JP2005238674A - Hydraulic pressure transfer sheet and method for manufacturing metallic molded article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hydraulic pressure transfer sheet capable of simultaneously applying a metallic luster and an uneven pattern such as a hairline pattern on a molded article and a method for manufacturing a metallic molded article using the hydraulic pressure transfer sheet. <P>SOLUTION: The hydraulic pressure transfer sheet is prepared by laminating a substrate sheet formed of a water-soluble or a water-swelling resin, and a transfer layer formed of a lustrous scaly thin piece and a water-insoluble transparent binder. The substrate sheet has an unevenness with a specified pattern on the face of the transfer layer side, and the transfer layer is formed so as to bury the unevenness. It is preferable in this hydraulic pressure transfer sheet that the mean particle diameter of the lustrous scaly thin pieces is smaller than the mean size of the openings of the recessed parts. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a hydraulic transfer sheet and a method for producing a metal-molded article using the hydraulic transfer sheet (referred to herein as a molded article having a metallic decoration on the surface). More specifically, the present invention relates to a hydraulic transfer sheet for applying a metallic decoration to a molded product and a method for producing a metallic molded product using the hydraulic transfer sheet.

  Molded products made of various non-metallic materials used in automobile interior parts, home appliances, OA equipment, etc., are molded products with a metallic decoration (metal luster) on the surface to reproduce the metal material Is being used. These various molded products often have a complicated three-dimensional shape, and as a method for easily applying a highly designed decoration to a molded product having such a complicated shape, a metal is applied to the molded product using water pressure. There is known a hydraulic transfer method that gives a decorative decoration.

  The hydraulic transfer method is a transfer method using a hydraulic transfer sheet in which a water-soluble or water-swellable base sheet and a transfer layer for applying a metallic decoration to a molded product are laminated in this order. The hydraulic transfer sheet is floated on the water surface so that the surface of the base sheet side faces the water surface, and the molded product is pressed on the hydraulic transfer sheet, and the hydraulic transfer sheet and the molded product are brought into close contact with each other by water pressure. The transfer layer is transferred to a molded product. According to such a hydraulic transfer method, when the molded product is pressed against the hydraulic transfer sheet suspended on the water surface, the base sheet dissolved or swollen in water is spread by the water pressure applied along the shape of the molded product. Therefore, the hydraulic transfer sheet can be easily brought into close contact with a molded product having a three-dimensional shape, and the transfer layer can be transferred to the molded product, so that a metal-like molded product can be easily obtained.

Conventionally, as a hydraulic transfer sheet for applying a metallic decoration to a molded product, a hydraulic transfer sheet in which a transfer layer is formed of a transparent synthetic resin containing a metal powder has been used (for example, see Patent Document 1). .)
JP 61-40200 A

  However, in recent years, there has been a demand for a metal-like molded product that reproduces a high-grade metal material with a concavo-convex pattern such as a hairline pattern. On the other hand, the conventional hydraulic transfer sheet described in Patent Document 1 only gives a metallic luster to a molded product, and cannot give a metallic luster and an uneven pattern such as a hairline pattern at the same time.

  The present invention has been made in order to solve the above-described problems, and its purpose is to provide a hydraulic transfer sheet capable of simultaneously applying a metallic luster and an uneven pattern such as a hairline pattern to a molded product, and the hydraulic transfer sheet thereof An object of the present invention is to provide a method for producing a metal-finished product using the above-mentioned.

  The hydraulic transfer sheet according to the first embodiment of the present invention for solving the above problems includes a base sheet formed of a water-soluble or water-swellable resin, a bright scaly flake, and a water-insoluble transparent binder. A hydraulic transfer sheet laminated with a transfer layer formed of a resin, wherein the base sheet has irregularities with a predetermined pattern on the surface on the transfer layer side, and the transfer layer is formed to fill the irregularities It is characterized by being.

  According to this invention, since the surface on the transfer layer side of the base sheet has irregularities of a predetermined pattern, the irregularities are shaped on the transfer layer that gives the molded product a metallic decoration. As a result, when this hydraulic transfer sheet is used for the production of a metal-like molded product, a metallic luster and an uneven pattern can be simultaneously applied to the molded product.

  The hydraulic transfer sheet according to the second embodiment of the present invention for solving the above problems is a base sheet formed of a water-soluble or water-swellable resin, an uneven layer formed of a water-soluble resin, A hydraulic transfer sheet in which a glittering flake-like flake and a transfer layer formed of a water-insoluble transparent binder resin are laminated in this order, the uneven layer having a predetermined pattern of unevenness on the surface on the transfer layer side. The transfer layer is formed so as to fill the unevenness.

  According to this invention, since the surface on the transfer layer side of the concavo-convex layer has the concavo-convex pattern of the predetermined pattern, the concavo-convex shape is formed on the transfer layer that gives the molded product a metallic decoration. As a result, when this hydraulic transfer sheet is used for the production of a metal-like molded product, a metallic luster and an uneven pattern can be simultaneously applied to the molded product.

  The hydraulic transfer sheet according to the third embodiment of the present invention for solving the above-mentioned problems is a base sheet formed of a water-soluble or water-swellable resin, a bright scaly flake, and a water-insoluble transparent binder. A hydraulic transfer sheet in which a transfer layer formed of a resin and an adhesive layer formed of a resin that dissolves or swells in an active agent made of an organic solvent are laminated in this order, and the base sheet is on the transfer layer side The surface has a predetermined pattern of irregularities, and the transfer layer is formed to fill the irregularities.

  According to this invention, since the surface on the transfer layer side of the base sheet has irregularities of a predetermined pattern, the irregularities are shaped on the transfer layer that gives the molded product a metallic decoration. As a result, when this hydraulic transfer sheet is used for the production of a metal-like molded product, a metallic luster and an uneven pattern can be simultaneously applied to the molded product. Further, according to the present invention, since the adhesive layer formed of a resin that dissolves or swells in an active agent made of an organic solvent is formed on the transfer layer, the adhesive layer dissolves or swells by the application of the active agent. The transfer layer and the molded product are easily bonded. Therefore, it is possible to easily adhere the transfer layer and the molded product without applying the activator directly to the transfer layer to dissolve or swell the transfer layer. Can be suppressed. As a result, when this hydraulic transfer sheet is used for the production of a metal-molded product, the uneven pattern applied to the metal-molded product becomes clear. Here, the activator is applied to the surface of the hydraulic transfer sheet on the side opposite to the base material sheet side to dissolve or swell the surface, thereby facilitating adhesion between the transfer layer and the molded product. Usually, it is applied directly to the transfer layer.

  The hydraulic transfer sheet according to the fourth embodiment of the present invention for solving the above problems is a base sheet formed of a water-soluble or water-swellable resin, an uneven layer formed of a water-soluble resin, A hydraulic transfer sheet in which a transfer layer formed of glitter scaly flakes and a water-insoluble transparent binder resin and an adhesive layer formed of a resin that dissolves or swells in an active agent composed of an organic solvent are laminated in this order. The uneven layer has a predetermined pattern of unevenness on the surface on the transfer layer side, and the transfer layer is formed so as to fill the unevenness.

  According to this invention, since the surface on the transfer layer side of the concavo-convex layer has the concavo-convex pattern of the predetermined pattern, the concavo-convex shape is formed on the transfer layer that gives the molded product a metallic decoration. As a result, when this hydraulic transfer sheet is used for the production of a metal-like molded product, the molded product can be provided with a concavo-convex pattern simultaneously with the metallic luster. Further, according to the present invention, since the adhesive layer formed of a resin that dissolves or swells in an active agent made of an organic solvent is formed on the transfer layer, the transfer agent is applied directly to the transfer layer. Even if it is not dissolved or swollen, the transfer layer and the molded product can be easily adhered. As a result, it is possible to suppress deformation of the unevenness of the transfer layer due to the transfer layer being dissolved or swollen in the activator. Therefore, when this hydraulic transfer sheet is used for the production of a metal molded product, it is applied to the metal molded product. The uneven pattern is clear.

  The hydraulic transfer sheet of the present invention is the hydraulic transfer sheet according to any one of the first to fourth embodiments, wherein the average particle size of the glittering scaly flakes is smaller than the average size of the opening of the recesses in the irregularities. Is preferred.

  According to this invention, since the average particle diameter of the glittering scaly flakes contained in the transfer layer is smaller than the average size of the opening of the concave portion of the base sheet or the concave and convex layer, it corresponds to the concave portion of the base sheet and the like. Thus, the flat surface of the glittering scaly flakes is easily orientated parallel to or substantially parallel to the in-plane direction. Therefore, when viewed from above, the uneven surface of the transfer layer is easily filled with the glitter flakes without gaps. As a result, when this hydraulic transfer sheet is used for the production of a metal-like molded product, the molded product can be given a uniform metallic luster, and the uneven pattern applied to the molded product due to the uniform metallic luster can be obtained. It becomes clear.

  The hydraulic transfer sheet of the present invention is preferably such that the transparent binder resin is hardly dissolved or swollen in the active agent in the hydraulic transfer sheet according to the third or fourth embodiment.

  According to this invention, since the transparent binder resin forming the transfer layer is difficult to dissolve or swell in the active agent, even when the active agent applied to the adhesive layer reaches the transfer layer by dissolving or swelling the adhesive layer, The transfer layer hardly dissolves or swells in the active agent, and the unevenness of the transfer layer is not easily deformed. As a result, when this hydraulic transfer sheet is used for the production of a metal-molded product, the uneven pattern applied to the metal-molded product becomes clear.

  In order to solve the above problems, the method for producing a metal-molded article of the present invention is such that the hydraulic transfer sheet is floated on the water surface so that the surface on the base sheet side faces the water surface, and molded from above the hydraulic transfer sheet. By pressing the product, the hydraulic transfer sheet is brought into close contact with the molded product with water pressure, and the transfer layer is transferred onto the surface of the molded product.

  According to the hydraulic transfer sheets according to the first to fourth embodiments of the present invention, the metallic luster and the uneven pattern can be simultaneously applied to the molded product. Moreover, according to the hydraulic transfer sheet according to the third and fourth embodiments of the present invention, the uneven pattern applied to the molded product becomes clearer.

  According to the method for producing a metal molded product of the present invention, since the hydraulic transfer sheet of the present invention is used, a metal molded product having various uneven patterns can be easily produced.

  Hereinafter, the hydraulic transfer sheet of the present invention and a method for producing a metal-molded article using the hydraulic transfer sheet will be described with reference to the drawings.

(Hydraulic transfer sheet)
The hydraulic transfer sheet of the present invention is a sheet for applying a metallic decoration to a molded article by a hydraulic transfer method. FIG. 1 shows cross sections of four typical forms of the hydraulic transfer sheet of the present invention. The hydraulic transfer sheet of the present invention includes a hydraulic transfer sheet 1 according to the first embodiment as shown in FIG. 1A, a hydraulic transfer sheet 1 according to the second embodiment as shown in FIG. There are four forms, a hydraulic transfer sheet 1 according to the third embodiment as shown in FIG. 1C and a hydraulic transfer sheet 1 according to the fourth embodiment as shown in FIG.

  As shown in FIG. 1 (A), the hydraulic transfer sheet 1 according to the first embodiment of the present invention has a substrate sheet 2 having irregularities on the surface formed of a water-soluble or water-swellable resin, and glitter. It has a structure in which a scaly flake and a transfer layer 3 formed of a water-insoluble transparent binder resin are laminated. The hydraulic transfer sheet 1 according to the second embodiment of the present invention has a structure in which an uneven layer 4 is provided between a base sheet 2 having a flat surface and a transfer layer 3, as shown in FIG. Have. As shown in FIG. 1C, the hydraulic transfer sheet 1 according to the third embodiment of the present invention has a structure in which an adhesive layer 5 is provided on the transfer layer 3 of the hydraulic transfer sheet according to the first embodiment. Have The hydraulic transfer sheet 1 according to the fourth embodiment of the present invention has a structure in which an adhesive layer 5 is provided on the transfer layer 3 of the hydraulic transfer sheet according to the second embodiment, as shown in FIG. Have

  FIG. 2 is a cross-sectional view showing an example of a metal-molded product manufactured using the hydraulic transfer sheet of the present invention. However, in FIG. 2, the concavo-convex pattern formed on the metal-finished molded product 6 is omitted for simplification of the drawing. As shown in FIGS. 2 (A) and 2 (B), the metallic tone molded product 6 is obtained by transferring the transfer layer 3 of the hydraulic transfer sheet 1 onto the surface of the molded product 7. As shown in FIG. 2 (B), a metal-finished molded product 6 manufactured using the hydraulic transfer sheet 1 according to the third and fourth aspects of the present invention has an adhesive layer 5 on the surface of the molded product 7. Thus, the transfer layer 3 is transferred.

[Base material sheet]
The base sheet 2 is formed of a water-soluble or water-swellable resin. Such a base sheet 2 dissolves or swells in water when the hydraulic transfer sheet 1 floats on the surface of the water, and then, when the molded article 7 is pressed against the hydraulic transfer sheet 1, the base sheet 2 is spread by the water pressure to be molded. Deforms along the three-dimensional shape. Therefore, the hydraulic transfer sheet 1 can easily follow the molded product 7 having a complicated three-dimensional shape. In addition, the base material sheet 2 is removed at the time of manufacture of the metal-formed product 6, and does not constitute the metal-formed product 6.

  Examples of the water-soluble or water-swellable resin that forms the base sheet 2 include polyvinyl alcohol resin, dextrin, gelatin, glue, casein, shellac, gum arabic, starch, protein, polyacrylic acid amide, and polyacrylic acid. Soda, polyvinyl methyl ether, copolymer of methyl vinyl ether and maleic anhydride, copolymer of vinyl acetate and itaconic acid, polyvinyl pyrrolidone, acetyl cellulose, acetyl butyl cellulose, carboxyl methyl cellulose, methyl cellulose, hydroxyl ethyl cellulose, sodium alginate, etc. Is mentioned. These resins may be used alone or in combination of two or more. The base sheet 2 may be added with rubber such as mannan, xanthan gum or guar gum. The base sheet 2 is usually formed by adding rubber or the like to a resin in which saponified polyvinyl alcohol and starch are mixed as necessary.

  The base material sheet 2 of the hydraulic transfer sheet 1 according to the first and third embodiments of the present invention has irregularities with a predetermined pattern on the surface on the transfer layer 3 side, as shown in FIGS. . When the base sheet 2 itself has such unevenness on the surface, an uneven pattern corresponding to the unevenness of the base sheet 2 can be formed on the adjacent transfer layer 3.

  The uneven pattern of the base material sheet 2 is an uneven pattern that can form a desired uneven pattern to be applied to the molded product 7 on the transfer layer 3, that is, a desired uneven pattern to be applied to the formed product 7 (shaped on the transfer layer 3). Is a concavo-convex pattern obtained by inverting the concavo-convex pattern. Examples of the concavo-convex pattern formed on the transfer layer 3 include various concavo-convex patterns that are usually used for decoration of molded products. For example, a hairline pattern, a grain pattern, a wood grain conduit groove pattern, a wood grain annual ring pattern, and a textured surface texture pattern. And cleaved patterns of granite. Here, in general, the hairline pattern is a pattern in which a large number of thin linear recesses are arranged in parallel or substantially in parallel, and the grain pattern is a pattern in which a large number of small dot-shaped recesses are scattered.

The size of the unevenness of the base material 2 (such as the size of the front of the concave portion and the height of the convex portion) varies depending on the concave / convex pattern formed on the transfer layer 3. Here, in this specification, “the size of the front of the concave portion” means the minimum distance between the tops of the convex portions forming the concave portion on the inner side and forming the outline of the concave portion. 3 is a groove-like uneven pattern like a pattern obtained by inverting the hairline pattern, “the size of the front of the recess” means the width W _L of the front of the recess as shown in FIG. .

For example, if the concavo-convex pattern of the base sheet 2 is a pattern obtained by inverting the hairline pattern as shown in FIG. 3 (A), the width W _H of the width W _L and the convex portion of the frontage of the recesses, respectively the mean value Usually, it is 30-1000 micrometers. Moreover, the height H of the convex part in this case should just be the range which does not exceed the thickness of the base material sheet 2, and is 10-100 micrometers normally by an average value. When the uneven | corrugated pattern of the base material sheet 2 is a pattern which reversed the grain pattern as shown in FIG.3 (B), the magnitude | size W of a frontage of a recessed part is 10-1000 micrometers normally with an average value. Moreover, the height H of the convex part in this case should just be the range which does not exceed the thickness of the base material sheet 2, and is 1-100 micrometers normally by an average value.

  As a method for forming the base sheet 2 in the hydraulic transfer sheet 1 according to the first and third embodiments, a T-die extrusion method in which a heat-melted resin is extruded from a T-die to a casting drum to be formed into a sheet or film. Alternatively, a solution casting method in which a solution or dispersion in which a resin is dissolved or dispersed in a solvent such as water or an organic solvent is cast on a casting drum and the solvent is dried to form a sheet or film is used. Can do. When the base sheet 2 is formed by the T-die extrusion method or the solution casting method, it is preferable to use a casting drum having a surface with unevenness capable of shaping the substrate sheet 2 with a predetermined pattern. In addition, it is preferable that the thickness (total thickness including the height of a convex part) of this base material sheet 2 is 30-200 micrometers.

  The method for forming the base sheet 2 included in the hydraulic transfer sheet according to the second and fourth embodiments is not particularly limited as long as it is a method capable of forming the above resin into a sheet or film, and is a T-die extrusion method, a solution. A casting method, a calendar method, or the like can be used. In addition, it is preferable that the thickness of this base material sheet 2 is 30-200 micrometers.

[Uneven layer]
The concavo-convex layer 4 is a base material in the hydraulic transfer sheet 1 according to the second embodiment of the present invention shown in FIG. 1B and the hydraulic transfer sheet 1 according to the fourth embodiment of the present invention shown in FIG. It is provided between the sheet 2 and the transfer layer 3, and has a role of forming a concavo-convex shape on the transfer layer 3. Since the hydraulic transfer sheet 1 according to the second and fourth embodiments of the present invention is provided with the concavo-convex layer 4, the concavo-convex shape is formed in the adjacent transfer layer 3 without providing the base sheet 2 with concavo-convex. Is done. In addition, the uneven | corrugated layer 4 is removed in the case of manufacture of the metal shaping product 6, and does not comprise the metal shaping product 6. FIG.

  The uneven layer 4 has unevenness of a predetermined pattern on the surface on the transfer layer 3 side. The uneven pattern of the uneven layer 4 is an uneven pattern obtained by inverting various uneven patterns exemplified in the column of the base sheet 2, and the dimensions of the unevenness (such as the size of the front of the recess and the height of the protrusion) This is the same as described for the base sheet 2. Moreover, it is preferable that the thickness (total thickness including the height of a convex part) of the uneven | corrugated layer 4 is 30-100 micrometers.

  Since the concavo-convex layer 4 needs to be easily removed with water when the metal-molded article 6 is manufactured, it is formed of a water-soluble resin. Examples of such a resin include a polyvinyl alcohol resin, a water-soluble urethane resin, or a resin in which a water-soluble acrylic resin and casein are mixed. The uneven layer 4 may contain additives such as extender pigments and thixotropic imparting agents. When a thixotropic imparting agent is contained, when a concavo-convex layer 4 is formed using a concavo-convex layer coating liquid as will be described later, after forming a liquid coating film having concavo-convex by printing or the like, the coating film It is possible to prevent the unevenness and flattening due to the liquid coating film flowing during drying and solidification.

  The concavo-convex layer 4 is prepared by adjusting a concavo-convex layer coating solution prepared by dissolving or dispersing the above resin with a solvent, and using a printing plate corresponding to various concavo-convex patterns for forming the transfer layer 3. It is formed by printing the working liquid on the base sheet 2 as printing ink and drying the coating film. Since the formation of the concavo-convex layer 4 is performed using a printing plate corresponding to various concavo-convex patterns, for example, the base material sheet 2 (first and third of the present invention) performed using a casting roll corresponding to various concavo-convex patterns. Compared with the formation of the base material sheet 2) of the hydraulic transfer sheet 1 according to the embodiment, it is simple and advantageous in terms of cost. Therefore, when manufacturing various types of metal-shaped molded products 6 by giving various types of uneven patterns to the molded product 7, using the hydraulic transfer sheet 1 according to the second and fourth embodiments of the present invention, manufacturing is possible. Cost can be reduced.

  As a printing method of the coating liquid for the uneven layer, it is preferable to use a silk screen printing method, a gravure printing method or the like. Moreover, as a solvent of the uneven | corrugated layer coating liquid, from the viewpoint of preventing the base sheet 2 from dissolving or swelling when forming the uneven layer 4, the base sheet 2 is dissolved or swollen without using water. It is preferable to use an organic solvent that is not allowed. Examples of such an organic solvent include alcohols such as ethyl alcohol, butyl alcohol and propyl alcohol, esters such as ethyl acetate and butyl acetate, ketones such as methyl ethyl ketone, acetone and methyl isobutyl ketone, or toluene and xylene. Aromatic hydrocarbons etc. can be mentioned. These organic solvents may be used alone or in combination of two or more.

[Transfer layer]
The transfer layer 3 is a layer that is transferred to the molded product 7 during hydraulic transfer using the hydraulic transfer sheet 1, and has a role of imparting a metallic decoration to the molded product 7.

  The transfer layer 3 of the hydraulic transfer sheet of the present invention has irregularities of a predetermined pattern representing a hairline pattern or the like on the surface that is visually recognized when transferred to the molded product 7. The unevenness is shaped by the unevenness of the base material sheet 2 itself provided adjacent to the transfer layer 3 or the unevenness of the uneven layer 4. When the transfer layer 3 has such unevenness, the molded product 7 can be provided with metallic luster and uneven patterns such as a hairline pattern at the same time.

  The transfer layer 3 is formed of bright scaly flakes and a water-insoluble transparent binder resin. Examples of such transparent binder resins include cellulose resins, acrylic resins, urethane resins, vinyl chloride-vinyl acetate copolymers, polyester resins, alkyd resins, and chlorinated polypropylene.

  As the cellulose resin, nitrocellulose (nitrified cotton), cellulose acetate, cellulose acetate propionate, or the like is used. As acrylic resins, polymethyl (meth) acrylate, polybutyl (meth) acrylate, methyl (meth) acrylate-ethyl (meth) acrylate copolymer, methyl (meth) acrylate-butyl (meth) acrylate copolymer, methyl (Meth) acrylate-styrene copolymer, methyl (meth) acrylate-2hydroxyethyl (meth) acrylate-styrene copolymer, and the like are used. In addition, (meth) acrylate means an acrylate or a methacrylate.

  The urethane resin is mainly produced by reacting a polyol and a polyisocyanate. As the polyol, for example, acrylic polyol, polyester polyol, polyether polyol, polyurethane polyol and the like are used. Examples of polyisocyanates include aromatic isocyanates such as 2,4-tolylene diisocyanate, xylene diisocyanate, naphthalene diisocyanate or diphenylmethane diisocyanate, or 1,6-hexamethylene diisocyanate, hydrogenated tolylene diisocyanate or isophorone. Aliphatic (or alicyclic) isocyanates such as diisocyanates are used. These polyisocyanates can be used in the form of adducts or multimers such as trimers and pentamers. In addition, these polyisocyanates may be used in the form of so-called blocked isocyanates that are reversibly bonded to alcohols, phenols, or the like in advance as required. Examples of the form of the urethane resin include a form of a one-part urethane resin, a form of a two-part curable urethane resin, and the like. The one-component urethane resin is a thermoplastic urethane resin obtained by polymerizing a polyol and a polyisocyanate so as to be a linear polymer in advance, and is used after being dissolved and diluted with a solvent. In addition, the two-component curable urethane resin adjusts a coating solution for a transfer layer in which a polyol is a main component and an isocyanate is a curing agent when the transfer layer 3 is formed on the base sheet 2. Is a urethane resin obtained by reacting both after printing or coating the base material sheet 2.

  In the hydraulic transfer sheet 1 according to the third or fourth embodiment of the present invention, the transparent binder resin forming the transfer layer 3 is preferably a resin that is difficult to dissolve or swell in an organic solvent that is an activator. The hydraulic transfer sheet 1 according to the third or fourth embodiment of the present invention is a resin that dissolves or swells in an activator made of an organic solvent on the surface of the transfer layer 3 opposite to the base material sheet 2 or the uneven layer 4. The adhesive layer 5 formed by the above is provided. Here, the “active agent” means that the transfer layer 3 can be easily adhered to the molded product 7 via the adhesive layer 5 by dissolving or swelling the adhesive layer 5 to express the adhesiveness or tackiness of the adhesive layer 5. It is something to be made. In these hydraulic transfer sheets 1, since the adhesive layer 5 is dissolved in the active agent instead of the transfer layer 3 as described later, deformation of the unevenness of the transfer layer 3 due to the active agent is suppressed, and the molded product 7 is clear. An uneven pattern can be applied.

  In the hydraulic transfer sheet 1 according to the third or fourth embodiment of the present invention, when the transfer layer 3 is formed of a resin that is difficult to dissolve or swell in the active agent, the applied active agent dissolves the adhesive layer 5 or the like. Even if the transfer layer 3 is reached, the transfer layer 3 is not easily dissolved or swollen in the active agent, so that the deformation of the unevenness of the transfer layer 3 is further suppressed, and these hydraulic transfer sheets 1 are applied to the molded product 7. The uneven pattern is clearer.

  In the hydraulic transfer sheet 1 according to the third or fourth embodiment of the present invention, the solubility or swellability of the transparent binder resin with respect to the active agent is such that at least the unevenness is not deformed when the active agent reaches the transfer layer 3. However, it is preferably as small as possible from the viewpoint of not deforming the unevenness of the transfer layer 3. The resin that hardly dissolves or swells in the activator is appropriately selected according to the activator used. For example, when toluene or methyl ethyl ketone is used as the activator, a polyvinylidene fluoride resin can be used.

  The glittering flake-like flake is not particularly limited as long as it has a metallic luster, and a metallic flake, an alloy flake or a pearlescent (pearl) pigment flake can be used. Preferably, alloy flakes are used. When metal flakes or alloy flakes are used as the glitter flakes, the metallic luster of the metallic luster applied to the molded article is improved, and a metal-like molded article with high reproducibility of the metal material can be obtained. Metal flakes include flakes of aluminum, gold, silver, copper, titanium, chromium, nickel, etc. Alloy flakes include flakes of brass, nickel chrome, stainless steel, etc. Are flakes such as mica coated with titanium dioxide. Among these flakes, it is preferable to use aluminum flakes that have high reflectivity over the entire visible light range and are inexpensive and easy to manufacture and obtain.

  The bright scaly flakes are flat and irregular in shape as shown in FIG. Since the glittering scaly flake 8 has such a shape, the flat surface F of the scaly scaly flake 8 is in the in-plane direction of the transfer layer 3 in the transfer layer 3 as shown in FIG. Parallel or substantially parallel. Therefore, when the metal-like molded product 6 obtained using this hydraulic transfer sheet 1 is viewed in a macroscopic plan view, the glittering scaly flakes 8 in the transfer layer 3 are planar as shown in FIG. The surface of the metal-shaped molded product 6 is filled with no gap. As a result, the molded product 7 to which the transfer layer 3 has been transferred has a metallic texture.

  The average particle size of the glitter scaly flakes is the size of the opening of the recess in the unevenness of the base sheet 2 (base sheet 2 in the hydraulic transfer sheet 1 according to the first and third embodiments) or the uneven layer 4. It is preferably smaller than the average. Here, the “particle diameter of the brilliant scaly flakes” referred to in the present specification refers to the maximum width D of the brilliant scaly flakes in the flat plate surface direction (see FIG. 4A), and an optical microscope. Or it measures by the microscope method (method which measures a particle size from the image of a microscope) using microscopes, such as an electron microscope. When the average particle size of the glitter flakes is smaller than the average size of the opening of the concave portion of the base sheet 2 or the like, as shown in FIG. 4 (B), it corresponds to the concave portion of the base sheet 2 or the like. Even at the convex portions of the shaped transfer layer 3, the glittering scaly flakes 8 are easily oriented parallel or substantially parallel to the in-plane direction. As a result, the concave and convex portions of the concavo-convex surface of the transfer layer 3 (the surface that is visible when transferred) are easily filled without any gaps with the glittering scaly flakes. When a metal-like molded product is produced using the metallic gloss, the metallic luster applied to the molded product 7 tends to be uniform over the entire surface, and the unevenness pattern applied to the molded product 7 is clear due to the uniform metallic luster. It becomes.

  The preferable average particle diameter of the glitter scaly flakes varies depending on the size of the unevenness of the base sheet 2 or the uneven layer 4 (the size of the unevenness formed on the transfer layer 3). In addition, the lower limit of the average particle diameter of the glittering scaly flakes is preferably about 0.1 μm, more preferably about 1 μm, from the viewpoint of improving the metallic gloss of the metal-molded product 6. The thickness of the glitter scaly flake is usually 0.1 to 1 μm.

  It is preferable that about 30-100 mass parts of glittering scaly flakes are contained with respect to 100 mass parts of the transparent binder resin. The transfer layer 3 may contain additives such as extender pigments, ultraviolet absorbers, plasticizers, heat stabilizers, light stabilizers, and surfactants as necessary.

  The transfer layer 3 is a transfer layer coating solution obtained by dissolving or dispersing the above materials in a solvent on the uneven surface of the base sheet 2 (on the uneven layer 4 when the uneven layer 4 is formed) It is formed by printing or coating so as to fill the irregularities and drying the solvent of the coating film. Solvents include alcohols such as ethyl alcohol, butyl alcohol and propyl alcohol, esters such as ethyl acetate and butyl acetate, ketones such as methyl ethyl ketone, acetone and methyl isobutyl ketone, or aromatic hydrocarbons such as toluene and xylene And the like. Further, as the printing method, gravure printing method, offset printing method, letterpress printing method, flexographic printing method, silk screen printing method, etc. can be used, and as the coating method, roll coating method, gravure roll coating method, bar printing method, etc. A coating method or the like can be used. The thickness of the transfer layer 3 (the total thickness including the height of the convex portions) is preferably 1 to 100 μm.

  In addition to the transfer layer 3 containing the above-described glittering scaly flakes, which is an essential component, the hydraulic transfer sheet 1 may be formed as necessary within a range that does not impair the metallic luster applied to the molded product 7. Other layers (hereinafter referred to as other transfer layers) to be transferred to the film may be included. Examples of the other transfer layer include a layer made of a water-insoluble transparent binder resin (ink) containing a normal colorant having no metallic luster. Such another transfer layer may be a solid layer on the entire surface, or may be a partially formed pattern layer. Examples of the pattern when the other transfer layer is a pattern-like layer include a hairline pattern, a grain pattern, a grain pattern, a stone pattern, and the like, as well as letters, symbols, numbers, and the like.

[Adhesive layer]
The adhesive layer 5 is a transfer layer in the hydraulic transfer sheet 1 according to the third embodiment of the present invention shown in FIG. 1 (C) and the hydraulic transfer sheet 1 according to the fourth embodiment of the present invention shown in FIG. 1 (D). 3 is provided on the surface opposite to the base material sheet 2 (or the uneven layer 4). The adhesive layer 5 is a layer that dissolves or swells when an activator, which is an organic solvent, is applied. The adhesive layer 5 is easily dissolved by application of the activator and adheres to the molded product 7. Therefore, when a metal-like molded product is manufactured using the hydraulic transfer sheet according to the third or fourth embodiment, the adhesion between the transfer layer 3 and the molded product 7 is improved.

  Further, since the adhesive layer 5 that dissolves or swells in the active agent is provided on the surface of the transfer layer 3 opposite to the base material sheet 2 or the like, the transfer layer can be formed without applying the active agent directly to the transfer layer 3. 3 and the molded product 7 can be bonded. As a result, since the deformation of the unevenness of the transfer layer 3 due to the transfer layer 3 being dissolved or swollen in the active agent can be suppressed, when a metal-shaped molded product is manufactured using such a hydraulic transfer sheet 1, the molded product 7 The uneven pattern to be applied becomes clear.

  The adhesive layer 5 is formed of a resin that dissolves or swells in an active agent that is an organic solvent. The resin forming the adhesive layer 5 is appropriately selected depending on the activator used, and examples of such resins include acrylic resins, thermoplastic polyester resins, vinyl chloride-vinyl acetate copolymers, cellulose resins, chlorinated polypropylene, and the like. Can be mentioned. These resins may be used alone or in combination of two or more.

  The thickness of the adhesive layer 5 is preferably about 1 to 30 μm. If the thickness of the adhesive layer 5 is less than 1 μm, the activator in which the adhesive layer 5 is dissolved or swollen easily reaches the transfer layer 3, and the transfer layer 3 may be deformed and the uneven pattern may not be clear. There is. Furthermore, when the thickness of the adhesive layer 5 is less than 1 μm, a sufficient amount of the adhesive layer 5 does not dissolve or swell in the active agent, and the adhesive force may be reduced. Further, even if the thickness of the adhesive layer 5 is made larger than 30 μm, no further effect can be expected and the material is consumed wastefully.

  The adhesive layer 5 is formed by printing or coating an adhesive layer coating solution obtained by dissolving or dispersing the above resin in a solvent on the transfer layer 3 and drying the coating film. As the solvent for the adhesive layer coating solution, one that can dissolve or disperse the above-mentioned resin among the organic solvents listed as the activator described later is selected. As the coating method, a roll coating method, a gravure roll coating method, a bar coating method, a curtain flow coating method, or the like is used. As a printing method, a gravure printing method, a silk screen printing method, or the like is used.

(Manufacturing method of metal-like molded product)
As shown in FIG. 5, the method for producing a metal-like molded product of the present invention pushes the molded product 7 from above the hydraulic transfer sheet 1 of the present invention suspended on the water surface S, and decorates the molded product 7 with water pressure. The transfer layer 3 of the hydraulic transfer sheet 1 is transferred to the surface of the molded article 7 by causing the hydraulic transfer sheet 1 to follow and adhere to the shape of the surface to be applied (hereinafter, this process is referred to as a hydraulic pressure application process). Is the method. The method for producing a metal-molded article of the present invention may include an activation step of applying an activator on the transfer layer 3 or the adhesive layer 5 of the hydraulic transfer sheet 1 before the hydraulic pressure application step, if necessary. In addition, for removing the base sheet 2 and the concavo-convex layer 4 transferred to the molded product 7 together with the transfer layer 3 after the water pressure applying step, and for protecting the transfer layer 3 transferred to the molded product 7. A coating process for forming a protective film may be included. Hereinafter, the activation process, the water pressure application process, the film removal process, and the coating process will be described.

[Activation process]
The activation process is a process for facilitating adhesion of the transfer layer 3 and the molded product 7 by applying an activator to the hydraulic transfer sheet 1 of the present invention.

  When the hydraulic transfer sheet 1 according to the first or second aspect of the present invention is used, the transfer layer 3 is coated with an activator, and at least a part of the transfer layer 3 is dissolved or swollen, thereby transferring the transfer layer. 3 is in a state of being easily attached to the molded product 7. Further, when using the hydraulic transfer sheet 1 of the third or fourth embodiment of the present invention, by applying an activator on the adhesive layer 5 and dissolving or swelling at least a part of the adhesive layer 5, The adhesive layer 5 is in a state of being easily attached to the molded product 7.

  As the activator, an organic solvent that dissolves or swells the transparent binder resin of the transfer layer 3 or the resin that forms the adhesive layer 5 is used. Examples of such organic solvents include aliphatic hydrocarbons such as hexane, heptane, and octane, aromatic hydrocarbons such as toluene, xylene, and cyclohexane, methyl alcohol, ethyl alcohol, propyl alcohol, and butyl alcohol. Monohydric alcohols, polyhydric alcohols such as ethylene glycol, propylene glycol, glycerin, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, isopropyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monoethyl Ethers, ethers such as diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol dibutyl ether, vinegar Ethyl, butyl acetate, ethylene glycol monoethyl ether acetate, can be mentioned esters such as diethylene glycol monoethyl ether acetate. These organic solvents may be used alone or in combination of two or more.

  The activator is preferably one that does not evaporate and does not erode the molded product 7 until the hydraulic pressure application step for bonding the transfer layer 3 to the molded product 7 is completed. When such an activator is used, it becomes easy to adjust the viscosity of the activator, so that it is possible to select a wide range of means for applying the activator, and even in the case where time is required for the water pressure application process, Since the solvent is difficult to evaporate, the adhesion between the transfer layer 3 and the molded product 7 is more stable.

  As such an activator, what made the following organic resin contain in the organic solvent illustrated above can be used. Examples of the resin to be included in the organic solvent include a halogenated vinyl polymer such as polyvinyl chloride or polyvinylidene chloride, a styrene polymer such as polystyrene or a styrene derivative, a vinyl ester polymer such as polyvinyl acetate, (meth) Polymers of ester derivatives of unsaturated carboxylic acids such as acrylic acid, itaconic acid, crotonic acid, maleic acid or fumaric acid, polymers of nitrile derivatives of unsaturated carboxylic acids, and acid amide derivatives of unsaturated carboxylic acids. N-methylol derivative of acid amide derivative of unsaturated carboxylic acid, N-alkylmethylol ether derivative of acid amide derivative of unsaturated carboxylic acid, glycidyl (meth) acrylate, acrylic glycidyl ether, vinyl isocyanate, allyl isocyanate Such as 2-hydroxyethyl- (meth) acrylate, 2-hydroxypropyl- (meth) acrylate, homopolymers of monomers such as ethylene and ethylene glycol-mono (meth) acrylate, or copolymers of the above monomers Examples thereof include thermoplastic resins, initial condensates such as the above homopolymers or copolymers, natural resins, rosin or derivatives thereof, cellulose derivatives, natural rubber or synthetic rubber, or petroleum resins. Such a resin is added in an amount of about 5 to 60% by mass with respect to the solvent.

  When the hydraulic transfer sheet 1 according to the third or fourth embodiment of the present invention is used for the production of the metallic molded article 6, as described above, the adhesive layer 5 is dissolved or swollen as an activator, but the transfer layer 3 is preferably an organic solvent that is difficult to dissolve or swell. By using such an activator, the deformation of the unevenness of the transfer layer 3 can be suppressed, so that a clear uneven pattern can be applied to the molded product 7.

Examples of the method for applying the activator onto the transfer layer 3 or the adhesive layer 5 of the hydraulic transfer sheet 1 include a gravure offset coating method, a gravure coating method, a roll coating method, a bar coating method, a spray coating method, and the like. . The coating amount of the activator is about ² to 30 g / m ² , preferably about 3 to 15 g / m ² .

  Application of the activator to the hydraulic transfer sheet 1 may be performed before the hydraulic transfer sheet 1 is suspended on the water surface, or may be performed after the hydraulic transfer sheet 1 is suspended on the water surface. In order to float the hydraulic transfer sheet 1 on the water surface, the single sheet hydraulic transfer sheet 1 may be floated one by one, or water is allowed to flow in one direction and a continuous belt-like hydraulic transfer sheet is formed on the water surface. 1 may be continuously supplied and floated.

[Water pressure application process]
In the water pressure applying step, as shown in FIG. 5, the water pressure transfer sheet 1 is floated on the water surface S so that the surface on the substrate sheet 2 side faces the water surface, and the surface on which the decoration is applied from above the water pressure transfer sheet 1. In this step, the molded product 7 facing downward is pushed in and the water pressure transfer sheet 1 is brought into close contact with the molded product 7 by water pressure. By this step, the transfer layer 3 of the hydraulic transfer sheet 1 and the molded product 7 are bonded, and the transfer layer 3 is transferred to the molded product 7. Further, in this step, since the base sheet 2 is spread by swelling or dissolving in water, the hydraulic transfer sheet 1 can easily follow the three-dimensional shape of the molded product 7. As a result, since the transfer layer 3 adheres along the three-dimensional shape of the molded product, the transfer layer 3 can be easily transferred even to the molded product 7 whose surface to be decorated has a complicated shape. it can.

  The water for applying the water pressure is preferably adjusted to a temperature at which the base sheet 2 of the hydraulic transfer sheet 1 to be used is easily dissolved or swollen. For example, when the base sheet 2 is formed of a resin containing starch, the water temperature is preferably 40 to 50 ° C. Moreover, an additive that dissolves the base sheet 2 and promotes the removal of the base sheet 2 from the transfer layer 3 may be added to the water, and the base sheet 2 is formed of a resin containing starch. For example, amylase can be added.

  The material of the molded product 7 includes polystyrene resin, acrylonitrile-butadiene-styrene copolymer (ABS resin), polycarbonate resin, melamine resin, phenol resin, urea resin, fiber-based resin, polyethylene, polypropylene, and other resins. In addition, ceramics such as ceramics, porcelain, and glass, wood, or metals such as iron, aluminum, and copper can be given. The molded product 7 is preferably a molded product made of a non-metallic material from the viewpoint that the hydraulic transfer sheet 1 of the present invention is a sheet having a metallic luster, but the molded product 7 is a molded product made of a metal material. Even in some cases, the hydraulic transfer sheet 1 of the present invention can give a metallic luster different from the metallic luster of the molded product, so that the effects of the present invention can be obtained. The shape of the molded product 7 may be a two-dimensional shape that is a planar shape, or may be a three-dimensional shape such as an uneven shape or a curved shape.

  In this step, when the base sheet 2 is formed of a water-swellable resin, the base sheet 2 is transferred to the molded product 7 together with the transfer layer 3. Even when the base sheet 2 is formed of a water-soluble resin, the base sheet 2 remaining without being dissolved in water may be transferred to the molded product 7 together with the transfer layer 3. is there. In such a case, in order to remove the base material sheet 2 from the molded product 7, it is necessary to perform a film removal step described below. Further, when the hydraulic transfer sheet 1 according to the second and fourth embodiments of the present invention is used and the concavo-convex layer 4 is transferred to the molded product 7 integrally with the transfer layer 3, it is similarly molded by the film removal process. It is necessary to remove the uneven layer 4 from the product 7.

[Defilming process]
The film removal step is a step of removing the base sheet 2 or the uneven layer 4 when the base sheet 2 or the uneven layer 4 of the hydraulic transfer sheet 1 is transferred onto the molded product 7 together with the transfer layer 3. . Accordingly, this step is not necessary when the base sheet 2 and the uneven layer 4 are not transferred to the molded product 7.

  The removal of the base material sheet 2 and the uneven | corrugated layer 4 is performed by wash | cleaning the molded article 7 with the shower using water, for example. At this time, since the transfer layer 3 is formed of a water-insoluble resin, it is not removed, and remains on the molded product 7 while the surface uneven pattern is maintained. The conditions for washing by shower vary depending on the type of resin forming the base sheet 2 and the concavo-convex layer 4, but it is usually preferable that the water temperature is 15 to 60 ° C. and the washing time is 0.5 to 10 minutes. After the film removal step, the molded product 7 is sufficiently dried to obtain the metal-molded product 6 in which the transfer layer 3 is transferred to the molded product 7.

[Painting process]
The coating process is a process of forming a protective film on the surface of the obtained metal molded product 6. By this process, the transferred transfer layer 3 is protected from scratches and contamination, and the surface of the metal molded product 6. It is possible to improve the strength and to adjust the metallic luster of the metallic molded product 6.

  Examples of the resin for forming the protective film include urethane resin, epoxy resin, acrylic resin, fluorine resin, silicon resin, and the like. For example, the same resin as the transparent binder resin of the transfer layer 3 described above is used as the urethane resin. be able to. The protective film is formed by applying a protective film coating solution obtained by diluting the above resin with a solvent onto the transfer layer 3 of the metal-molded product 6. Examples of the coating method include spray coating, electrostatic coating, brush coating, and immersion. The thickness of the protective film is preferably about 1 to 30 μm.

  Hereinafter, the present invention will be described in more detail based on examples and comparative examples. In addition, below, a part is a mass part.

(Example 1)
(Preparation of hydraulic transfer sheet)
First, 100 parts of polyvinyl alcohol resin (average degree of polymerization 1700, saponification rate: 88%), 10 parts of guar gum, 5 parts of glycerin and 0.5 part of a surfactant are dissolved in 450 parts of water to prepare a base sheet forming solution. A substrate sheet having water swellability was prepared under the condition of a temperature of 95 ° C. by the solution casting method. At this time, a casting drum having a hairline uneven pattern on the surface for use in a molded product was used. The substrate sheet has an average width W _H of the mean and the convex portion of the width W _L of the frontage of the recess (see Figure 3 (A).) Is 300μm, respectively, the average height of the convex portion is located at 25μm The total thickness including the height of the convex portion was 60 μm.

  Next, aluminum flakes having an average particle size of 15 μm are used as the glitter flakes, 5 parts of nitrocellulose and 1 part of alkyd resin are used as the transparent binder resin, and the flakes flakes in 100 parts of the transparent binder resin. 60 parts were kneaded with a dyno mill and dispersed, and this was diluted with a mixed solvent of ethyl acetate and toluene (mass ratio = 1: 1) to prepare a transfer layer coating solution.

  Thereafter, the coating liquid for the transfer layer is applied to the uneven surface of the base sheet by a roll coating method, and this coating film is dried to have a transfer layer having a total thickness of 30 μm including the height of the convex portion. The hydraulic transfer sheet of Example 1 was produced.

(Manufacture of metal-like molded products)
An activator A composed of 80 parts of methyl carbitol cellosolve acetate, 15 parts of alkyd resin and 5 parts of precipitated barium carbonate was applied to the surface of the obtained hydraulic transfer sheet on the transfer layer side by a gravure roll coating method. Thereafter, the hydraulic transfer sheet was floated so that the surface on the base sheet side faced the water surface.

  After 1 minute had passed, a molded article made of ABS resin having a three-dimensional shape shown in FIG. 6 was pressed from above the hydraulic transfer sheet, and the hydraulic transfer sheet was brought into close contact with the molded article by water pressure. Thereafter, the molded product with the water pressure transfer sheet adhered thereto was taken out from the water, and a 40 ° C. hot water shower was sprayed for 30 seconds, and then a fresh water shower was sprayed to remove the base material sheet attached to the molded product. Thereafter, the molded product to which the transfer layer was transferred was dried to obtain a metal-like molded product.

(Example 2)
First, the same base sheet forming solution as that used in Example 1 was prepared, and the surface was flat at a temperature of 95 ° C. by a solution casting method using a casting drum having a flat and smooth surface. A base sheet (thickness: 40 μm) having water swellability was prepared.

Next, an uneven layer coating solution obtained by diluting 100 parts of water-soluble urethane resin with a mixed solvent of toluene and ethyl acetate (mass ratio = 1: 1) is printed on one side of the base sheet by a silk screen printing method. The coating film was dried to form an uneven layer. At this time, it printed so that the uneven | corrugated pattern of the uneven | corrugated layer after drying might turn into the pattern which reversed the hairline pattern for giving to a molded article. The uneven layer has an average width W _H of the mean and the convex portion of the width W _L of the frontage of the recess is 300μm respectively, the average height of the projections is 25 [mu] m, the total thickness including the convex height Was 30 μm.

  The same coating liquid for transfer layer as that used in Example 1 was applied on the uneven layer by the roll coating method, and this coating film was dried, so that the total thickness including the height of the convex portion was 30 μm. A hydraulic transfer sheet of Example 2 having the transfer layer was prepared.

  Next, a metal-molded article was produced in the same manner as in Example 1 except that the hydraulic transfer sheet of Example 2 was used as the hydraulic transfer sheet.

(Example 3)
In the production of the hydraulic transfer sheet of Example 1, 5 parts of nitrocellulose resin and 1 part of alkyd resin were diluted with a mixed solvent of ethyl acetate, toluene and isopropyl alcohol (mass ratio = 1: 1: 1). The hydraulic transfer sheet of Example 3 was applied in the same manner as in Example 1 except that the coating liquid was applied onto the transfer layer by a roll coating method, the coating film was dried, and an adhesive layer having a thickness of 5 μm was provided. Produced.

  Next, a metal-molded article was produced in the same manner as in Example 1 except that the hydraulic transfer sheet of Example 3 was used as the hydraulic transfer sheet.

Example 4
In the production of the hydraulic transfer sheet of Example 2, the same adhesive layer coating liquid as used in Example 3 was applied onto the transfer layer by the roll coating method, and the coating film was dried. A hydraulic transfer sheet of Example 4 was produced in the same manner as Example 2 except that an adhesive layer was provided.

  Next, a metal-molded article was produced in the same manner as in Example 1 except that the hydraulic transfer sheet of Example 4 was used as the hydraulic transfer sheet.

(Example 5)
In the preparation of the water pressure transfer sheet of Example 1, the average of the width W _H of the mean and the convex portion of the width W _L of the frontage of the recess of the base sheet and 35μm respectively, also have an average particle size as glittering scaly flakes A hydraulic transfer sheet of Example 5 was produced in the same manner as in Example 1 except that an aluminum flake of 40 μm was used.

  Next, a metal-molded article was produced in the same manner as in Example 1 except that the hydraulic transfer sheet of Example 5 was used as the hydraulic transfer sheet.

(Example 6)
In the preparation of the hydraulic transfer sheet of Example 4, when adjusting the transfer layer coating solution, a mixture of 80 parts of polyvinylidene fluoride resin and 20 parts of acrylic resin was used as the transparent binder resin, and the solvent for the transfer layer coating solution A hydraulic transfer sheet of Example 6 was prepared in the same manner as in Example 4 except that a mixed solvent of 50 parts of methyl ethyl ketone and 50 parts of toluene was used.

  Next, a metal-molded article was produced in the same manner as in Example 1 except that the hydraulic transfer sheet of Example 6 was used as the hydraulic transfer sheet.

(Comparative Example 1)
As a hydraulic transfer sheet of Comparative Example 1, a hydraulic transfer sheet provided with a transfer layer formed by printing a hairline pattern was produced.

  A water-swellable sheet (thickness: 40 μm) having a flat surface similar to the base sheet prepared in Example 2 was used as the base sheet. Next, a colored ink obtained by diluting 5 parts of nitrocellulose, 1 part of an alkyd resin, 0.5 part of carbon black and 0.5 part of a petite with a mixed solvent of ethyl acetate and toluene (mass ratio = 1: 1). A colored layer (thickness: 2 μm) having a hairline pattern was formed on one side of the base sheet by gravure printing. The average distance between the hairlines in the colored layer and the average width of the hairlines were each 300 μm. Thereafter, the transfer layer coating solution prepared in the same manner as in Example 1 was applied onto the colored layer by a roll coating method, and the coating film was dried, so that the hydraulic transfer sheet of Comparative Example 1 having a 30 μm thick transfer layer was used. Was made.

  Next, a metal-molded article was produced in the same manner as in Example 1 except that the hydraulic transfer sheet of Comparative Example 1 was used as the hydraulic transfer sheet. In addition, the coloring layer and the transfer layer were transcribe | transferred to the obtained metal-tone molded product.

(Evaluation of the appearance of metal-molded products)
The appearance of the metal-like molded products obtained from the hydraulic transfer sheets of Examples and Comparative Examples was visually evaluated.

  As a result, the appearance of the metal-molded article produced by the hydraulic transfer sheet of Examples 1 to 6 reproduces the unevenness of the hairline pattern and the shadow of the recess, and the metal material with the hairline pattern is satisfactorily used. It was something to reproduce. On the other hand, although the metal-tone molded product by the hydraulic transfer sheet of Comparative Example 1 has a metallic luster, the hairline pattern has no unevenness and no shadow of the recesses, and becomes flat, and the hydraulic pressure of Examples 1 to 6 Compared to a metal-molded product using a transfer sheet, the reproducibility of a metal material with a hairline pattern was inferior.

  In addition, the metal-molded product using the hydraulic transfer sheet of Examples 1 to 4 and 6 has a more uniform metallic luster and a sharp hairline pattern than the metal-molded product using the hydraulic transfer sheet of Example 5. there were. The reason is that, in the hydraulic transfer sheets of Examples 1 to 4 and 6, the flat surface of the glittering scaly flakes is aligned parallel to the in-plane direction on the convex part of the transfer layer, and the unevenness of the transfer layer is glittered. It is inferred that the scaly flakes were filled without any gaps.

FIG. 1A is a sectional view showing an example of a hydraulic transfer sheet according to the first embodiment of the present invention, and FIG. 1B is a sectional view showing an example of a hydraulic transfer sheet according to the second embodiment of the present invention. FIG. 1 (C) is a cross-sectional view showing an example of a hydraulic transfer sheet according to the third embodiment of the present invention, and FIG. 1 (D) shows a hydraulic transfer sheet according to the fourth embodiment of the present invention. It is sectional drawing which shows an example. FIG. 2 (A) is a cross-sectional view for showing an example of a metal molded product obtained by the hydraulic transfer sheet of the present invention, and FIG. 2 (B) shows a metal molded product obtained by the hydraulic transfer sheet of the present invention. It is sectional drawing for showing another example. FIG. 3 (A) is a perspective view showing an example of a base sheet of a hydraulic transfer sheet according to the first or third embodiment of the present invention, and FIG. 3 (B) is the first or third of the present invention. It is a perspective view which shows another example of the base material sheet | seat of the hydraulic transfer sheet which concerns on this form. FIG. 4 (A) is a schematic view showing an example of the bright scaly flakes contained in the transfer layer of the hydraulic transfer sheet of the present invention, and FIG. 4 (B) is contained in the transfer layer of the hydraulic transfer sheet of the present invention. FIG. 4C is a cross-sectional view showing an example of the state of the brilliant scaly flakes formed, and FIG. 4C is a schematic view showing the state of the scaly scaly flakes in a metal-molded product in plan view. It is sectional drawing for demonstrating the manufacturing method of the metal tone molded product of this invention. It is a perspective view for demonstrating the shape of the molded article which gives a metallic decoration.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Hydraulic transfer sheet 2 Base material sheet 3 Transfer layer 4 Concavity and convexity layer 5 Adhesive layer 6 Metal-tone molded product 7 Molded product 8 Bright scaly flake

Claims (10)

A hydraulic transfer sheet in which a substrate sheet formed of a water-soluble or water-swellable resin, and a transfer layer formed of glittering scaly flakes and a water-insoluble transparent binder resin are laminated,
The hydraulic transfer sheet, wherein the base sheet has irregularities of a predetermined pattern on the surface on the transfer layer side, and the transfer layer is formed to fill the irregularities.   2. The hydraulic transfer sheet according to claim 1, wherein an average particle diameter of the glittering scaly flakes is smaller than an average size of a front end of the concave portion in the unevenness. A substrate sheet formed of a water-soluble or water-swellable resin, an uneven layer formed of a water-soluble resin, and a transfer layer formed of glittering scaly flakes and a water-insoluble transparent binder resin It is a hydraulic transfer sheet laminated in this order,
The hydraulic transfer sheet, wherein the uneven layer has unevenness of a predetermined pattern on the surface on the transfer layer side, and the transfer layer is formed to fill the unevenness.   4. The hydraulic transfer sheet according to claim 3, wherein an average particle diameter of the glittering scaly flakes is smaller than an average size of a front edge of the concave portion in the unevenness. Resin that dissolves or swells in an active agent composed of a base sheet formed of a water-soluble or water-swellable resin, a transfer layer formed of glittering scaly flakes and a water-insoluble transparent binder resin, and an organic solvent Is a hydraulic transfer sheet laminated with the adhesive layer formed in this order,
The hydraulic transfer sheet, wherein the base sheet has irregularities of a predetermined pattern on the surface on the transfer layer side, and the transfer layer is formed to fill the irregularities.   6. The hydraulic transfer sheet according to claim 5, wherein an average particle diameter of the glittering scaly flakes is smaller than an average size of an opening of the concave portion in the unevenness. A base sheet formed of a water-soluble or water-swellable resin, a concavo-convex layer formed of a water-soluble resin, a transfer layer formed of glittering scaly flakes and a water-insoluble transparent binder resin, A hydraulic transfer sheet in which an adhesive layer formed of a resin that dissolves or swells in an active agent composed of an organic solvent is laminated in this order,
The hydraulic transfer sheet, wherein the uneven layer has unevenness of a predetermined pattern on the surface on the transfer layer side, and the transfer layer is formed to fill the unevenness.   8. The hydraulic transfer sheet according to claim 7, wherein an average particle diameter of the glittering scaly flakes is smaller than an average size of a front end of the concave portion in the unevenness.   The hydraulic transfer sheet according to any one of claims 5 to 8, wherein the transparent binder resin hardly dissolves or swells in the activator.   The hydraulic transfer sheet according to any one of claims 1 to 9 is floated on the water surface such that the surface on the base sheet side faces the water surface, and a molded product is pushed in from above the hydraulic transfer sheet, A method for producing a metal-finished molded article, wherein the hydraulic transfer sheet is brought into close contact with the molded article with water pressure, and the transfer layer is transferred to the surface of the molded article.

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