on the first surface 21 of the water-soluble resin layer 20. As the water-insoluble resin constituting the water-insoluble resin layer 30, alkyd resin-based, aminoalkyd resin-based, acrylic resin-based, acrylic-urethane resin-based, polyurethane resin-based, epoxy resin-based, chlorinated rubber-based, olefin resin-based, ultraviolet curable-based, silicone resin-based, electron beam curable-based, silicon resin-based, petroleum-based, vinyl resin-based, phenol resin-based, fluororesin-based, polyester resin-based, melamine resin-based, lacquer-based, etc. can be used. Further, as the water-insoluble resin layer 30, by using polyhedral oligomeric silsesquioxane (POSS)-modified polyurethane, or a shape memory elastomer containing polyurethane, silicone, epoxy, polysulfide, ethylene propylene diene, fluorosilicone, and fluoroelastomer, etc., the advantage of not being deformed can be obtained.

[0042] Among these, polyurethane resin and acrylic resin are particularly preferable from the viewpoints of resin strength, durability, cost, etc. <<<Polyurethane, Acrylic>>> The polyurethane resin is a reaction product of a polyol having a plurality of hydroxyl groups and a polyisocyanate. Examples of the polyol include polyester polyol, acrylic polyol, epoxy polyol, polyether polyol, hydroxyl-terminated polybutadiene, polyolefin polyol, polycarbonate polyol, hydroxyl-containing silicone resin, etc. As the polyol, those containing a hydroxyl value of about 200 to 800 mgKOH / g are preferable. Examples of the isocyanate include 1,6-hexamethylene diisocyanate, cyclo butane-1,3-diisocyanate, cyclohexane-1,3 diisocyanate, isophorone diisocyanate (IPDI), isocyanatomethyl octylene diisocyanate (TTI), 2,4-hexahydrotoluylene diisocyanate (H6TDI), he xahydro-1,3-phenylene diisocyanate, perhydro 2,4'-diphenyl Aromatic isocyanates such as methane diisocyanate (H12MDI), 2-methylpentamethylene diisocyanate (MPDI), and tetramethylxylylene diisocyanate (TXMDI), aliphatic isocyanates, and alicyclic isocyanates can be used. Among these, aliphatic isocyanates are particularly preferred from the viewpoints of durability and mechanical properties of the resin. The molecular weight of the polyurethane resin is preferably about 1,500 to 150,000, more preferably about 2,000 to 120,000.

[0043] The acrylic resin is a resin obtained by radical polymerization of acrylic monomers such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl acrylate, methoxyethylene glycol acrylate, and ethoxyethylene glycol acrylate. To the acrylic resin of the present invention, 2-hydroxy (meth) acrylate, (meth) acrylic acid, glycidyl (meth) acrylate, etc. may be copolymerized as necessary to introduce hydroxyl groups, carboxyl groups, epoxy groups, etc. The molecular weight of the alkyl resin is preferably about 1,500 to 150,000, more preferably about 2,000 to 120,000. <<<UV-curable resin>>> The UV-curable resin composition is one that cures by ultraviolet rays to form a hydrophobic polymer, and is a composition containing a curable monomer, a curable oligomer, a photoinitiator, and, if necessary, a sensitizer and a solvent.

[0044] The viscosity of the UV-curable resin composition is preferably 20 mPa·s or more and 1,000 mPa·s or less, more preferably 50 mPa·s or more and 800 mPa·s or less. When the viscosity is less than 20 mPa·s, it may be difficult to laminate the liquid UV-curable resin composition, and when it exceeds 1,000 mPa·s, the liquid UV-curable resin composition may not sufficiently penetrate into the concave portion of the water-soluble resin sheet.

[0045] The curable monomer and the curable oligomer are monomers or oligomers having a functional group that can be polymerized by radicals generated by an initiator or an acid. Examples of such functional groups include vinyl groups, (meth)acryloyloxy groups, vinyloxy groups, epoxy groups, etc. Among these, the (meth)acryloyloxy group is particularly preferred. Among these are polyethylene glycol diacrylate, propoxylated ethoxylated bisphenol A diacrylate (about 600 mPa·s), 1,10-decanediol diacrylate (about 10 mPa·s), pentaerythritol triacrylate (about 800 mPa·s), ethoxylated bisphenol A dimethacrylate (about 500 mPa·s), tripropylene glycol diacrylate (about 10 mPa·s), polyethylene glycol #400 dimethacrylate (about 35 mPa·s), 2-hydroxy-3-acryloyloxypropyl methacrylate (about 45 mPa·s), polyethylene glycol #200 diacrylate (about 20 mPa·s), ethoxylated pentaerythritol tetraacrylate (about 350 mPa·s), ethoxylated glycerin triacrylate (about 200 mPa·s), ethoxylated bisphenol A diacrylate (about 1100 mPa·s), ethoxylated isocyanuric acid triacrylate (about 1000 mPa·s), etc. These may be used alone or in combination of a plurality. acrylate (about 500 mPa·s), tripropylene glycol diacrylate (about 10 mPa·s), polyethylene glycol #400 dimethacrylate (about 35 mPa·s), 2-hydroxy-3-acryloyloxypropyl methacrylate (about 45 mPa·s), polyethylene glycol #200 diacrylate (about 20 mPa·s), ethoxylated pentaerythritol tetraacrylate (about 350 mPa·s), ethoxylated glycerin triacrylate (about 200 mPa·s), ethoxylated bisphenol A diacrylate (about 1100 mPa·s), ethoxylated isocyanuric acid triacrylate (about 1000 mPa·s), etc. There are . These may be used alone or in combination of a plurality.

[0046] As the photopolymerization initiator, known ones can be used. For example, there are benzoin compounds, benzophenone compounds, acylphosphine oxide compounds, iodonium salt compounds, sulfonium salt compounds, etc.

[0047] In the present invention, known photosensitizers such as xanthone compounds and anthracene compounds may be used in combination as necessary.

[0048] As other materials, fillers such as silica, reactive diluents such as ethyl methacrylate and butyl methacrylate, ultraviolet absorbers, antistatic agents, etc. may be added to the ultraviolet curable resin composition as required.

[0049] In the present invention, these resins are laminated on the first surface 21 of the water-soluble resin layer 20 as a coating solution (coating material) dissolved in a solvent. As the solvent, known solvents such as toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, and acetone can be used. Also, the above-mentioned resin may be in the form of a latex and used as a coating solution with water as the dispersion medium.

[0050] It is preferable to use a crosslinking agent in the coating solution of the present invention. As the crosslinking agent, known ones such as isocyanate-based, epoxy-based, and oxazoline-based can be used, but from the viewpoint of reactivity, an isocyanate-based crosslinking agent is preferable. As the isocyanate-based crosslinking agent, those described in the above-mentioned urethane resin can be used.

[0051] A known surfactant can be added to the coating solution of the present invention as required.

[0052] There is no particular limitation on the solid content concentration of the coating solution of the present invention, but it is preferably about 5% by mass to 80% by mass.

[0053] Also, there is no particular limitation on the viscosity of the coating solution of the present invention, but a range of about 10 mPa·s to 150 mPa·s is preferable.

[0054] The water-insoluble resin layer 30 has irregularities 32 corresponding to the irregularities 22 of the first surface 21 of the water-soluble resin layer 20 on the second surface 31 facing the first surface 21 of the water-soluble resin layer 20 by applying a coating solution containing a water-insoluble resin and then drying it. The thickness of the water-insoluble resin layer 30 excluding the irregularities 32 is typically 5 μm to 70 μm.

[0055] The height of the irregularities 32 of the water-insoluble resin layer 30 is typically 10 μm or more and 150 μm Followingand more preferably, it is preferably 20 μm or more and 120 μm or less. The interval between the unevenness is typically 10 μm or more and 400 μm or less, and more preferably 20 μm or more and 300 μm or less. The width of the tip of the peak of the unevenness 32 is 0 μm or more and 40 μm or less, and more preferably 0 μm or more and 30 μm or less.

[0056] The shape of the peak of the unevenness 32 is typically a triangle with an apex angle of 20° or more and 45° or less. The shape of the peak of the unevenness 32 may be other shapes. The shape of the unevenness 32 is determined by the shape of the unevenness 22 of the water-soluble resin layer 20. <<Adhesive layer>> In addition, as needed, an adhesive layer 60 may be provided on the opposite surface of the water-insoluble resin layer 30 on the side of the water-soluble resin layer 20 as shown in FIG. 4.

[0057] As the adhesive of the adhesive layer 60, known ones such as acrylic, rubber-based, and silicone-based ones can be used. The thickness of the adhesive layer 60 is preferably about 10 μm to 30 μm. It is preferable to laminate a release film (not shown) on the opposite surface of the adhesive layer 60 on the side of the water-insoluble resin layer 30.

[0058] Also, as shown in FIG. 5, a base material 70 may be provided on the opposite surface of the water-insoluble resin layer 30 on the side of the water-soluble resin layer 20. The base material 70 is not particularly limited as long as it is flexible. For example, known polymer sheets such as polyester and polyolefin can be used. Among them, polyethylene terephthalate is preferable in terms of strength and cost. There is no particular limitation on the thickness of the base material 70, and for example, those having a thickness of about 20 μm to 100 μm can be used. In order to improve the adhesiveness on both sides of the base material 70, surface treatments such as corona treatment and flame treatment may be performed, or an undercoat layer such as acrylic or urethane may be provided. Further, a decorative layer, a coloring layer, etc. may be provided on the base material 70 as needed, or symbols, identification marks, etc. may be applied.

[0059] Further, as shown in FIG. 6, an adhesive layer 80 may be provided on the opposite surface of the water-insoluble resin layer 30 of the base material 70. As the adhesive layer 80, known ones such as acrylic, rubber, and silicone can be used. The thickness of the adhesive layer 80 is preferably about 10 μm to 30 μm. It is preferable to laminate a release film (not shown) on the surface of the adhesive layer 80 opposite to the base material 70. <Method for manufacturing transfer sheet for forming uneven shape> FIG. 3 is an explanatory diagram showing the process of manufacturing the transfer sheet 10 for forming uneven shape. <<Method for forming water-soluble resin layer>> Prepare a supply roll 1 in which a water-soluble resin sheet 2 made of a water-soluble resin having a dissolution time in distilled water at 25 ° C. of 0.2 seconds / μm or more and 1.0 second / μm or less is in a roll shape.

[0060] Note that the method for preparing the water-soluble resin sheet 2 is not particularly limited. For example, it can be prepared by a method such as applying an aqueous solution containing polyvinyl alcohol on the support layer 50 and then drying it. The coating method is not particularly limited, and known methods such as a slide coater, a gravure coater, and a curtain coater can be used. The water-soluble resin sheet 2 may be composed of one layer or two or more layers. Also, two sets of those obtained by applying an aqueous solution containing polyvinyl alcohol on the water-soluble resin sheet support and drying are prepared, and the respective coating layers are bonded with a polyvinyl alcohol-based adhesive, and then the water-soluble resin sheet support is peeled off. It may be formed by a method. The water-soluble resin sheet may be one from which the water-soluble resin sheet support is peeled off, or one having the water-soluble resin sheet support on one surface.

[0061] Further, the support layer 50 may be provided with a surface treatment (not shown) for adjusting the adhesive force between the support layer 50 and the water-soluble resin layer 20. As the surface treatment, corona treatment, primer treatment, adhesion treatment, anchor treatment, etc. can be used. The peel-off force between the support layer and the water-soluble resin layer is 2 g / cm or more and 70 or less, more preferably 20 g / cm or more and 50 g / cm or less, so that peeling does not occur during uneven shape formation or processing in subsequent steps.

[0062] Furthermore, a layer (not shown) for improving slipperiness may be provided on the surface of the support layer 50 opposite to the surface facing the water-soluble resin layer 20, may be provided in advance, or may be provided after manufacturing the transfer sheet 10 for forming the concavo-convex shape. <<Method for Processing Concave Portions>> The water-soluble resin sheet 2 fed out from the supply roll 1 is run between the heat-concavo-convex roller 3 and the pressure roller 4. As a result, concavo-convexities formed on the surface of the heat-concavo-convex roller 3 are formed on the first surface of the water-soluble resin sheet 2. The water-soluble resin sheet 2 having the concavo-convexities formed thereon constitutes the water-soluble resin layer 20 shown in FIG. 1. That is, a water-soluble resin layer 20 made of a water-soluble resin having a dissolution time in distilled water at 25° C. of 0.2 seconds / μm or more and 1.0 second / μm or less and having concavo-convexities on the first surface is prepared. In the manufacturing method according to the present embodiment, the water-soluble resin layer 20 contains latex or a plasticizer, and since the water-soluble resin layer 20 is made of a water-soluble resin having a dissolution time in distilled water at 25° C. of 1.0 / μm or less, when forming the concavo-convex shape using the heat-concavo-convex roller 3, the concavo-convex shape can be accurately transferred. <<Method for Forming Water-Insoluble Resin Layer>> Hereinafter, a coating liquid (coating material) in which a water-insoluble resin is dissolved in a solvent will be described as an example.

[0063] The coating material 6 is supplied from the coating material feeder 5 to the first surface of the water-soluble resin sheet 2 having the concavo-convexities formed thereon, and the coating material 6 is applied to the first surface. The coating material 6 applied to the first surface of the water-soluble resin sheet 2 constitutes the water-insoluble resin layer 30 shown in FIG. 1. That is, the coating liquid is applied to the first surface. The coating method is not particularly limited, and known methods such as a bar coater, a slide coater, a gravure coater, a curtain coater, and a die coater can be used. The wet coating amount of the water-insoluble resin at this time is 10 g / m 2 or more and 200 g / m 2 or less is preferable.

[0064] There are no particular restrictions on the conditions for drying the coating solution, and methods such as natural drying at room temperature or heat drying at about 40°C to 150°C can be used. Furthermore, it is also preferable to perform heat treatment at a temperature of about 40°C to 80°C for about 2 hours to 24 hours in order to promote the reaction of the crosslinking agent after drying.

[0065] For example, the water-soluble resin sheet 2 coated with the coating material 6 is heated by the heating device 7 at 80 to 120°C for 2 to 30 minutes. By this heating, the solvent of the coating material 6 is volatilized and dried and cured. Thereby, the transfer sheet 10 for forming the concavo-convex shape in which the water-soluble resin layer 20 and the water-insoluble resin layer 30 are laminated as shown in FIG. 1 is manufactured. That is, the water-insoluble resin layer 30 is formed on the first surface of the water-soluble resin layer 20.

[0066] In addition, a protective sheet (not shown) or the like may be laminated on the water-insoluble resin layer 30 as necessary.

[0067] When the water-insoluble resin layer is a polyurethane or an acrylic resin, a cured layer is formed by the above-described heating. When the water-insoluble resin layer is an ultraviolet-curable resin composition, the ultraviolet-curable resin composition is cured by ultraviolet irradiation to form a cured layer. In the method of forming a cured layer by ultraviolet irradiation, heating at a high temperature for a long time is not required, so the transfer sheet for forming the concavo-convex shape is not damaged by heat.

[0068] The ultraviolet-curable resin composition according to the present invention may be cured by irradiating ultraviolet rays from the ultraviolet-curable resin composition side or may be cured by irradiating ultraviolet rays from the water-soluble resin sheet side. When providing the base material 70, by irradiating ultraviolet rays from the water-soluble resin sheet side, the base material side does not need to be transparent so that ultraviolet rays can pass through, and the base material can be colored or an opaque layer can be freely laminated on the base material. Further, when providing the base material 70, the ultraviolet-curable resin composition may be applied to the first surface of the water-soluble resin layer 20, and then the base material 70 may be laminated and then irradiated with ultraviolet rays, or the ultraviolet-curable resin composition may be applied to the base material 70, and then the first surface of the water-soluble resin layer 20 may be laminated thereon and then irradiated with ultraviolet rays. As the light source, a xenon lamp, a mercury lamp, a metal halide lamp, an ultraviolet LED lamp, etc. can be used. The irradiation energy depends on the type of polymerization initiator and the ultraviolet curable resin composition, but is desirably about 10 to 10000 mJ / cm 2 degree.

[0069] In the present invention, after curing with ultraviolet rays, heat treatment may be performed as necessary. The heating temperature and time are preferably about 100°C to 200°C and 10 minutes to 120 minutes. By this heating, the curing of the ultraviolet curable resin composition further proceeds, and the strength of the water-insoluble resin layer 30 is improved.

[0070] The transfer sheet 10 for forming an uneven shape, which is a water-soluble resin sheet 2 on which the coating material 6 is cured, is wound into a roll. By making it a roll winding 11, the bulk of the transfer sheet 10 for forming an uneven shape is reduced, and it becomes easier to transport and store. In addition, the exposed area of the transfer sheet 10 for forming an uneven shape is reduced, and it becomes difficult for moisture to be absorbed from the sheet surface into the sheet interior. On the other hand, since the water-soluble resin layer 20 is made of a water-soluble resin having a dissolution time in distilled water at 25°C of 1.0 / μm or less, the shape of the water-soluble resin layer does not collapse during the above-mentioned transportation and storage. <<Method for forming an adhesive layer>> In the present invention, an adhesive layer 60 may be provided on the opposite surface of the water-insoluble resin layer 30 of the transfer sheet 10 for forming an uneven shape that contacts the water-soluble resin layer. The method for laminating the adhesive layer is not particularly limited. For example, after applying an adhesive on a hydrophobic polymer sheet, it may be heat-cured at 80 to 150°C for 1 to 30 minutes and laminated to the water-insoluble resin layer 30, or it may be formed by directly applying it to the water-insoluble resin layer 30. <Method for forming an uneven shape on the surface of the object to be transferred> Hereinafter, a coating liquid (coating material) in which a water-insoluble resin is dissolved in a solvent will be described as an example. FIG. 7 is a diagram showing an example of a process of forming an uneven shape on an object to be transferred using the transfer sheet 10 for forming an uneven shape.

[0071] Apply a coating material 41 to the surface of the object to be transferred 40 (Fig. 7(a)). It is preferable to use the same material as the water-insoluble resin layer 30 of the transfer sheet 10 for forming the uneven shape for the coating material 41. However, the present invention is not limited to using the same material as the water-insoluble resin layer 30 for the coating material 41. As the coating material 41, an alkyd resin type, amino alkyd resin type, acrylic resin type, acrylic-urethane resin type, polyurethane resin type, epoxy resin type, chlorinated rubber type, olefin resin type, ultraviolet curable type, silicone resin type, electron beam curable type, silicon resin type, petroleum type, vinyl resin type, phenol resin type, fluororesin type, polyester resin type, melamine resin type, lacquer type, etc. can be used. A primer paint or the like may be used as the coating material 41.

[0072] Attach the transfer sheet 10 for forming the uneven shape to the surface of the object to be transferred 40 via the coating material 41 (Fig. 7(b)). Arrange the transfer sheet 10 for forming the uneven shape on the surface of the object to be transferred 40 so that the water-insoluble resin layer 30 of the transfer sheet 10 for forming the uneven shape is in contact with the coating material 41, and apply pressure from the water-soluble resin layer 20 side of the transfer sheet 10 for forming the uneven shape to attach the transfer sheet 10 for forming the uneven shape to the surface of the object to be transferred 40. Typically, the sheet fed out from the transfer sheet 10 for forming the uneven shape of the roll winding 11 is cut to a predetermined size, and the cut transfer sheet 10 for forming the uneven shape is attached to the surface of the object to be transferred 40.

[0073] The water-soluble resin layer 20 of the transfer sheet 10 for forming the uneven shape attached to the surface of the object to be transferred 40 is removed, and the water-insoluble resin layer 30 is left on the surface of the object to be transferred 40, so that the uneven shape composed of the water-insoluble resin layer 30 is exposed on the surface of the object to be transferred 40 (Fig. 7(c)). The removal of the water-soluble resin layer 20 is typically carried out by an operator washing with water, that is, spraying water from a hose onto the surface of the transfer sheet 10 for forming the uneven shape attached to the surface of the object to be transferred 40 to remove the water-soluble resin layer 20 by water pressure. As the conditions for washing with water, it is advisable to use warm water, for example, and a sponge, brush, etc. may be used at that time. In the forming method according to the present embodiment, since the water-soluble resin layer 20 is made of a water-soluble resin having a dissolution time in distilled water at 25 °C of 0.2 seconds / μm or more, the water-soluble resin layer 20 can be removed in a shorter time during washing with water.

[0074] Note that the forming method according to the present invention is not limited to the above-described aspect.

[0075] For example, as shown in Fig. 8, instead of applying the coating material 41 to the surface of the object to be transferred 40, the coating material 41 is applied to the water-insoluble resin layer 30 of the transfer sheet 10 for forming the uneven shape, and then it is attached to the surface of the object to be transferred 40. Thereafter, although not shown, the water-soluble resin layer 20 of the transfer sheet 10 for forming the uneven shape may be removed to leave the water-insoluble resin layer 30 on the surface of the object to be transferred 40, and the uneven shape composed of the water-insoluble resin layer 30 may be exposed on the surface of the object to be transferred 40.

[0076] Also, when the transfer sheet 10 for forming the uneven shape having the configuration shown in Fig. 4 is used, as shown in Fig. 9, the adhesive layer 60 of the transfer sheet 10 for forming the uneven shape is directly attached to the surface of the object to be transferred 40. Thereafter, although not shown, the water-soluble resin layer 20 of the transfer sheet 10 for forming the uneven shape may be removed to leave the water-insoluble resin layer 30 on the surface of the object to be transferred 40, and the uneven shape composed of the water-insoluble resin layer 30 may be exposed on the surface of the object to be transferred 40.

[0077] Furthermore, using the transfer sheet 10 for forming the concavo-convex shape shown in FIG. 6, as shown in FIG. 10, the adhesive layer 80 of the transfer sheet 10 for forming the concavo-convex shape is directly attached to the surface of the object to be transferred 40. Here, for example, after that, although not shown, the water-soluble resin layer 20 of the transfer sheet 10 for forming the concavo-convex shape may be removed and the water-insoluble resin layer 30 may be left on the surface of the object to be transferred 40, and the concavo-convex shape composed of the water-insoluble resin layer 30 may be exposed on the surface of the object to be transferred 40.

[0078] In these examples, the water-insoluble resin layer 30 made of a coating material is taken as an example for explanation. However, the insoluble resin layer may be made of polyurethane or acrylic resin, and the water-insoluble resin layer may be made of a resin obtained by curing an ultraviolet curable resin composition. Further, a support layer 50 and a layer for improving slipperiness may be provided on the water-soluble resin layer 20 shown in FIGS. 7 to 10.

[0079] <Example 1> The present invention will be described more specifically with reference to the following examples. However, the present invention is not limited to the following examples. Of course, the present invention includes those in which the content of the examples is changed from the gist of the present invention.

[0080] First, the experimental results obtained to evaluate the "solubility" and "concavo-convex processability" of the water-soluble resin layer 20 are shown below.

[0081] In this experiment, the following components of polyvinyl alcohol (PVA) and polyvinylpyrrolidone (PVP) were used as the materials of the water-soluble resin sheet constituting the water-soluble resin layer 20 of the transfer sheet 10 for forming the concavo-convex shape. Depending on the case, latex was added. Also, a dye was added.

[0082] PVA: "PVA-117" Kuraray Poval 28-98 Kuraray Co., Ltd. "PVA-205" Kuraray Poval 5-88 Kuraray Co., Ltd. "PVA-217" Kuraray Poval 22-88 Kuraray Co., Ltd.

Table 1

Table 2

[0083] 1. A water-soluble resin sheet was produced as follows. (1) PVA particles were added to distilled water and heated to 90 °C until completely dissolved. After cooling this solution to room temperature, PVP particles and latex were added in sequence and mixed. Further, a trace amount of dye was added to color the solution, and an aqueous solution was prepared.

[0084] (2) The obtained aqueous solution was applied using a bar coater and dried at room temperature to form a film (water-soluble resin sheet) with a thickness of 100 μm.

[0085] 2. Method for evaluating solubility (1) Excluding the ears for fixing the jig of the water-soluble resin sheet cut into 2 × 3 cm, the film thickness of the 2 cm square range was measured with a thickness gauge.

[0086] (2) 800 mL of distilled water was placed in a 1 L beaker and stirred with a stirrer (600 rpm) while maintaining 25 °C. A 2 cm square water-soluble resin sheet fixed to a jig was immersed, and the time from immersion until dissolution was measured. Here, dissolution was defined as the state of becoming insoluble fine particles with a diameter of 1 mm or less.

[0087] 3. Method for evaluating embossing processability (1) A mold (corresponding to the heating uneven roller 3) with convex portions of uneven shapes was heated to 130 °C in an oven. The convex portions are grooves in which 20 isosceles triangles with a height of 50 μm and an apex angle of 45 degrees are arranged in parallel, and the interval between the grooves is 100 μm.

[0088] (2) The mold was taken out of the oven and pressed against a water-soluble resin sheet at 50 kgf / cm to process the concave portions.

[0089] (3) The transfer condition of the unevenness to the water-soluble resin sheet was evaluated by cross-section using a dinolite.

[0090] The evaluation results are shown in Table 3.

Table 3

[0091] 1. Regarding PVA "PVA-117" has poor solubility. It is considered that the degree of saponification is high. "PVA-205" has good solubility when combined with PVP. "PVA-217" has improved solubility when combined with PVP, but is inferior to "PVA-205".

[0092] 2. Regarding the combination of "PVA-205" and PVP (1) The combination with "K15" When the mass ratio of "PVA-205" to "K15" is 1:1, cracks occurred due to bending at 130 °C. When the mass ratio of "PVA-205" to "K15" is 1:3, the moisture absorption at room temperature is high.

[0093] (2) The combination with "K30" When the mass ratio of "PVA-205" to "K30" is 1:1, cracks occurred due to bending at 130 °C.

[0094] When the mass ratio of "PVA-205" to "K30" is 1:3, the moisture absorption at room temperature is lower than that of "K15" under the same conditions.

[0095] (3) Combination with "K90" When the mass ratio of "PVA-205" to "K90" is 1:1, the solubility is inferior to that of "K15" and "K30" under the same conditions. 3. Regarding latex It was found that it is effective to contain latex in order to prevent cracking at 130°C while maintaining solubility.

[0096] In addition, the method of increasing the degree of polymerization of PVA or the degree of polymerization of PVP is effective as a countermeasure against cracking at 130°C, but the solubility decreases. Also, if the content of latex or plasticizer is too high, the retention of the uneven shape deteriorates. 4. Conclusion From the above, the following conclusions were obtained.

[0097] When 10 - 40 mass percent of latex is contained with respect to PVA:PVP = 1:1, better results can be obtained in terms of "solubility", "film strength at 130°C", and "processability of unevenness at 130°C".

[0098] <Example 2> Next, the experimental results conducted to evaluate the "peeling force" between the water-soluble resin layer and the support layer of the water-soluble resin sheet having a support are shown below. In this experiment, the following polyvinyl alcohol (PVA), polyvinylpyrrolidone (PVP), and latex were used as materials for the water-soluble resin sheet.

[0099] PVA: "PVA-205" Kuraray Poval 5-88 Kuraray Co., Ltd. PVP: "K30" Polyvinylpyrrolidone K30 Tokyo Chemical Industry Co., Ltd. Latex: Styrene-butadiene-based latex "LX407S6" Nippon Zeon Co., Ltd.

[0100] 1. A water-soluble resin sheet having a support was produced as follows. (1) A sheet of biaxially stretched polyethylene terephthalate with a thickness of 50 μm was prepared as the support of the water-soluble resin sheet, and surface treatment (corona treatment at a treatment intensity of 100 W·min / m 2 ) was carried out on one side.

[0101] (2) An aqueous solution in which 30 mass percent of latex was dissolved in PVA:PVP = 1:1 was applied to the treated surface using a bar coater, and a film (water-soluble resin sheet) with a thickness of 100 μm was produced by drying at room temperature.

[0102] 2. Evaluation method of peel force (1) A mold (corresponding to the heated concavo-convex roller 3) with convex portions of a concavo-convex shape was heated to 130 °C. The convex portions are grooves in which 1000 isosceles triangles with a height of 50 μm and a vertex angle of 45 degrees are arranged in parallel, and the interval between the grooves is 100 μm.

[0103] (2) The mold was pressed against the water-soluble resin layer surface of the water-soluble resin sheet at 50 kgf / cm to form concave portions, and the presence or absence of peeling between the water-soluble resin layer and the support layer at this time was evaluated. The evaluation results are shown in Table 4.

Table 4

[0104] <Example 3> Furthermore, the experimental results with the water-insoluble resin layer changed are shown below. In this experiment, the following polyvinyl alcohol (PVA), polyvinylpyrrolidone (PVP), and latex were used as the materials of the water-soluble resin sheet. A pigment was also added. PVA: "PVA-205", Kuraray Co., Ltd. Kuraray PVP: "K30", Polyvinylpyrrolidone K30, Tokyo Chemical Industry Co., Ltd. Latex: Styrene-butadiene latex "LX407S6", Nippon Zeon Co., Ltd. Dye: G, Tokyo Chemical Industry Co., Ltd.

[0105] 1. A water-soluble resin sheet having a support was produced as follows. (1) A sheet of biaxially oriented polyethylene terephthalate with a thickness of 50 μm was prepared as the support of the water-soluble resin sheet, and surface treatment (corona treatment at a treatment intensity of 100 W·min / m 2 ) was carried out on one side. (2) An aqueous solution in which 30 mass percent of latex was dissolved with PVA:PVP = 1:1 was applied to the treated surface using a bar coater and dried at 80 °C for 15 minutes to form a coating layer with a thickness of 80 μm. This coating operation was repeated one more time to form a coating layer with a thickness of 160 μm.

[0106] 2. Embossing of the water-soluble resin sheet (1) A mold (corresponding to the heated embossing roller 3) with convex portions of the embossed shape was heated to 130 °C. The convex portions are grooves in which 1000 isosceles triangles with a height of 50 μm and a vertex angle of 45 degrees are arranged in parallel, and the interval between the grooves is 100 μm.

[0107] (2) The mold was pressed against the water-soluble resin layer surface of the water-soluble resin sheet at 50 kgf / cm to form concave portions.

[0108] ≪Example 3A-1≫ 3. The following were used as the water-insoluble resin.

[0109] UV curable resin: UV681, Permabond (Viscosity: 90 mPa·s)

[0110] 4. A transfer sheet for forming an embossed shape was produced as follows. First, a base material was produced as follows. (Corresponding to 70 and 80 in Figure 6) One side of a 50-μm thick biaxially stretched polyethylene terephthalate sheet was corona-treated at a treatment intensity of 100 W·min / m 2 . A black stripe pattern was formed on this treated surface with an ultraviolet-curable ink. Furthermore, an adhesive sheet with a release film was laminated on the opposite side. Next, the aforementioned ultraviolet-curable resin composition was applied to a thickness of 200 μm using a doctor blade on the surface of the substrate where the stripe pattern was formed. Then, the above water-soluble resin sheet was laminated thereon and pressed at a pressure of 0.03 Kg / cm 2 for 20 seconds. The water-soluble resin sheet was laminated with the surface having the recesses in contact with the ultraviolet-curable resin composition.

[0111] Next, the ultraviolet-curable resin composition was cured with an energy of 500 mJ / cm 2 using a high-pressure mercury lamp to obtain a cured layer.

[0112] Then, a heat treatment was performed at 110°C for 20 minutes.

[0113] The transfer sheet for forming the concavo-convex shape was manufactured through the above steps. 5. The formation of the concavo-convex shape was carried out as follows.

[0114] A 10 cm × 10 cm sample was cut out from the transfer sheet for forming the concavo-convex shape prepared above. The release film on the back surface of the substrate side of this sample was peeled off, and the transfer sheet for forming the concavo-convex shape was laminated on the duralumin plate through the adhesive layer. A plastic spatula was used for lamination.

[0115] Next, the water-soluble resin sheet support on the surface was peeled off.

[0116] Thereafter, the water-soluble resin sheet on the surface was removed by washing with water. Washing with water was performed by spraying tap water onto the surface of the water-soluble resin sheet. It was visually confirmed that the water-soluble resin sheet was removed.

[0117] The concavo-convex shape was formed through the above steps.

[0118] When the formed uneven shape was observed with an optical microscope, there was no damage such as chipping, and the shape of the concave part was correctly reproduced. <<Example 3A-2>> Example 3A-2 was carried out in the same manner as Example 3A-1 except that the ultraviolet curable resin composition was changed as follows. When the ultraviolet curable resin composition was applied on the substrate, the end portion spread, and except that the thickness of this portion became thinner, a favorable uneven shape similar to that of Example 3A-1 could be obtained. · Ultraviolet curable resin composition Viscosity: about 10 mPa·s 1,10 - Decanediol diacrylate: 80 parts by mass Tripropylene glycol diacrylate: 20 parts by mass Photoinitiator Irgacure 907: 6 parts by mass

[0119] <<Example 3A-3>> When Example 3A-3 was carried out in the same manner as Example 3A-1 except that the ultraviolet curable resin composition was changed as follows, a favorable uneven shape similar to that of Example 3A-1 could be obtained. · Ultraviolet curable resin composition Viscosity: about 35 mPa·s Polyethylene glycol #400 dimethacrylate: 60 parts by mass 2 - Hydroxy - 3 - acryloyloxypropyl methacrylate: 30 parts by mass Polyethylene glycol #200 diacrylate: 10 parts by mass Photoinitiator Irgacure 907: 6 parts by mass

[0120] <<Example 3A-4>> When Example 3A-4 was carried out in the same manner as Example 3A-1 except that the ultraviolet curable resin composition was changed as follows, a favorable uneven shape similar to that of Example 3A-1 could be obtained. · Ultraviolet curable resin composition Viscosity: about 300 mPa·s Ethoxylated pentaerythritol tetraacrylate: 80 parts by mass Ethoxy glycerin triacrylate: 20 parts by mass Photoinitiator Irgacure 907: 6 parts by mass

[0121] ≪Example 3A-5≫ Example 3A-5 was carried out in the same manner as Example 3A-1 except that the ultraviolet curable resin composition was changed as follows, and a good uneven shape similar to that of Example 3A-1 was obtained. · Ultraviolet curable resin composition Viscosity: about 700 mPa·s Ethoxylated bisphenol A dimethacrylate: 20 parts by mass Pentaerythritol triacrylate: 80 parts by mass Photoinitiator Irgacure 907: 6 parts by mass

[0122] ≪Example 3A-6≫ Example 3A-6 was carried out in the same manner as Example 3A-1 except that the ultraviolet curable resin composition was changed as follows and a water-soluble resin sheet was laminated and pressed at a pressure of 0.06 Kg / cm 2 for 30 seconds, and a good uneven shape similar to that of Example 3A-1 was obtained. · Ultraviolet curable resin composition Viscosity: about 1500 mPa·s Ethoxylated bisphenol A diacrylate: 80 parts by mass Ethoxylated isocyanuric acid triacrylate: 10 parts by mass Dipentaerythritol polyacrylate: 10 parts by mass Photoinitiator Irgacure 907: 6 parts by mass

[0123] ≪Example 3A-7≫ A transfer sheet for forming an uneven shape was prepared in the same manner as in Example 3A-1. Subsequently, paper (sliding layer) with a basis weight of 70 g / m 2 was laminated via an adhesive on the surface of the water-soluble resin sheet support side of the transfer sheet for forming an uneven shape. Thereafter, an uneven shape was formed in the same manner as in Example 1. When the transfer sheet for forming an uneven shape was laminated on the duralumin plate, the plastic spatula had good slipperiness and good workability. When the formed uneven shape was observed with an optical microscope, there was no damage such as chipping, and the shape of the concave part was correctly reproduced.

[0124] ≪Example 3A-8≫ Both sides of a 50-μm-thick biaxially stretched polyethylene terephthalate sheet as a water-soluble resin sheet support were subjected to corona treatment at a treatment intensity of 100 W·min / m. 2 The following coating liquid was applied to one side of this sheet so that the dry coating amount was 18 g / m. 2 Then, it was dried at 120°C for 20 minutes to form a coating layer (sliding layer). · Coating liquid for coating layer Bironal MD1245 (aqueous polyester resin manufactured by Toyobo Co., Ltd., concentration 30%) 30 parts by mass Acrylic fine particles MX2000 (manufactured by Soken Chemical & Engineering Co., Ltd., particle size 20 μm) 8 parts by mass Pure water was added to make it 100 g. Next, a water-soluble resin sheet was formed on the opposite side in the same manner as in Example 3A-1. Using this water-soluble resin sheet, an uneven shape was formed in the same manner as in Example 3A-1. When the transfer sheet for forming the uneven shape was bonded to the duralumin plate, the sliding of the plastic spatula was good and the workability was good. When the formed uneven shape was observed with an optical microscope, there was no damage such as chipping, and the shape of the concave part was correctly reproduced.

[0125] ≪Example 3A-9≫ Example 3A-9 was carried out in the same manner as Example 3A-1 except that brilliant blue was not added to the water-soluble resin sheet. Attention was paid to the fact that the degree of removal was difficult to judge visually when the water-soluble resin sheet was removed by washing. When the obtained uneven shape was observed with an optical microscope, there was no damage such as chipping, and the shape of the concave part was correctly reproduced.

[0126] ≪Example 3A-10≫ The irradiation energy when curing the ultraviolet curable resin composition was 700 mJ / cm.2 Example 3A-10 was carried out in the same manner as Example 3A-1, except that the heat treatment at 110 °C for 20 minutes after curing was not performed. When the obtained concavo-convex shape was observed with an optical microscope, there was no damage such as chipping, and the shape of the concave portion was correctly reproduced.

[0127] ≪Example 3A-11≫ Example 3A-11 was carried out in the same manner as Example 3A-1, except that the concavo-convex shape was formed through a water-insoluble resin layer. After laminating the ultraviolet-curable resin composition of Example 3A-1 on the surface of a water-soluble resin sheet cut into 10 cm × 10 cm to form concave portions to prepare a transfer sheet for forming a concavo-convex shape, it was bonded to an aluminum alloy plate. Then, using a high-pressure mercury lamp, the ultraviolet-curable resin composition was cured with an energy of 500 mJ / cm 2 Thereafter, Example 3A-11 was carried out in the same manner as Example 3A-1. When the obtained concavo-convex shape was observed with an optical microscope, there was no damage such as chipping, and the shape of the concave portion was correctly reproduced.

[0128] ≪Example 3B-1≫ The ultraviolet-curable resin composition was changed to the following polyurethane resin. 3. The following was used as the water-insoluble resin. Aerodur 3002 Clear Coat (AkzoNobel) 4. The transfer sheet for forming a concavo-convex shape was prepared as follows. Using a doctor blade, the aforementioned polyurethane resin was applied to a water-soluble resin layer having concavities and convexities on the first surface to a thickness of 20 μm, and cured by natural drying for 12 hours to obtain a cured layer, thereby preparing a transfer sheet for forming a concavo-convex shape. 5. The formation of the concavo-convex shape was carried out as follows. A 10 cm × 10 cm sample was cut out from the transfer sheet for forming a concavo-convex shape prepared above. Using a doctor blade, the aforementioned polyurethane resin was applied to the surface of this sample on the water-insoluble resin layer side to a thickness of 20 μm and bonded to an aluminum alloy plate. A plastic spatula was used for bonding. Next, when the water-soluble resin sheet was removed by washing in the same manner as in Example 3A-1, a favorable concavo-convex shape could be obtained in the same manner as in Example 3A-1.

[0129] ≪Example 3B-2≫ Example 3B-2 was carried out in the same manner as Example 3B-1 except that the polyurethane resin was changed as follows, and a favorable concavo-convex shape similar to that of Example 3B-1 could be obtained. Aerodur 3001 Base Coat (AkzoNobel)

[0130] ≪Example 3B-3≫ Example 3B-3 was carried out in the same manner as Example 3B-1 except that the polyurethane resin was changed as follows, and a favorable concavo-convex shape similar to that of Example 3B-1 could be obtained. Desothane Hard Disk 9008 Buffable Clear Coat (PPG)

[0131] ≪Example 3B-4≫ It was carried out using the polyurethane resin of Example 3B-1 except that a concavo-convex shape was formed through an adhesive layer. 4. The transfer sheet for forming a concavo-convex shape was produced as follows. The above-mentioned polyurethane resin was applied to the water-soluble resin layer having concavo-convexities on the first surface to a thickness of 20 μm using a doctor blade, and cured by natural drying for 12 hours to obtain a water-insoluble resin layer. Then, an adhesive sheet with a release film was laminated to produce a transfer sheet for forming a concavo-convex shape. 5. The formation of the concavo-convex shape was carried out as follows. A 10 cm × 10 cm sample was cut out from the transfer sheet for forming a concavo-convex shape prepared above. The release film on the back surface of the substrate side of this sample was peeled off, and the transfer sheet for forming a concavo-convex shape was laminated to an aluminum alloy plate through an adhesive layer. A plastic spatula was used for lamination. Next, the water-soluble resin sheet support on the surface was peeled off. Thereafter, the water-soluble resin sheet on the surface was removed by washing with water. Washing with water was performed by spraying tap water onto the surface of the water-soluble resin sheet. It was visually confirmed that the water-soluble resin sheet had been removed. When the obtained uneven shape was observed with an optical microscope, there were no damages such as chipping, and the shape of the concave portions was correctly reproduced.

[0132] ≪Example 3B-5≫ A transfer sheet for forming an uneven shape was produced in the same manner as in Example 3B-4. Next, paper (sliding layer) with a basis weight of 70 g / m 2 was laminated via an adhesive on the surface of the water-soluble resin sheet support of the transfer sheet for forming an uneven shape. Thereafter, an uneven shape was formed in the same manner as in Example 3B-4. When laminating the transfer sheet for forming an uneven shape on the duralumin plate, the plastic spatula had good slipperiness and good workability. When the formed uneven shape was observed with an optical microscope, there were no damages such as chipping, and the shape of the concave portions was correctly reproduced.

[0133] ≪Example 3B-6≫ Both sides of a sheet of biaxially oriented polyethylene terephthalate with a thickness of 50 μm were corona-treated at a treatment intensity of 100 W·min / m 2 . The following coating solution was applied to one of these surfaces so that the dry coating amount was 18 g / m 2 , and dried at 120°C for 20 minutes to form a coating layer (sliding layer). · Coating solution for coating layer Bironal MD1245 (aqueous polyester resin manufactured by Toyobo Co., Ltd., concentration 30%) 30 parts by mass Acrylic fine particles MX2000 (manufactured by Soken Chemical & Engineering Co., Ltd., particle size 20 μm) 8 parts by mass Pure water was added to make 100 g. Next, a water-soluble resin sheet was formed on the opposite surface in the same manner as in Example 3. Using this water-soluble resin sheet, a concavo-convex shape was formed in the same manner as in Example 3B-4. When attaching the transfer sheet for forming the concavo-convex shape to the duralumin plate, the sliding of the plastic spatula was good and the workability was good. When the formed concavo-convex shape was observed with an optical microscope, there was no damage such as chipping, and the shape of the concave part was correctly reproduced.

[0134] <Others> When applying the present invention to an aircraft, it is assumed that the aircraft is placed in a maintenance dock and the coating operation according to the present invention is performed. According to the present invention, the number of working days can be shortened, and the cost required for the coating operation can be suppressed. In addition, since the number of working days can be shortened, the influence on the operation schedule can be reduced.

[0135] The present invention is not limited to the above-described embodiments, and it goes without saying that various modifications can be made.

[0136] The present invention can be applied not only to the fuselage of an aircraft but also to the body of an automobile, the surface of a ship's hull, the surface of a screw, a rocket, a train, and other transportation fields. It can also be applied to sports fields such as skiing, which involves high speeds, and swimming, and can also be applied to ski boards, clothing, swimsuits, etc. It can also be applied to pipelines through which fluids flow. It can also be applied to windmills, which are rotating objects.

Explanation of Signs

[0137] 2: Water-soluble resin sheet 3: Heating concavo-convex roller 6: Coating material 10: Transfer sheet for forming concavo-convex shape 11: Roll winding of transfer sheet for forming concavo-convex shape 20: Water-soluble resin layer 21: First surface 22: Concavo-convex 30: Water-insoluble resin layer 32: Concavo-convex 40: Object to be transferred 41: Coating material 50: Support layer 60: Adhesive layer 70: Substrate 80: Adhesive layer

Claims

1. A water-soluble resin layer made of a water-soluble resin, having a dissolution time in distilled water at 25°C of 0.2 seconds / μm or more and 1.0 second / μm or less, containing latex, having unevenness on its first surface, and the opposite surface of the first surface being smooth, and a water-insoluble resin layer laminated on the first surface. A transfer sheet for forming an uneven shape, comprising the above.

2. The transfer sheet for forming an uneven shape according to Claim 1, wherein the water-soluble resin contains polyvinyl alcohol and polyvinylpyrrolidone, and the total mass of polyvinyl alcohol and polyvinylpyrrolidone is 40 mass percent or more and less than 100 mass percent of the total amount of the water-soluble resin. A transfer sheet for forming an uneven shape.

3. The transfer sheet for forming an uneven shape according to Claim 1 or 2, wherein the water-soluble resin contains polyvinyl alcohol and polyvinylpyrrolidone, the degree of polymerization of polyvinyl alcohol is 250 or more and 1000 or less, and the degree of polymerization of polyvinylpyrrolidone is 100 or more and 2000 or less. A transfer sheet for forming an uneven shape.

4. The transfer sheet for forming an uneven shape according to any one of Claims 1 to 3, wherein the water-soluble resin contains polyvinyl alcohol and polyvinylpyrrolidone, and the mass ratio of polyvinyl alcohol to polyvinylpyrrolidone is in the range of 80:20 to 20:

80. A transfer sheet for forming an uneven shape.

5. The transfer sheet for forming an uneven shape according to any one of Claims 2 to 4, wherein the saponification degree of the polyvinyl alcohol in the water-soluble resin is 70% or more and 99% or less. A transfer sheet for forming an uneven shape.

6. The transfer sheet for forming an uneven shape according to any one of Claims 1 to 5, wherein the water-soluble resin layer contains 2 mass percent or more and 50 mass percent or less of latex. A transfer sheet for forming an uneven shape.

7. The transfer sheet for forming an uneven shape according to any one of Claims 1 to 6, wherein the transfer sheet for forming an uneven shape is composed of a long sheet wound in a roll shape. A transfer sheet for forming an uneven shape.

8. The transfer sheet for forming an uneven shape according to any one of Claims 1 to 7, wherein it further comprises a support layer laminated on the opposite surface of the first surface of the water-soluble resin layer and peelable from the opposite surface, and the peel peel strength between the support layer and the water-soluble resin layer is 2 g / cm or more and 70 g / cm or less. Transfer sheet for forming concavo-convex shapes.

9. The transfer sheet for forming concavo-convex shapes according to claim 8, further comprising a sliding layer formed on the surface of the support layer opposite to the surface in contact with the water-soluble resin layer. Transfer sheet for forming concavo-convex shapes.

10. The transfer sheet for forming concavo-convex shapes according to any one of claims 1 to 9, further comprising an adhesive layer laminated on the side of the water-insoluble resin layer opposite to the surface facing the first surface of the water-soluble resin layer. Transfer sheet for forming concavo-convex shapes.

11. The transfer sheet for forming concavo-convex shapes according to any one of claims 1 to 10, wherein the water-insoluble resin layer is made of polyurethane or acrylic resin. Transfer sheet for forming concavo-convex shapes.

12. The transfer sheet for forming concavo-convex shapes according to any one of claims 1 to 11, wherein the water-insoluble resin layer is made of a resin obtained by curing an ultraviolet-curable resin composition. Transfer sheet for forming concavo-convex shapes.

13. A method for manufacturing a transfer sheet for forming concavo-convex shapes according to any one of claims 1 to 12, comprising the steps of preparing the water-soluble resin layer having concavo-convexities on the first surface, and forming a water-insoluble resin layer on the first surface of the prepared water-soluble resin layer. Method for manufacturing a transfer sheet for forming concavo-convex shapes.

14. A method for manufacturing a transfer sheet for forming concavo-convex shapes according to claim 13, wherein the step of preparing the water-soluble resin layer having concavo-convexities on the first surface includes feeding a roll-shaped water-soluble resin sheet constituting the water-soluble resin layer, and transferring concavo-convexities to the first surface of the fed water-soluble resin sheet using a heated concavo-convex roller. Method for manufacturing a transfer sheet for forming concavo-convex shapes.

15. A method for manufacturing a transfer sheet for forming concavo-convex shapes according to claim 13 or 14, further comprising the step of winding the transfer sheet for forming concavo-convex shapes into a roll after the step of forming the water-insoluble resin layer on the first surface. Method for manufacturing a transfer sheet for forming concavo-convex shapes.

16. A method for manufacturing a transfer sheet for forming concavo-convex shapes according to any one of claims 13 to 15, before the step of forming the water-insoluble resin layer on the first surface, comprising the steps of preparing a support, performing a surface treatment on the support, and laminating the water-soluble resin layer on the surface of the support subjected to the surface treatment. Method for manufacturing a transfer sheet for forming concavo-convex shapes.

17. A method for manufacturing a transfer sheet for forming an uneven shape according to any one of claims 13 to 16, wherein the method further comprises a step of laminating an adhesive layer on a surface of the water-insoluble resin layer opposite to the surface facing the first surface of the water-soluble resin layer; A method for manufacturing a transfer sheet for forming an uneven shape, further comprising the above step.

18. A method for manufacturing a transfer sheet for forming an uneven shape according to any one of claims 13 to 17, wherein the step of forming the water-insoluble resin layer on the first surface comprises a step of laminating a coating solution obtained by dissolving a resin constituting the water-soluble resin layer in a solvent on the first surface, and a step of drying the laminated coating solution to form the water-insoluble resin layer on the first surface of the water-soluble resin layer. A method for manufacturing a transfer sheet for forming an uneven shape.

19. A method for manufacturing a transfer sheet for forming an uneven shape according to any one of claims 13 to 18, wherein the water-insoluble resin layer is made of a resin obtained by curing an ultraviolet-curable resin composition, and the step of forming the water-insoluble resin layer on the first surface comprises a step of laminating a coating solution that becomes the ultraviolet-curable resin composition on the first surface, and a step of curing the laminated coating solution to form the water-insoluble resin layer made of a resin obtained by curing the ultraviolet-curable resin composition on the first surface of the water-soluble resin layer. A method for manufacturing a transfer sheet for forming an uneven shape.

20. A step of attaching the water-insoluble resin layer side of the transfer sheet for forming an uneven shape according to any one of claims 1 to 12 to the surface of a transfer object, and a step of removing the water-soluble resin layer of the transfer sheet for forming an uneven shape attached to the surface of the transfer object to leave the water-insoluble resin layer on the surface of the transfer object, and exposing the uneven shape made of the water-insoluble resin layer on the surface of the transfer object A method for forming an uneven shape, comprising the above steps.

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