JP2007253617A - Manufacturing method of hydraulic pressure transfer body and hydraulic pressure transfer body - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hydraulic pressure transfer method for obtaining a molded article on which a complex design in combination of a metal-resembling design or luster pattern and general printing pattern, is performed in a base body such as plastics. <P>SOLUTION: The film for hydraulic pressure transfer comprises a water soluble support film and an organic-solvent soluble transfer layer provided over the support film. The manufacturing method for the hydraulic pressure transfer body comprises the step 1 of activating the transfer layer, in a state with the film for hydraulic pressure transfer, floating on the water with the support film underneath, the step 2 of transferring the transfer layer onto the body to be transferred and the step 3 of removing the support film. The body to be transferred is a molded body comprising resin as a base material and has a decorative layer for supplying metal-like design covered with a transparent resin layer, partially on the surface thereof, and a masking film is pasted partially or wholly onto the top surface of the decorative layer. The method further includes the step 4 of removing the masking film during the step 3 or after the completion of the step 3. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a hydraulic transfer member partially having a metallic design and a method for producing the same.

  In the hydraulic transfer method, a hydraulic transfer film having a support film made of a water-soluble or water-swellable resin and a transfer layer imparting designability is floated on the water surface with the support film facing downward, and is usually called an activator. In this method, the organic layer is sprayed to soften the transfer layer, and then the transfer layer is transferred to the transfer target by being submerged in water while pressing the transfer target from above. By selecting the pattern of the transfer layer that imparts designability, the hydraulic transfer method can uniformly and neatly give an arbitrary pattern to a molded product having a complicated three-dimensional shape made of metal or plastic. it can.

  On the other hand, in recent years, a molded product in which a metal-like design or a complicated design combining a metal-like glossy pattern and a general-purpose printed pattern is applied to a base material such as plastic is used as a metal part, for example, an automobile bumper or the like. With the rapid increase in applications used as instrument panel substitutes and the like, many attempts have been made to apply metal-like designs to substrates such as plastics. Until now, there have not been many attempts to obtain a molded product having a metal-like design or a complicated design combining a metal-like glossy pattern and a general-purpose printed pattern by a hydraulic transfer method. For metal-like designs, a method using a hydraulic transfer film having a transfer layer made of a transparent resin containing metal powder (see, for example, Patent Document 1), a base 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, wherein the base sheet has irregularities of a predetermined pattern on the surface on the transfer layer side. A hydraulic transfer sheet having a hairline pattern in which the transfer layer is formed so as to fill the unevenness is known (see, for example, Patent Document 2). In addition, as a method of obtaining a molded product with a complex design that combines a pattern with gloss similar to metal and a general-purpose printed pattern by a hydraulic transfer method, for example, a metal surface layer is formed by metal vapor deposition or metal plating. A method in which a metal-like surface pattern such as a streak pattern or corrosion pattern is formed on the surface of the molded product by hydraulic transfer (for example, see Patent Document 3), a molded product in which a metal foil is applied to the surface, a hydraulic transfer method, etc. A method of combining a molded product with a printed pattern by a method to obtain a molded product having a desired shape, a method of printing a metal foil or a metallic ink on a molded product having a printed pattern by a hydraulic transfer method, etc. There is a way.

However, in the methods of Patent Documents 1 and 2 in which a hydraulic transfer film using a metal ink is used to obtain a hydraulic transfer body, no matter how high the metallic gloss is used, the current hydraulic transfer method does not give the gloss. It was difficult to reproduce 100%, and it was difficult to obtain a pattern having a gloss similar to metal.
Further, in the method of Patent Document 3 in which a pattern is formed by hydraulic transfer on the surface of a molded product in which a metal surface layer is formed by metal vapor deposition or metal plating, since the metal part becomes a transferred part, a primer or the like is provided on the transfer surface. If not provided, peeling may occur between the transferred portion and the hydraulic transfer film.
On the other hand, a method for forming a molded product having a desired shape by combining a molded product with a metal foil on the surface and a molded product with a printed pattern by a hydraulic transfer method or the like is It will be formed from two or more parts and is inferior in strength and the like. In addition, the process of creating a molded product with a metal foil applied to the surface, the step of obtaining a molded product with a printed pattern by a hydraulic transfer method, etc., and the process of combining these molded products are complicated and complicated. . Also, the method of printing a metal foil or metallic ink on a molded product that has been printed with a hydraulic transfer method is very difficult and unrealistic when the molded product has a three-dimensional solid shape.
Therefore, in the conventional method, it has still been difficult to obtain a molded product having a complicated design combining a pattern having gloss similar to metal and a general-purpose printed pattern.
JP 61-40200 A JP 2005-238664 A JP-A-11-28898

  An object of the present invention is to obtain a molded product in which a metal-like design or a complex design combining a metal-like gloss pattern and a general-purpose printed pattern is applied to a substrate such as plastic by a hydraulic transfer method. It is to provide a method.

  The present inventors include a metallic glossy ink layer containing a metal thin film strip and a binder resin, in which a masking film is provided on the outermost surface in advance at an arbitrary position on the surface of a substrate such as plastic to be transferred. A decorative layer providing a metallic design is provided, and after transferring the water pressure using a hydraulic transfer film having a general-purpose printed pattern with the substrate surface as a transfer surface, the masking film is removed to remove the metal at any location. The inventors found that a hydraulic transfer body having a design can be obtained, and solved the problems of the present invention.

That is, the present invention provides a hydraulic transfer film having a support film made of a water-soluble or water-swellable resin and a transfer layer soluble in an organic solvent provided on the support film. Manufacturing a hydraulic transfer body comprising: a step 1 for activating the transfer layer in a floating state; a step 2 for transferring the transfer layer to a transfer target; and a step 3 for removing the support film. In the method, the transferred object has a decorative layer that provides a metallic design covered with a transparent resin layer on a part of the transferred surface, and a masking film on a part or all of the outermost surface of the decorative layer Is a molded body based on resin,
Provided is a method for producing a hydraulic transfer body, which comprises the step 4 of removing the masking film in the step 3 or after the step 3.

  The present invention also provides a hydraulic transfer body obtained by the production method described above.

In the present invention, a pattern having a gloss similar to metal and a general-purpose printed pattern is applied to an arbitrary place on one transferred body having a three-dimensional solid shape such as plastic without requiring a complicated process. Can do. The material to be transferred used in the present invention has a resin as a base, and a decorative layer for providing a metallic design is also covered with a transparent resin layer. That is, since all the parts to which the hydraulic transfer film adheres are covered with resin, the adhesive property between the transfer object and the film is excellent, and the obtained hydraulic transfer object is peeled off between the film and the transfer object. There is nothing.
Specifically, the decorative layer portion that provides the metallic design of the transfer object comprises a thermoforming laminated sheet in which a transparent resin film layer, a metallic gloss ink layer, and a supporting base resin layer are laminated in this order, Since the transparent resin film layer comes to the outermost surface, it is possible to obtain a hydraulic transfer body excellent in adhesiveness by appropriately selecting the type of transparent resin to be used.
Moreover, as a to-be-transferred body, it is a molded body having a three-dimensional solid shape obtained by an insert molding method, and as a decorative sheet to be mounted in a mold at the time of insert molding, a masking film layer, a transparent resin film layer, a metal It is a laminated sheet in which a thin metallic strip, a metallic glossy ink layer containing a binder resin, and a supporting base resin layer are laminated in this order, and after the laminated sheet is thermoformed into a decorative sheet, a desired shape is obtained. When a molded body cut and insert-molded according to the above is used, a hydraulic transfer body having a strong metallic design portion without peeling or the like and a general-purpose printed pattern can be obtained.

The method for producing a hydraulic transfer body of the present invention comprises a step 1 of activating the transfer layer in a state where the hydraulic transfer film is floated on water with the support film down, and the transfer layer is transferred to a transfer object. And a step 3 for removing the support film, and the transferred body has a decorative layer that provides a metallic design covered with a transparent resin layer on a part of the transferred surface. A resin-based molded body in which a masking film is pasted on a part or all of the outermost surface of the decorative layer, and the masking film is removed in the step 3 or after the step 3 It is characterized by having step 4.
In the manufacturing method of this invention, the schematic diagram of the process 1-the process 4 is shown in FIG. In FIG. 1, 1 is a molded body based on a resin, 2 is a decorative layer providing a metallic design, and 3 is a masking film. 1 to 3, 4 to 1, 5 denotes a hydraulic transfer film, and 6 denotes a water tank. The water transfer film 5 is floated on water with the support film facing down in the water tank 6 to activate the transfer layer (Step 1), and the transfer layer 4 is transferred to the water tank 6 by pressing it into the water. (Step 2), the support film of the hydraulic transfer film 5 is removed (Step 3), and the masking film 3 is removed (Step 4).

(Hydraulic transfer film)
The hydraulic transfer film used in the production method of the present invention is a hydraulic transfer film having a known support film made of a water-soluble or water-swellable resin and a transfer layer soluble in an organic solvent provided on the support film. Film. In the present invention, it is necessary to conceal the portion of the decorative layer portion provided with the metallic design on the transfer surface of the transfer body that is not subjected to the masking film with a hydraulic transfer film. Therefore, the hydraulic transfer layer preferably has a decorative layer composed of a colored ink layer capable of concealing the transfer target. Since the resulting hydraulic transfer body is excellent in appearance and surface hardness, it can be activated by active energy rays or heat. It is more preferable to have a curable curable resin layer and a decorative layer.

(Hydraulic transfer film Support film)
The support film of the hydraulic transfer film used in the present invention is a film made of a water-soluble or water-swellable resin.
Examples of resins comprising water-soluble or water-swellable resins include polyvinyl alcohol (PVA), polyvinyl pyrrolidone, acetyl cellulose, polyacrylamide, acetyl butyl cellulose, gelatin, glue, sodium alginate, hydroxyethyl cellulose, carboxymethyl cellulose, etc. it can. Among them, a PVA film generally used as a hydraulic transfer film is particularly preferable because it is easily dissolved in water, easily available, and suitable for printing a curable resin layer. These resin layers may be a single layer or multiple layers, and the layer thickness is preferably about 10 to 200 μm.

(Hydraulic transfer film, transfer layer, decorative layer)
In the transfer layer of the hydraulic transfer film used in the present invention, the decorative layer is obtained by printing a single layer or a plurality of layers of ink on the support film by a method such as printing. The printing method is not particularly limited, and for example, it can be produced by printing or coating by a method such as gravure printing, offset printing, screen printing, ink jet printing, roll coating, comma coating, rod gravure coating, or micro gravure coating. . The entire surface of the ink layer may be printed or coated with the same ink (100% in the case of halftone dots), or may be partially printed so as to form a pattern. Furthermore, even if an ink receiving layer, a curable resin layer curable with at least one of active energy ray irradiation and heating (hereinafter abbreviated as a curable resin layer), or the like is laminated between the support and the ink layer. good.

  There are no particular restrictions on the ink used. As the colorant contained in the ink, a pigment is preferable, and any of an inorganic pigment and an organic pigment can be used. For example, general-purpose coloring pigments include carbon black as a black pigment; yellow lead, yellow lead, anthraquinone yellow, mineral fast yellow, titanium yellow; red pigments such as Bengala, cadmium red, quinacridone red, permanent red 4R, and risol red. , Pyrazolone red, watching red calcium salt, lake red D, brilliant carmine 6B, eosin lake; blue pigment, bitumen, cobalt blue, alkali blue lake, Victoria blue lake, phthalocyanine blue, metal-free phthalocyanine blue; Chrome green, chromium oxide, pigment green B, malachite green lake; examples of white pigments include titanium white. Examples of pigments that exhibit a metallic tone include metal powder pigments (aluminum, bronze, etc.), metal foil pigments (aluminum, bronze, etc.), metal vapor-deposited foil pigments (pulverized films of plastics, etc., on which aluminum, bronze, etc. are deposited). It is done. Pearl pigments (such as those obtained by pulverizing natural pearls, flaky materials such as mica, aluminum, glass, etc., coated with titanium oxide, iron oxide, etc.) as pigments that exhibit pearl tone, multicolor effect, polarization effect, hologram, etc. Etc. Inorganic extender pigments such as lime carbonate powder, precipitated calcium carbonate, gypsum, clay (China Clay), silica powder, diatomaceous earth, talc, kaolin, alumina white, barium sulfate, aluminum stearate, magnesium carbonate, barite powder, abrasive powder, Silicone, glass beads and the like can also be used. The varnish resin contained in the ink is, for example, an acrylic resin system, a polyurethane resin system, a polyester resin system, a vinyl resin system (vinyl chloride, vinyl acetate, vinyl chloride-vinyl acetate copolymer resin), a chlorinated olefin resin system, Known inks such as ethylene-acrylic resin, petroleum resin, and cellulose derivative resin can be used. Among these, polyurethane resins, polyester resins, vinyl chloride-vinyl acetate copolymer resins, cellulose derivative resin systems are preferably used because they are excellent in solubility in organic solvents, fluidity, pigment dispersibility, and transferability. Polyester resin system and cellulose derivative resin system are preferable, and polyurethane resin system and cellulose derivative resin system are particularly preferable.

(Hydraulic transfer film, transfer layer, curable resin layer)
When the hydraulic transfer film used in the present invention has a curable resin layer as a transfer layer, the curable resin layer is a resin layer containing a resin that can be cured by irradiation with active energy rays or heating. Active energy ray curing and heat curing may be used in combination. The curable resin layer is preferably transparent since the design of the decorative layer of the resulting hydraulic transfer body can be expressed well, but depending on the required properties and design characteristics of the transfer body. Basically, it is sufficient that the color and pattern of the decorative layer of the hydraulic transfer body obtained can be seen through, and it is not necessary to be completely transparent. That is, from transparent to translucent ones are included. Moreover, it may be colored.

(Hydraulic transfer film Transfer layer Active energy ray curable resin)
The resin layer containing a resin curable by active energy ray irradiation includes, for example, a known radical polymerizable compound and, if necessary, a photopolymerization initiator. As the radically polymerizable compound, an oligomer or polymer having three or more (meth) acryloyl groups in one molecule is preferable, and a mass average molecular weight having three or more (meth) acryloyl groups in one molecule is 300 to 1. Ten thousand, more preferably 300 to 5,000 active energy ray-curable oligomers or polymers are preferably used. Also, it contains a reactive monomer having a (meth) acryloyl group for the purpose of adjusting the viscosity, reduces the tackiness of the curable resin layer, improves the glass transition temperature (Tg), or cohesive failure of the curable resin layer For the purpose of improving the strength, a thermoplastic resin may be contained.

  Examples of the oligomer or polymer having a (meth) acryloyl group include, for example, polyurethane (meth) acrylate, polyester (meth) acrylate, polyacryl (meth) acrylate, epoxy (meth) acrylate, and polyalkylene glycol poly (meth) acrylate. , Polyether (meth) acrylate, etc., among which polyurethane (meth) acrylate, polyester (meth) acrylate and epoxy (meth) acrylate are preferably used.

  Examples of the reactive monomer having a (meth) acryloyl group include, for example, methyl acrylate, methyl methacrylate (hereinafter collectively referred to as methyl (meth) acrylate), ethyl (meth) acrylate, n-butyl (meta ) Acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, phenyl ( (Meth) acrylate, phenyl cellosolve (meth) acrylate, 2-methoxyethyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 2-acryloyloxyethyl Monofunctional monomers such as idrogen phthalate, dimethylaminoethyl (meth) acrylate, trifluoroethyl (meth) acrylate, trimethylsiloxyethyl methacrylate, N-vinylpyrrolidone, styrene, diethylene glycol di (meth) acrylate, neopentyl glycol di (meth) ) Acrylate, 1,6-hexanediol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 2,2′-bis (4- (meth) acryloyloxypolyethyleneoxyphenyl) propane, 2,2′-bis ( 3-functional monomers such as 4- (meth) acryloyloxypolypropyleneoxyphenyl) propane, 3 such as trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, etc. Ability monomers, tetrafunctional monomers such as pentaerythritol tetra (meth) acrylate, hexafunctional monomers such as dipentaerythritol hexaacrylate. A maleimide compound such as butylene glycol bis (maleimide acetate) can also be used. Of course, it is also possible to use a mixture of two or more of these monomers.

  Examples of photopolymerization initiators include, for example, acetophenone compounds such as diethoxyacetophenone and 1-hydroxycyclohexyl-phenyl ketone; benzoin compounds such as benzoin and benzoin isopropyl ether; 2,4,6-trimethylbenzoin diphenylphosphine oxide Acyl phosphine oxide compounds such as: benzophenone, benzophenone compounds such as methyl 4-phenylbenzophenone o-benzoylbenzoate; thioxanthone compounds such as 2,4-dimethylthioxanthone; aminobenzophenones such as 4,4′-diethylaminobenzophenone Compounds such as polyether-based maleimide carboxylic acid ester compounds, and the like, which can be used in combination. The usage-amount of a photoinitiator is 0.1-15 mass% normally with respect to the active energy ray curable resin to be used, Preferably it is 0.5-8 mass%. Examples of the photosensitizer include amines such as triethanolamine and ethyl 4-dimethylaminobenzoate. Furthermore, onium salts such as benzylsulfonium salt, benzylpyridinium salt, and arylsulfonium salt are known as photocationic initiators, and these initiators can also be used, and are used in combination with the above photopolymerization initiators. You can also

  The thermoplastic resin used is preferably compatible with the active energy ray curable resin, and specific examples include polymethacrylate, polystyrene, polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate, and polyester. These may be a homopolymer or a copolymer of a plurality of monomers. The thermoplastic resin is preferably non-polymerizable. Among them, polystyrene and polymethacrylate are preferable because they have high Tg and are suitable for reducing the adhesiveness of the curable resin layer, and in particular, polymethacrylate mainly composed of polymethyl methacrylate is transparent, solvent resistant, and It is preferable at the point which is excellent in abrasion resistance.

  Further, the molecular weight and Tg of the thermoplastic resin have a great influence on the film-forming ability. In order to suppress fluidity of the curable resin and facilitate activation of the curable resin layer, the mass average molecular weight of the thermoplastic resin is preferably 3,000 to 400,000, more preferably 10,000 to 200,000. Tg is preferably 35 ° C to 200 ° C, more preferably 35 ° C to 150 ° C. When using a thermoplastic resin having a relatively low Tg of around 35 ° C., the mass average molecular weight of the thermoplastic resin is preferably 100,000 or more. If the amount of the thermoplastic resin is too large, the curing reaction of the curable resin is inhibited. Therefore, the thermoplastic resin is preferably added in a range not exceeding 70 parts by mass with respect to 100 parts by mass of the total resin amount of the curable resin layer. .

(Hydraulic transfer film, transfer layer, thermosetting resin)
The resin layer containing a resin curable by heating is a compound having a functional group that polymerizes by the action of heat or a catalyst in the molecule, or a thermoreactive compound that becomes a curing agent to a thermosetting compound that becomes a main agent including. Further, similar to the active energy ray curable resin, the thermoplastic resin is used for the purpose of reducing the tackiness of the curable resin layer, improving the glass transition temperature (Tg), or improving the cohesive fracture strength of the curable resin layer. May be included.

  The thermal polymerization initiator is not particularly limited. However, when the transfer object is a plastic having a low heat resistant temperature, it is preferable to use a thermal polymerization initiator having a starting temperature as low as possible. It is preferred to use a thermal polymerization initiator having an initiation temperature. Moreover, a well-known thing can be used as a thermosetting compound, for example, it has a functional group which superposes | polymerizes by the effect | action of a heat | fever or a catalyst, for example, N-methylol group, N-alkoxymethyl group, an epoxy group, a methylol group, an acid. A compound or resin having an anhydride, a carbon-carbon double bond, or the like can be used.

  The thicker the curable resin layer, the greater the protective effect of the resulting molded product, and the greater the effect of absorbing the irregularities of the decorative layer, so that the molded product can have excellent gloss. Therefore, the film thickness of the curable resin layer is specifically 3 μm or more, preferably 15 μm or more. When the thickness of the curable resin layer exceeds 200 μm, it is difficult to sufficiently activate the curable resin layer with an organic solvent. From the viewpoints of sufficient activation of the curable resin layer by the organic solvent, function as a protective layer for the decoration layer, absorption of unevenness of the decoration layer, and the like, the dry film thickness of the curable resin layer should be 3 to 200 μm. More preferably, it is 15-70 micrometers.

(Transfer)
The transferred object used in the present invention has a decorative layer that provides a metallic design covered with a transparent resin layer on a part of the transferred surface, and a masking film is applied to a part or all of the outermost surface of the decorative layer. It is a molded article based on a resin, which is affixed. Here, the “transfer surface” refers to all surfaces on the transfer body onto which the hydraulic transfer film is transferred. Further, “having a decorative layer providing a metallic design covered with a transparent resin layer on a part of the transferred surface, and having a masking film affixed to a part or all of the outermost surface of the decorative layer” means that This represents a state in which a decorative layer for providing a metallic design covered with a transparent resin layer is provided on a part of the transfer surface, and a masking film is attached to a part or all of the decorative layer for providing the metallic design. In the present invention, the shape of the decorative layer that provides the metal design of the obtained hydraulic transfer body is obtained in the shape of a masking film, and the shape of the decorative layer that provides the metal design is viewed from above the surface to be transferred. It is not necessary for the shape of the case to represent design. For example, as shown in FIG. 2, a transfer target provided with a masking film having the same shape as the decorative layer providing the metal design, covering the entire decorative layer providing the metal design, may be used. As shown in FIG. 3, you may use the to-be-transferred object which provided the masking film so that a part of decoration layer which provides a metallic design may be covered.

  The decorative layer that provides the metal design on a part of the transferred surface is a metallic gloss ink layer or metal vapor deposition that can be provided with the metal design covered with a transparent resin layer on a resin-based molded body. Obtained by providing a layer. The metallic gloss ink layer or the metal vapor deposition layer may be a single layer or may be laminated. When laminating, they may be combined with each other.

(Metallic ink layer to be transferred)
The metallic gloss ink used in the present invention usually contains a metal powder and a binder resin. As metal powders, metal strips obtained from pearlescent pigments such as basic lead carbonate, lead hydrogen arsenate, bismuth oxychloride, titanium dioxide-coated mica, iron oxide-coated mica and vapor-deposited metal films commonly used in metallic inks Aluminum, chromium, nickel, gold, platinum, silver, copper, germanium, brass, titanium, indium, molybdenum, tungsten, palladium, iridium, silicon, tantalum, nickel chromium, stainless steel, chromium copper, aluminum silcon, zinc oxide Metal powders such as tin oxide, pearls, shells, ground products such as fish scales, metal powders such as glass powder, metal-coated glass powder, glittering components, metal thin film strips, and the like are used. In particular, metallic glossy inks using metal thin film strips cannot be obtained with conventional metal powders as a result of the metal thin film strips being oriented parallel to the surface of the object when the ink is printed or applied. A glossy surface with high brightness and a high metallic tone is particularly preferable. As metals, aluminum, chromium, nickel, gold, platinum, silver, copper, germanium, brass, titanium, indium, molybdenum, tungsten, palladium, iridium, silicon, tantalum, nickel chromium, stainless steel, chromium copper, aluminum silcon A metal, an alloy, or a compound such as zinc oxide or tin oxide is used.

  As the binder resin, conventional gravure inks, flexo inks, screen inks, resins usually used for paints, and the like can be used. Specific examples include acrylic resin, polyurethane resin, polyamide resin, urea resin, polyester resin, vinyl chloride resin, vinylidene chloride resin, vinyl chloride-vinyl acetate copolymer resin, ethylene-vinyl acetate copolymer resin, olefin resin, chlorination. Olefin resins, epoxy resins, petroleum resins, cellulose derivative resins and the like are used. These resins may be used in combination or in combination with those obtained by chemically bonding polar groups such as carboxylic acid groups, phosphoric acid groups, sulfonic acid groups, amino groups, and quaternary ammonium bases.

  Various additives that are usually used in conventional gravure inks, flexo inks, screen inks, paints, etc. can be used as necessary for the metallic gloss ink as long as it does not impair the design and moldability. . Various organic solvents can also be used for the purpose of adjusting the viscosity and the like.

  In the case of an ink using metal thin film strips as the metallic gloss ink, the metal thin film strips to be blended for developing the metallic gloss are preferably 5 to 25 μm. Therefore, when ordinary kneaded meat or the like is performed, the metal thin film pieces may become fine particles and the metallic luster may be extremely lowered. Therefore, in this case, it is desirable that the kneaded meat is not used and that the above-described blended raw materials are simply mixed to form an ink. For that purpose, it is preferable to surface-treat the metal thin film strip for the purpose of improving dispersibility.

(Metal vapor deposition layer to be transferred)
As a metal used for the metal vapor deposition layer used by this invention, metals, alloys, or compounds, such as aluminum, chromium, nickel, gold | metal | money, silver, copper, germanium, zinc oxide, a tin oxide, are used. The metal vapor deposition layer is formed by vacuum vapor deposition, sputtering, ion plating, plating, or the like. The metal vapor deposition layer may be implemented on the entire surface, or may be partially implemented by masking and patterned in combination with color ink.

The method for providing a decorative layer for providing the metal design on a resin-based molded body includes (a) printing or applying a metallic gloss ink on the surface of the resin substrate, or directly depositing a metal vapor deposition layer on a vacuum vapor deposition method. Or a transparent resin layer is printed or applied, or (b) a thermoformed laminated sheet including a metallic glossy ink layer or a metal vapor-deposited layer is thermoformed to obtain a decorative sheet. There is a method in which a sheet is cut according to a desired shape as necessary and then insert-molded in a state of being mounted in a mold. Among these, the method (b) is simple and preferable because there is no unevenness in the metal design portion, and the use of metallic glossy ink is more preferable because the metal design portion is not cracked during thermoforming. In addition, a decorative sheet for mounting a thermoformed decorative sheet in a mold at the time of insert molding in a state where a masking film is provided in advance on a side to be a decorative surface of a thermoformed laminated sheet including a decorative layer for providing a metallic design When used as, it is more preferable because it saves the trouble of providing a masking film later.
Hereinafter, a molded body having a three-dimensional solid shape obtained by an insert molding method, which is a preferable embodiment of the transfer body used in the present invention, will be described in detail. Hereinafter, a lithographic sheet before thermoforming including a decorative layer providing a metallic design is referred to as a “thermoforming laminate sheet” and has a three-dimensional solid shape obtained by thermoforming the thermoforming laminate sheet. The sheet is referred to as a “decorative sheet”.

(Layer to be transferred, laminated sheet for thermoforming)
The laminated sheet for thermoforming used in the present invention is a laminated sheet in which at least a transparent resin film layer, a decorative layer providing a metal design, and a supporting base resin layer are laminated in this order. As the decorative layer for providing a metallic design, a metallic glossy ink layer containing a metal thin film strip and a binder resin is particularly preferable because excellent gloss is obtained.

(Transfer material: Laminated sheet for thermoforming, transparent resin film layer)
In the transparent resin film layer used in the present invention, “transparent” may be transparent as long as it does not impair the sharpness of the decorative layer, and may be colored. Physically, the haze (cloudiness value) of the film is preferably less than 20%. The haze (haze value) is measured according to JIS K-7105.
The transparent resin that can be used in the present invention is not particularly limited as long as it is a resin that exhibits spreadability by heating and can be formed into a film, but a thermoplastic resin is preferably used because of its easy spreadability. Further, as long as the thermoformability is not impaired, a heat-crosslinking resin such as lacquer, isocyanate or epoxy, UV-crosslinking resin, EB cross-linking resin, or the like may be used.
The transparent resin film layer used in the present invention is a layer in which these transparent resins are formed into a single layer or a plurality of layers. One transparent resin layer is usually composed of one kind of resin as a main component. When the layer structure is one layer, the transparent resin is preferably a thermoplastic resin from the viewpoint of ease of spreading by heating. In the case of multiple layers, it is possible to impart performance such as designability, abrasion resistance, scratch resistance, weather resistance, stain resistance, water resistance, chemical resistance, heat resistance, etc. to the surface side during thermoforming. Various layers can be provided. Among these, a transparent resin film laminated with a thermoplastic resin layer so that the crosslinkable resin layer is the outermost layer is preferable in order to achieve both the spreadability by heating and the surface hardness. Since the transferred material having the cross-linked resin layer as the outermost layer is resistant to water at the time of hydraulic transfer or an organic solvent which is an activator, it is excellent in aesthetics of the obtained hydraulic transfer material. As the crosslinkable resin, a heat crosslinkable resin is preferable because it can be cross-linked by utilizing heat at the time of molding. In this case, it is preferable to use the resin in a state of being semi-crosslinked before molding. This is preferable because it can be completely crosslinked only by heat. These resins are preferably hydroxyl group-containing vinyl copolymer / isocyanate curing as a curing system, and may contain a colorant such as a pigment or a dye as long as the transparency is not impaired.
The method for producing the transparent resin film is not particularly limited, and may be formed into a film by a conventional method. Further, the transparent resin film may be stretched in a uniaxial or biaxial direction as long as the spreadability during thermoforming is not impaired.
Although there is no restriction | limiting in particular in the thickness of the whole transparent resin film, The range of 10-2000 micrometers is preferable from the applicability | paintability and thermoformability of a metallic luster ink layer, More preferably, it is 30-500 micrometers.

The thermoplastic resin used in the present invention is preferably a thermoplastic resin having a softening point in the range of 30 to 300 ° C, more preferably a softening point of 50 to 250 ° C in order to perform a molding step by heat such as vacuum molding. It is a range. Examples of the thermoplastic resin include polyolefin resins such as polyethylene and polypropylene, polyester resins such as polyethylene terephthalate and polybutylene terephthalate, acrylic resins such as polymethyl methacrylate and polyethyl methacrylate, ionomer resins, polystyrene, polyacrylonitrile and acrylonitrile. -Styrene resin, methyl methacrylate-styrene resin, polyacrylonitrile, polyamide resin such as nylon 6 and nylon 66, ethylene-vinyl acetate, ethylene-acrylic acid resin, ethylene-ethyl acrylate resin, ethylene-vinyl alcohol resin, polyvinyl chloride, Chlorine resin such as polyvinylidene chloride, fluorine resin such as polyvinyl fluoride and polyvinylidene fluoride, polycarbonate resin, cyclic polyolefin Fin, modified polyphenylene ether resins, methylpentene resins, cellulose resins, acrylonitrile - butadiene - styrene (ABS) copolymer resin, etc. are preferably used. Among these thermoplastic resins, they are selected from the group of acrylic resins, polyester resins, polycarbonate resins, and cyclic polyolefin resins because they are excellent in adhesion to the hydraulic transfer film, thermoformability, and metal design. A film mainly containing at least one kind is preferred.
Moreover, these blends and polymer alloys can be used as long as the transparency of the film is not impaired. These may be used in a single layer or multiple layers. Further, these thermoplastic resins may be modified with rubber as long as the transparency is not impaired. There is no particular limitation on the method of making the rubber modified, but a method of copolymerizing by adding a rubber component monomer such as butadiene at the time of polymerization of each resin, and hot melting of each resin and synthetic rubber or thermoplastic elastomer. The method of blending is mentioned. In addition, conventional additives may be added to these thermoplastic resins as long as transparency and moldability are not hindered. For example, plasticizers, light-resistant additives (ultraviolet absorbers, stabilizers, etc.), oxidation Inhibitors, antiozonants, activators, antistatic agents, lubricants, antifriction agents, surface conditioners (leveling agents, antifoaming agents, antiblocking agents, etc.), antifungal agents, antibacterial agents, dispersants, flame retardant In addition, additives such as a flow accelerator and a flow accelerator aid may be blended. These additives may be used alone or in combination of two or more.

  In order to obtain a laminated sheet for thermoforming in which the metallic gloss ink layer and the transparent resin film layer are laminated as a decorative layer, the metal ink may be spread on the transparent resin film. Examples of the spreading method include printing methods such as gravure printing, flexographic printing, screen printing, gravure coater, gravure reverse coater, flexo coater, blanket coater, roll coater, knife coater, knife knife coater, kiss touch coater, and kiss touch coater. Coating methods such as a touch reverse coater, a comma coater, a comma reverse coater, and a micro gravure coater can be used.

  Moreover, when using a metal vapor deposition layer as a decoration layer, it vapor-deposits on the said transparent resin film by a vacuum evaporation method, sputtering method, a plating method, etc. Each of these layers may be a single layer or may be laminated. When laminating, they may be combined with each other.

  If the decorative layer is too thin, the concealability may be inferior and the design may be impaired. If the decorative layer is too thick, color unevenness is likely to occur during thermoforming. Therefore, when the metallic gloss ink is used as the decorative layer, the thickness is 0. 0.01 to 5 μm is preferable, and 0.05 to 3 μm is more preferable. Moreover, when using a metal thin film as a decoration layer, 0.01-0.1 micrometer is preferable, More preferably, it is 0.02-0.08 micrometer. Further, for the purpose of controlling the adhesion between the transparent resin film layer and the decorative layer, the surface of the transparent resin film is subjected to surface treatment such as plasma treatment, corona treatment, flame treatment, electron beam irradiation treatment, sanding treatment, ozone treatment, or the like. Surface treatment such as dry plating treatment such as vacuum deposition, sputtering, ion plating, and primer coating may be performed.

(Substrate to be transferred Laminated sheet for thermoforming, ink protective layer)
When using metallic glossy ink that uses thin metal strips as a decorative layer, the ink is used to improve heat resistance, solvent resistance, design, weather resistance, etc. between the decorative layer and the transparent resin film layer. One or more protective layers may be provided. Especially, since the ink solvent resistance and the heat resistance at the time of shaping | molding are favorable, the ink protective layer which consists of a thermosetting composition is preferable. The type of resin that can be used for the ink protective layer is not particularly limited as long as it does not impair the moldability, but it is acrylic from the viewpoints of easy adjustment of crosslink density, weather resistance, adhesion to the transparent resin film layer, etc. Resins are preferred. There are no particular restrictions on the crosslinking mechanism, and in the case of acrylic resins, UV curing, EB curing, hydroxyl group-containing vinyl copolymer / isocyanate curing, silanol / water curing, epoxy / amine curing, etc. can be used. From the viewpoints of easiness, weather resistance, reaction rate, presence or absence of reaction byproducts, production cost, etc., hydroxyl group-containing vinyl copolymer / isocyanate curing is preferable. The ink protective layer can also be a colored layer in order to impart design properties. In this case, the amount of the colorant added is preferably 20% or more of the total light transmittance of the colorant and the target color tone or the protective layer, and the total light transmittance is particularly preferably 40% or more. More preferred. A pigment is preferred as the colorant. The pigment to be used is not particularly limited, and known pigments such as colored pigments, metallic pigments, interference color pigments, fluorescent pigments, extender pigments and rust preventive pigments can be used. Examples of the color pigment include quinacridone series such as quinacridone red, azo series such as pigment red, phthalocyanine series organic pigments such as phthalocyanine blue, phthalocyanine green, and perylene red; and inorganic pigments such as titanium oxide and carbon black. Examples of metallic pigments include aluminum powder, nickel powder, copper powder, brass powder, and chromium powder. Examples of interference color pigments include pearlescent pearl mica powder and pearlescent colored pearl mica powder, and fluorescent pigments include quinacridone, anthraquinone, perylene, perinone, and diketopyrrolopyrrole. , Isoindolinone, condensed azo, benzimidazolone, monoazo, insoluble azo, naphthol, flavanthrone, anthrapyrimidine, quinophthalone, pyranthrone, pyrazolone, thioindigo, anthanthrone, dioxazine , Phthalocyanine and indanthrone organic pigments, metal complexes such as nickel dioxin yellow and copper azomethine yellow, metal oxides such as titanium oxide, iron oxide and zinc oxide, barium sulfate and calcium carbonate, etc. Metal salts, carbon black, aluminum and And inorganic pigments such as mica.

(Substrate to be transferred Thermoformed laminated sheet Support base resin layer)
After the decorative layer is formed on the transparent resin film layer, a supporting base resin layer can be further laminated. For this layer, a thermoplastic film is used, and a thermoplastic resin having a softening point in the range of 30 to 300 ° C is preferred, and a more preferable softening point is in the range of 50 to 250 ° C. Specific examples include ABS (acrylonitrile butadiene styrene) resin, ABS polymer alloy, PVC (polyvinyl chloride) / ABS resin, PA (polyamide) / ABS resin, PC (polycarbonate) / ABS resin. , PBT (polybutylene terephthalate) / ABS resin, AAS (acrylonitrile / acrylic rubber / styrene) resin, AS (acrylonitrile / styrene) resin, AES (acrylonitrile / ethylene rubber / styrene) resin, MS ((meth) acrylic acid Ester / styrene resin, PC (polycarbonate) resin, PMMA (polymethyl methacrylate) resin, PMMA / ABS / AS resin, polyolefin resin such as polyethylene and polypropylene, polyethylene terephthalate and polybutylene terf Polyester resin such as rate, acrylic resin such as polymethyl methacrylate and polyethyl methacrylate, ionomer resin, polyamide resin such as nylon 6 and nylon 66, ethylene-vinyl acetate, ethylene-acrylic acid resin, ethylene-ethyl acrylate resin, ethylene- Vinyl alcohol resins, chlorine resins such as polyvinyl chloride and polyvinylidene chloride, fluororesins such as polyvinyl fluoride and polyvinylidene fluoride, etc. are preferably used. Among these thermoplastic resins, polypropylene resins, polyethylene resins, blends thereof, and films mainly composed of ABS resins and AAS resins are preferable because of their excellent thermoformability among these thermoplastic resins. For resin For the purpose of improving impact strength, etc., ethylene propylene rubber (EPR), styrene / butadiene / styrene (SBS) resin, styrene / isoprene / butadiene / styrene (SIBS) resin, styrene / ethylene / butadiene / styrene (SIBS) resin, etc. These rubber modifiers may be added as long as they do not impair the transparency of the film, and these blends and polymer alloys can be used. The thickness of the supporting base resin layer is not particularly limited, but is preferably 10 to 3000 μm, for example, and conventional additives may be added to these supporting base resin layers as long as the moldability is not hindered. , For example, plasticizers, light resistant additives (ultraviolet absorbers, stabilizers, etc.), antioxidants, antiozonants, activators, antistatic agents , Lubricants, anti-friction agents, surface conditioners (leveling agents, antifoaming agents, anti-blocking agents, etc.), anti-fungal agents, antibacterial agents, dispersants, flame retardants, wake accelerators and auxiliaries aids An agent may be blended. These additives may be used alone or in combination of two or more. As a method for laminating the supporting base resin layer, a co-extrusion method by heat melting is preferable because a film forming cost is low and an efficient sheet with little thickness unevenness can be obtained.

  The laminated sheet is made into a three-dimensional decorative sheet by thermoforming. At this time, if the molding shrinkage of the transparent resin used for the supporting base resin layer and the transparent resin film layer, especially thermoplastic resin, is different, Deformation occurs and it becomes difficult to maintain a good shape. In order to improve this, an inorganic filler can be mix | blended in a support base resin layer. The kind of the inorganic filler is not particularly limited, and examples thereof include talc, calcium carbonate, clay, diatomaceous earth, mica, magnesium silicate, and silica. The added amount of the inorganic filler is preferably 5 to 60% by mass. The particle size is not particularly limited, but if it is too large, irregularities may occur on the surface of the supporting base resin layer, which may adversely affect the appearance and gloss of the laminated sheet. Therefore, the average particle size of the inorganic filler in the support base resin layer is preferably 8 μm or less, and more preferably 4 μm or less.

  When a colorant is contained in the supporting base resin layer, the concealability of the decorative sheet base is improved, and it is more preferable because the design of the transfer object can be unified. The colorant is not particularly limited, and similarly to the colorant used for the thermoplastic resin of the base material, conventional inorganic pigments and organic pigments used for coloring general thermoplastic resins according to the intended design. And dyes can be used. For example, inorganic pigments such as titanium oxide, titanium yellow, iron oxide, complex oxide pigments, ultramarine, cobalt blue, chromium oxide, bismuth vanadate, carbon black, zinc oxide, calcium carbonate, barium sulfate, silica, talc; azo Pigments, phthalocyanine pigments, quinacridone pigments, dioxazine pigments, anthraquinone pigments, isoindolinone pigments, isoindoline pigments, perylene pigments, perinone pigments, quinophthalone pigments, thioindigo pigments and diketopyrrolo Organic pigments such as pyrrole pigments; metal complex pigments and the like. Moreover, it is preferable to use 1 type or 2 types mainly chosen from the group of an oil-soluble dye as a dye. The blending amount of the colorant varies depending on the type and the thickness and color tone of the supporting base resin sheet, but in order to secure the hue and concealment and maintain the impact strength, the resin constituting the supporting base resin layer is used. The mass percentage is preferably in the range of 0.1 to 20 mass%, more preferably in the range of 0.5 to 15 mass%.

(Substrate to be transferred, laminated sheet for thermoforming, adhesive layer)
After forming a decoration layer in a transparent resin film layer, when further laminating | supporting a support base resin layer, it can laminate | stack via an adhesive bond layer. As an adhesion method, lamination can be performed by a dry lamination method, a wet lamination method, a hot melt lamination method, or the like using a conventional solvent-type adhesive.

Components constituting the adhesive include conventional phenol resin adhesives, resorcinol resin adhesives, phenol-resorcinol resin adhesives, epoxy resin adhesives, urea resin adhesives, polyurethane adhesives, and polyaromatics. Thermosetting resin adhesives such as tic adhesives and reactive adhesives using ethylene unsaturated carboxylic acid, vinyl acetate resin, acrylic resin, ethylene vinyl acetate resin, polyvinyl alcohol, polyvinyl acetal, vinyl chloride, nylon, And thermoplastic resin adhesives such as cyanoacrylate resins, chloroprene adhesives, nitrile rubber adhesives, SBR adhesives, and rubber adhesives such as natural rubber adhesives. These adhesives can be applied on the decorative layer or on the supporting base resin layer with a gravure coater, gravure reverse coater, flexo coater, blanket coater, roll coater, knife coater, kiss touch coater, comma coater, etc. .
The application amount of the adhesive is preferably in the range of 0.1 to 30 g / m <2>, particularly preferably 2 to 10 g / m <2> in order that the adhesive force is sufficient and the drying property is good. If it is less than 2 g / m 2, the adhesive strength becomes weak, and if it is more than 10 g / m 2, the drying property is lowered. The thickness of the adhesive layer is preferably in the range of 0.1 to 30 μm, more preferably 1 to 20 μm, and particularly preferably 2 to 10 μm. In addition, the adhesive surface of the supporting base resin layer is surface treatment such as plasma treatment, corona treatment, flame treatment, electron beam irradiation treatment, sanding treatment, ozone treatment, or vacuum for the purpose of improving the affinity with the adhesive. Dry plating treatment such as vapor deposition, sputtering, or ion plating may be performed. Moreover, it can replace with an adhesive bond layer and can also provide an adhesive layer. As the adhesive, acrylic, rubber, polyalkyl silicon, urethane, polyester, and the like are preferably used.

(Transfered material Masking film)
The transferred object used in the present invention has a decorative layer that provides a metallic design covered with a transparent resin layer on a part of the transferred surface, and a masking film is applied to a part or all of the outermost surface of the decorative layer. It is a molded article based on a resin, which is affixed. The masking film is not particularly limited as long as it is a film used for the purpose of temporarily sticking on a decorative layer providing a metallic design and peeling in a subsequent process, and a known masking film may be used. it can. Usually, a thermoplastic film having an adhesive layer on one side is used. Specifically, stretched or unstretched polypropylene resin film, polyethylene resin film such as high density polyethylene, low density polyethylene, linear low density polyethylene, polyester (PET, PBT) resin film, soft vinyl chloride resin film, Polyvinyl alcohol (PVA) resin films and polyamide resin films such as nylon 6 and nylon 66 can be used. Also, for the purpose of imparting flexibility to polypropylene resin film, high density polyethylene, low density polyethylene, linear low density polyethylene, styrene-ethylene-butadiene-styrene copolymer, and styrene-ethylene-propylene-styrene copolymer A blend of styrene elastomer such as coalescence, olefin elastomer such as ethylene-propylene copolymer and ethylene-propylene-diene copolymer can also be used. Resins used for the adhesive layer of the masking film include ethylene-vinyl acetate copolymer resin (EVA), low density polyethylene, linear low density polyethylene, styrene-ethylene-butadiene-styrene copolymer, and styrene. Styrene elastomer such as ethylene-propylene-styrene copolymer, ethylene-propylene copolymer, olefin elastomer such as ethylene-propylene-diene copolymer, soft vinyl chloride resin, acrylonitrile-butadiene copolymer, acrylic Examples thereof include rubber and natural rubber. It is also possible to use a masking film in which these resin layers are a single layer or a laminate. As the masking film, a water-soluble or water-swellable resin such as polyvinyl alcohol resin, polyacrylic acid resin, or polyvinyl pyrrolidone resin may be used. When a water-soluble or water-swellable resin is used, the masking film can be removed at the same time in the water-washing / removing step of the water-soluble or water-swellable support after hydraulic transfer.

  The masking film may be attached in advance to the transparent resin film layer side of the thermoforming laminate sheet, and thermoformed together with the thermoforming laminate sheet to form a decorative sheet with a masking film. In addition, the decorative sheet can be cut according to the desired design shape of the transferred body and insert-molded as necessary. Or a masking film can also be affixed on the decoration sheet | seat after thermoforming the said laminated sheet for thermoforming. In this case, a masking film may be affixed on the decoration layer which provides a metallic design after insert molding, or it may be insert-molded after a masking film is affixed on a decoration sheet.

(Method of manufacturing transfer object decorative sheet)
The thermoforming laminated sheet obtained by the above method or the thermoforming laminated sheet with a masking film is thermoformed to obtain a decorative sheet. As a method of thermoforming the laminated sheet for thermoforming, a hot plate forming method, a vacuum forming method, an ultra-high pressure forming method, a pressure forming method, a pressure air forming method, a match forming method, a press forming method, a vacuum forming press forming method, It can be formed by an existing thermoforming method such as Further, if necessary, a straight method using a plug, a drape method, a plug assist method, an air slip method, a method, a snapback method and the like may be used in combination. As the heating method, either an indirect heating method such as radiant heat or dielectric heating, or a direct heating method in which heating is performed in contact with a hot plate or the like may be used. As the thermoforming method, it is preferable to use a match mold forming method or a compressed air vacuum forming method, which is high in mass productivity and easily obtains good mold reproducibility even at low temperature forming.

(Transfer to be transferred Decorative sheet manufacturing method Compressed air vacuum forming method)
The compressed air vacuum forming method is a forming method in which a male mold or a female mold is pressed against a sheet heated in a heating zone, and the sheet is shaped using compressed air and vacuum pressure. The molding conditions are not particularly limited, but when a far infrared heater is used, the heater temperature is 200 to 500 ° C., the indirect heating time is 2 to 30 seconds, and heating is performed until the sheet reaches a desired temperature. To do. The mold temperature needs to be determined while confirming the appearance and the degree of shrinkage of the resulting decorative sheet, but is preferably 20 to 80 ° C. and the cooling time by the mold is preferably 1 to 60 seconds. The molding pressure is preferably 0.1 to 1 MPa, but 0.3 to 0.7 MPa is more preferably used in terms of mold reproducibility and equipment investment. In the case of the ultra-high pressure molding method, molding is performed by applying a molding pressure of about 30 MPa, so that good mold reproducibility can be obtained even at low temperatures.

(Transfer material: decorative sheet manufacturing method, match mold forming method)
The match mold molding method is characterized in that a male mold and a female mold are matched and molded so as to sandwich a sheet heated in a heating zone. The mold used here is usually provided with a vacuum hole as an air escape path in the mold. However, vacuum suction may be supplementarily performed using this hole. Since the molding pressure can use the power of servo motor, hydraulic pressure, etc., the force is about 10 to 1000 times that of normal pressure forming, so that sufficient mold reproducibility can be obtained unless the sheet is torn. I can do it. Further, molding at a lower temperature is possible, and in match molding, it is possible to make a decorative sheet while maintaining the surface gloss having the metallic gloss ink of the thermoforming laminated sheet. Although there is no particular limitation on the molding conditions, when a far infrared heater is used, the heater temperature is 200 to 500 ° C., the indirect heating time is 2 to 30 seconds, and the sheet is heated until it reaches a desired temperature. . The mold temperature needs to be determined while confirming the appearance and the degree of shrinkage of the resulting decorative sheet, but is preferably 20 to 100 ° C. and the cooling time by the mold is preferably 10 to 5 minutes. Moreover, it is more preferable to cool the decorative sheet obtained after completion of molding with air or the like because deformation that easily occurs during mold release can be prevented.

(Method for producing a transfer object having a decorative layer for providing a metallic design)
After trimming the decorative sheet obtained by the above method or the decorative sheet with a masking film as necessary, it is mounted in an injection mold and molded by an insert molding method to obtain a transfer object. it can. The trimming method is not particularly limited, and examples thereof include a die cutting method, a laser cutting method, a water jet method, and a punching blade press method.

(Process for producing a transfer body having a decorative layer for providing a metallic design, insert molding)
The resin used for insert molding becomes the base material of the transfer target as it is. Therefore, it is preferable to select according to the compatibility with the thermoforming laminated sheet or the hydraulic transfer film to be used. Specifically, a resin of the same system as the supporting base resin layer of the thermoforming laminated sheet is preferable. For example, when the supporting base resin layer is ABS (acrylonitrile butadiene styrene) resin, the base material resin for injection is preferably ABS resin, but if the adhesion to the supporting base resin layer is sufficient, an ABS-based resin Polymer alloys such as PVC (polyvinyl chloride) / ABS resin, PA (polyamide) / ABS resin, PC (polycarbonate) / ABS resin, and PBT (polybutylene terephthalate) / ABS may be used. Similarly, if the adhesion is good, AAS (acrylonitrile / acrylic rubber / styrene) resin, AS (acrylonitrile / styrene) resin, AES (acrylonitrile / ethylene rubber / styrene) resin, MS ((meth) acrylic ester / styrene) It may be a different resin such as resin, PC resin, PMMA (polymethyl methacrylate) resin, PMMA / ABS / AS resin.

  When the support base resin layer is a polypropylene resin, the base material resin for injection is also preferably a polypropylene resin. From the viewpoint of adhesion to the support base resin layer of the laminated sheet, 40% of the injection resin is contained in the injection resin. It is preferable to contain polypropylene in an amount of not less than mass%. Other components may include a resin component that can be melt-mixed with polypropylene. Polypropylene resins and meltable resins include high-density polyethylene, low-density polyethylene, linear low-density polyethylene, styrene-ethylene-propylene-styrene copolymers, and styrene-based copolymers such as styrene-ethylene-propylene-styrene copolymers Examples thereof include olefin elastomers such as elastomers, ethylene-propylene copolymers, and ethylene-propylene-diene copolymers.

  In addition, an inorganic filler can be added to the injection resin in order to prevent deformation during or after molding. The inorganic filler is not particularly limited, and examples thereof include talc, calcium carbonate, clay, diatomaceous earth, mica, magnesium silicate, silica and the like. Furthermore, conventional additives may be added as long as the moldability is not inhibited. For example, plasticizers, light-resistant additives (ultraviolet absorbers, stabilizers, etc.), antioxidants, ozonization inhibitors, activators , Antistatic agents, lubricants, antifriction agents, surface conditioners (leveling agents, antifoaming agents, antiblocking agents, etc.), antifungal agents, antibacterial agents, dispersants, flame retardants and wake accelerators You may mix | blend additives, such as an agent. These additives may be used alone or in combination of two or more.

  Further, a colorant may be added to the injection resin in accordance with the color or pattern of the hydraulic transfer film to be used. Although the addition amount of a coloring agent changes with kinds of coloring agent and the target color tone, it is preferable that it is 30 mass parts or less with respect to 100 mass parts of injection resin, More preferably, it is 20 mass parts or less. The colorant to be used is not particularly limited, and conventional inorganic pigments, organic pigments and dyes used for coloring general thermoplastic resins can be used according to the intended design. For example, inorganic pigments such as titanium oxide, titanium yellow, iron oxide, complex oxide pigments, ultramarine, cobalt blue, chromium oxide, bismuth vanadate, carbon black, zinc oxide, calcium carbonate, barium sulfate, silica, talc; azo Pigments, phthalocyanine pigments, quinacridone pigments, dioxazine pigments, anthraquinone pigments, isoindolinone pigments, isoindoline pigments, perylene pigments, perinone pigments, quinophthalone pigments, thioindigo pigments and diketopyrrolo Organic pigments such as pyrrole pigments; metal complex pigments and the like. Moreover, it is preferable to use 1 type or 2 types mainly chosen from the group of an oil-soluble dye as a dye.

  The insert molding conditions are not particularly limited. The injection conditions and the mold temperature may be set according to the injection resin, but if the injection resin temperature or the mold temperature is too low, the supporting base resin layer and the injection resin However, if the injection resin temperature or the mold temperature is too high, the injection resin may wash away the supporting base resin layer near the gate. For this reason, for example, in the case of polypropylene resin, the filling temperature is preferably 180 to 270 ° C, and more preferably 190 to 260 ° C. In the case of ABS resin, 190-290 degreeC is preferable and 200-270 degreeC is more preferable. The mold temperature may be controlled by water cooling to about 100 ° C for both cavity side mold and core side mold in polypropylene resin and ABS resin insert molding, but warpage may occur depending on the shape of the transferred material after insert molding. In such a case, mold temperature control may be performed by providing a temperature difference between the cavity side mold and the core side mold. In addition, in order to warm the decorative sheet inserted in the mold to the mold temperature before filling with the injection resin, an injection delay time for holding the decorative sheet in the range of 1 to 100 seconds in the mold clamped may be set. good.

(Water pressure transfer method)
The method for producing a hydraulic transfer member of the present invention will be described. The method for producing a hydraulic transfer according to the present invention includes a support film comprising a water-soluble or water-swellable resin and a hydraulic transfer film having a transfer layer soluble in an organic solvent provided on the support film. A step 1 of activating the transfer layer in a state where the body film is floated on water, a step 2 of transferring the transfer layer to a transfer target, and a step 3 of removing the support film. The step 4 of removing the masking film is performed simultaneously with the step 3 or after the step 3 from the obtained hydraulic transfer body.

(Water pressure transfer method, step 1)
Step 1 refers to a hydraulic transfer film having a support film made of a water-soluble or water-swellable resin and a transfer layer soluble in an organic solvent provided on the support film, with the support film on the bottom. In this step, the transfer layer is activated while floating in water. Specifically, the hydraulic transfer film is floated in water in a water tank with the support film on the bottom, the transfer layer on the top, and the support film is dissolved or swollen with water. In this step, the transfer layer is activated by applying or spraying an activator to the transfer layer. The activation of the transfer layer may be performed before the film is floated on water.

(Water pressure transfer method, step 1 water)
The water in the water tank in the hydraulic transfer functions as a hydraulic medium that swells or dissolves the support film and also causes the hydraulic transfer film to adhere to the three-dimensional curved surface of the transfer target when transferring the transfer layer. Specifically, water such as tap water, distilled water and ion exchange water may be used, and depending on the support film used, inorganic salts such as boric acid and alcohols may be dissolved in water within 10%. But you can.

(Water pressure transfer method, step 1 activation)
The transfer layer of the hydraulic transfer film used in the present invention is activated and sufficiently solubilized by applying or spraying an organic solvent or an activator such as an active energy ray curable composition or a thermosetting composition. Or it becomes flexible. The activation mentioned here means that the transfer layer is solubilized without being completely dissolved by applying or dispersing the activator to the transfer layer, and flexibility is imparted to the transfer layer. It means improving the followability and adhesion to the transfer body. This activation may be performed to such an extent that when the transfer layer is transferred from the hydraulic transfer film to the transfer body, these transfer layers are softened and can sufficiently follow the three-dimensional curved surface of the transfer body.

(Hydraulic transfer method Step 1 Activator)
A known activator can be used. Specifically, an organic solvent that solubilizes the curable resin layer and the decorative layer and imparts flexibility, or a low-viscosity radically polymerizable composition can be used. Among these, it is preferable to use an organic solvent because it is easy to handle. Specifically, as the organic solvent, toluene, xylene, ethylbenzene, hexane, cyclohexane, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, propyl acetate, isobutyl acetate, 1-propanol, 2-propanol, 1-butanol, Examples include 2-butanol, ethyl cellosolve, cellosolve acetate, butyl cellosolve, carbitol, carbitol acetate, butyl carbitol acetate, sorbite acetate, and mixtures thereof. The low-viscosity radical polymerizable composition contains a photopolymerizable prepolymer, a photopolymerizable monomer, and a photopolymerization initiator as essential components, and known ones can be used. Moreover, you may add suitably with an organic solvent in order to adjust a viscosity.

  In order to improve the adhesion between the printing ink or paint and the molded product, this activator may contain some resin components. For example, adhesion may be increased by including 1 to 10% of an ink binder having a similar structure such as polyurethane, acrylic resin, or epoxy resin.

(Water pressure transfer method, step 2)
In step 2, the transfer layer is transferred to a transfer target. Specifically, while the transfer target is pressed against the transfer layer of the hydraulic transfer film, the transfer target and the hydraulic transfer film are submerged in water, and the transfer layer is brought into close contact with the transfer target by water pressure and transferred. .

(Water pressure transfer method, step 3)
Step 3 is a step of removing the support film from the transferred material after transfer. Specifically, the support film is removed from the transfer medium taken out of water and dried. The support film is removed from the transfer target by dissolving or peeling the support film with a water flow in the same manner as in the conventional hydraulic transfer method. It is preferable that the drying step is heat drying because drying can be performed in a short time and the blocking agent of the blocked isocyanate compound can be dissociated. The drying temperature at this time is preferably a temperature that does not exceed the heat resistance temperature of the base material so that the material to be transferred does not cause thermal deformation when the material to be transferred is a plastic having a low heat resistance temperature. In this case, it is preferable that the NCO dissociation temperature of the polymerizable compound (A) in the hydraulic transfer film to be used is designed to be in the range of 70 ° C. or higher and 130 ° C. or lower. When not heating at the time of a drying process, in order to dissociate a blocking agent, it is also possible to perform post-heating after light irradiation. Also in this case, it is preferable to carry out at a temperature not exceeding the heat-resistant temperature of the base material so as not to cause thermal deformation of the transferred body. For these, an oven or a drying furnace can be used.

(Water pressure transfer method, step 4)
At the same time as step 3 or after step 3, the masking film is removed. To remove the masking film, the boundary end face may be lifted and peeled off. When it is difficult to lift the boundary end face, an adhesive tape or the like may be attached to make a peeling end and then peeled off. When a water-soluble or water-swellable resin is used as the masking film, the masking film also dissolves or swells due to the water flow for removing the support film in step 3, so that the masking film is simultaneously removed from the transfer member surface in step 3. Can be removed.

  Also, between the step 3 for removing the support film and the step 4 for removing the masking film, or after the step 4 for removing the masking film, spray coating, brush coating, curtain coter, etc. In the transfer surface, a step 5 of forming a curable resin composition curable by active energy rays or heat may be included. In particular, spray coating can be suitably used because it can easily form a coating film having a good appearance with respect to various shapes. Specifically, a known surface protecting paint may be applied using a mechanical device such as a spray gun or a ricin gun. Since the curable resin used for the hydraulic transfer film having the curable resin layer in the present invention has sufficient adhesion to the ink layer, the curable resin can be diluted to an appropriate viscosity and used. However, in the case of the thermosetting resin in the present invention, from the viewpoint of the storage stability of the hydraulic transfer film, a curing agent such as a blocked isocyanate that is dissociated by heat as in the case of a blocked isocyanate to generate a reactive functional group is added. However, when spray coating or the like is performed, polyisocyanate having no protecting group may be used as a curing agent. After Step 5, when the masking film remains, the masking film is removed, and then the curable resin layer is cured by active energy rays or heat (Step 6).

  Or when the hydraulic transfer film to be used has a curable resin layer, after passing through the process 4 which removes a masking film, a curable resin layer is hardened with an active energy ray or a heat | fever (process 6).

  As the active energy ray used in the step 6, it is preferable to use visible light or ultraviolet light. In particular, ultraviolet rays are suitable. As the ultraviolet light source, sunlight, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, or the like is used. Moreover, as a heat source used at the said process 6, well-known heat sources, such as a hot air and a near infrared ray, are applicable.

  Hereinafter, the present invention will be described with reference to examples. Unless otherwise specified, “part” and “%” are based on mass. The measurement method and determination method used are described below.

(Production Examples 1 to 7 Comparative Production Example 1 Production Method of Hydraulic Transfer Film)
(Production Example 1 Production of Curable Resin A1)
60 parts (mass average molecular weight 890) of an average hexafunctional urethane acrylate (UA1) obtained by reacting 2 molar equivalents of pentaerythritol, 7 molar equivalents of hexamethylene diisocyanate and 6 molar equivalents of hydroxyethyl methacrylate at 60 ° C., manufactured by Rohm and Haas A curable resin A1 having a solid content of 42% was produced with 40 parts of acrylic resin paraloid A-11 (Tg 100 ° C., mass average molecular weight 125,000) and a mixed solvent of ethyl acetate and methyl ethyl ketone (mixing ratio 1/1).

(Production Example 2 Production of Curable Resin A2)
For 81 parts of acrylic polyol (a) (mass average molecular weight 25,000) obtained by copolymerizing hydroxyethyl methacrylate, methyl methacrylate, ethyl acrylate, butyl acrylate and styrene in a molar ratio of 20: 30: 15: 15: 20, 19 parts of a mixture of a hexamethylene diisocyanate phenol adduct having an isocyanate value 1.1 times equivalent to the hydroxyl value of the acrylic polyol and a trimer phenol adduct of hexamethylene diisocyanate was added to toluene and ethyl acetate (1/1). The curable resin A6 having a solid content of 35% was prepared by dissolving in the above mixed solvent.

(Production Example 3 Production of Film (B) B1 Having Decoration Layer)
As the peelable film, a 50 μm thick unstretched polypropylene film (hereinafter abbreviated as “PP film”) manufactured by Toyobo Co., Ltd. was used, and urethane ink (trade name: Univia A) was applied to the film with a gravure 4-color printer A decorative film (B) B1 was produced by printing a 3 μm wood grain pattern.

(Ink composition, black, brown, white)
Polyurethane (Polyurethane 2569 manufactured by Arakawa Chemical Co., Ltd.): 20 parts Pigment (black, brown, white): 10 parts Ethyl acetate / toluene (1/1): 60 parts Additives such as wax: 10 parts

(Production Example 4 Production Method of Hydraulic Transfer Film C1)
A film C1 for hydraulic transfer is manufactured by printing the same ink as in Production Example 3 on a 30 μm-thick PVA film made by Aicero Chemical Co., Ltd., which is a support film, using a gravure 4-color printing machine with a 3 μm thick wood grain pattern. did.

(Production Example 5 Production Method for Hydraulic Transfer Film C2)
Using a 30 μm thick PVA film manufactured by Aisero Chemical Co., Ltd., which is a support film, using a gravure 7-color printing machine, 3 plates of the curable resin A1 of Production Example 1 and 4 plates of the same ink as in Production Example 3 are used to form a solid. A hydraulic transfer film C2 was produced by printing a curable resin layer having a thickness of about 3 μm and a wood grain pattern (ink layer) having a thickness of 3 μm.

(Production Example 6 Production Method for Hydraulic Transfer Film C3)
The curable resin A1 of Production Example 1 is applied to a 30 μm thick PVA film manufactured by Aicero Chemical Co., Ltd., which is a support film, with a comma coater to a solid content film thickness of 20 μm, and then dried at 60 ° C. for 2 minutes. Thus, a film (A) was produced. The curable resin layer of this film (A) and the ink layer of the decorative film (B) B1 were faced and laminated at 60 ° C. The laminated film was wound up as it was to produce a hydraulic transfer film C3.

(Production Method 7 Production Method for Hydraulic Transfer Film C4)
A hydraulic transfer film C4 was produced in the same manner as in Example 3 except that A2 was used as the curable resin, and a paint in which an equivalent amount of blocked isocyanate was mixed was used.

(Comparative Production Example 1 Production Method of Hydraulic Transfer Film C5)
The film C5 for hydraulic transfer was manufactured by carrying out the metallic-tone printing of the high brightness silver solid of 3 micrometers in thickness with the gravure 3 color printer by the method similar to Example 1. FIG.
(Ink composition, high brightness silver)
Polyurethane (Polyurethane 2569 manufactured by Arakawa Chemical Co., Ltd.): 20 parts Pigment (high brightness silver): 10 parts Ethyl acetate / toluene (1/1): 60 parts Additives such as wax: 10 parts

(Production Examples 8 to 12: Method for producing transferred object)
(Masking film)
As the masking film, a surface protective film (trade name “EC700”, manufactured by Sumilon Co., Ltd.) having a thickness of 50 μm was used.

(Transparent resin film)
As the transparent resin film layer, a rubber-modified PMMA film (trade name “Technoloy S-001”, manufactured by Sumitomo Chemical Co., Ltd.) having a haze of 0.1% and a thickness of 125 μm was used.

(adhesive)
A two-component polyester urethane adhesive (a two-component mixed adhesive of “LX-630PX” and “KR-90” manufactured by Dainippon Ink and Chemicals, Inc.) is mixed at a ratio of 30: 1 and adhesive D is added. It was adjusted.

(Supporting base resin layer)
As a supporting base resin layer, ABS (Clarastic MTH-2) manufactured by Nippon A & L Co., Ltd. was introduced from an extruder hopper, extruded from a T die at a processing temperature of 240 ° C, and passed through a cast roll heated to 100 ° C. Then, winding and unstretched raw sheet were produced.

(Production Example 8 Method for producing metallic gloss ink)
(1) Aluminum thin film strip Nitrocellulose (HIG7) was dissolved in a mixed solvent of ethyl acetate: isopropyl alcohol = 6: 4 to obtain a 6% solution. The solution was applied onto a polyester film with a gravure plate having a screen line number of 175 lines / inch and a cell depth of 25 μm to form a release layer. After sufficiently drying, aluminum is vapor-deposited on the release layer to a thickness of 0.04 μm, and the same nitrocellulose solution as that used for the release layer is applied to the deposited film surface under the same conditions as in the release layer. The top coat layer was formed by coating.
After peeling the aluminum vapor-deposited film from the polyester film immersed in the mixed solvent of ethyl acetate: isopropyl alcohol = 6: 4, the aluminum vapor-deposited film was pulverized with a stirrer so as to have a size of about 150 μm, An aluminum thin film strip was prepared.

(2) Aluminum thin film strip slurry Aluminum thin film strip 10 parts Ethyl acetate 35 parts Methyl ethyl ketone 30 parts Isopropyl alcohol 30 parts The above components were mixed and stirred, and 5 parts of a nitrocellulose solution having the following composition was added.
Nitrocellulose (HIG 1/4) 25%
Ethyl acetate: isopropyl alcohol = 6: 4 mixed solvent 75%
While maintaining the temperature at 35 ° C. or lower, the above mixture was stirred using a turbo mixer until the size of the aluminum thin film pieces became 5 to 25 μm, thereby adjusting the aluminum thin film piece slurry (nonvolatile content 10%). did.

(Production Example 9 Method for producing surface protective layer and ink protective layer)
850 parts of butyl acetate and 1 part of perbutyl Z (trade name, manufactured by NOF Corporation, t-butyl peroxybenzoate) are added to a reaction vessel equipped with a temperature controller, a nitrogen introducing tube, a dropping device (2 units), and a stirring device. After charging and nitrogen substitution, the temperature was raised to 110 ° C. over 1.5 hours.
Separately, 660 parts of methyl methacrylate, 150 parts of t-butyl methacrylate and 190 parts of 2-hydroxyethyl methacrylate (hereinafter referred to as monomer solution), 200 parts of isobutyl acetate, and perbutyl O (trade name, manufactured by NOF Corporation) , T-butyl peroxy-2-ethylhexanoate) 9 parts, perbutyl Z (trade name, manufactured by NOF Corporation, t-butyl peroxybenzoate) 2 parts well stirred solution (hereinafter referred to as catalyst solution) Each was charged into a dropping device and immediately purged with nitrogen.
The above monomer solution and catalyst solution were dropped in a reaction vessel under a nitrogen atmosphere over 5 hours while monitoring the reaction temperature so as not to increase rapidly. As a result of continuing stirring for about 15 hours after completion of the dropping, a hydroxyl group-containing copolymer having a solid content of 60% was obtained. The weight average molecular weight of the obtained resin was 100,000, the hydroxyl value of the solid content was 79 KOHmg / g, and Tg was 95 ° C. The hydroxyl group-containing copolymer and the polyisocyanate compound “BURNOCK DN-981” (trade name, manufactured by Dainippon Ink & Chemicals, Inc., isocyanurate ring-containing polyisocyanate, number average molecular weight of about 1000, non-volatile content 75% (solvent: Ethyl acetate), 3 functional groups, and 13 to 14% NCO concentration) were blended and mixed at a solid content ratio of 1: 1 to prepare an ink protective layer solution.

  (Here, the weight average molecular weight is a polystyrene equivalent value of the GPC measurement result. In addition, the solid content was measured by taking 1 g of a sample on an aluminum dish and spreading it thinly and uniformly with toluene, followed by air drying and further at 108 ° C. It was dried for 1 hour in a hot air dryer and calculated from the weight after drying.The hydroxyl value was calculated as a KOH neutralized amount from the monomer charge composition, the polymer Tg was DSC, and the acid value was 0.05 mol · dm−. (Measured by titration with 3 potassium hydroxide-toluene solution.)

(Production Example 10 Method for Producing Laminate Sheet for Thermoforming)
A solution prepared for the ink protective layer was applied to the thermoplastic film layer using a microgravure coater so as to have a dry film thickness of 2 μm, and then subjected to an aging treatment at 40 ° C. for 3 days. Next, high gloss ink was applied to the ink protective layer using a micro gravure coater so that the dry film thickness was 1 μm. Next, a corona treatment is applied to the adhesive surface of the supporting base resin layer, coating is performed using a gravure coater so as to have a dry film thickness of 5 μm, and bonding with the metallic glossy ink layer is performed, followed by 3 at 40 ° C. Aging treatment was performed for a day.
Next, using a gravure coater, a masking film was laminated on the PMMA film side of the multilayer sheet.

(Manufacturing method 11 decorative sheet manufacturing method)
The laminated sheet for thermoforming obtained by the method for producing a laminated sheet for thermoforming is subjected to pressure vacuum forming at a mold temperature of 60 ° C. and a heater temperature of 300 ° C. using a PLAVAC vacuum forming machine manufactured by Sanwa Kogyo Co., Ltd. A decorative sheet was obtained.

(trimming)
The decorative sheet obtained by the decorative sheet manufacturing method was set on a Thomson blade and cut with a press machine, and trimming was performed so as to leave a convex portion as shown in FIG.

(Production Example 12 Production Method of Transferred Body Insert Molding)
Trimming the decorative sheet so that the injection resin is filled in the support base resin layer side against the injection mold having the same three-dimensional shape as that used in the decorative sheet manufacturing method. It was mounted and subjected to insert molding to obtain a transferred body having a decorative layer for providing a metallic design having a masking film on the outermost layer on a part of the transferred surface. As the resin for injection molding, ABS resin (trade name “Polylac PA-756”) manufactured by Kitami Jitsugyo Co., Ltd. was used. As the injection molding machine, Sumitomo Nestal C160 manufactured by Sumitomo Heavy Industries, Ltd. was used. The mold has a structure in which an injection resin having a thickness of 2.5 mm can be filled on the thermoplastic film side with respect to a three-dimensional thermoformed body.

(Comparative Production Example 2 Production Method of Transferred Body)
An injection-molded product was obtained by the same method as in Production Example 12 except that ABS resin (trade name “Polylac PA-727”) manufactured by Kitami Jitsugyo Co., Ltd. was used as the resin for injection molding. Next, the transferred product was obtained by subjecting this injection molded product to copper plating, nickel plating, and chromium plating sequentially by electroplating.

(Example 1 water pressure transfer)
Warm water at 28 ° C. was put in a water tank, and the water pressure transfer film C1 was floated on the water surface with the PVA side facing down. An activator (xylene: MIBK: butyl acetate: Solfit acetate, 5: 2: 2: 1) is sprayed at 20 g / m ² , and a masking film is provided on a part of the transfer surface as the outermost layer. An ABS transfer object having a decorative layer providing a metallic design, including a metallic glossy ink layer containing a piece and a binder resin, was inserted from the ink surface toward the water and hydraulically transferred. After the PVA was washed away with water and dried at 80 ° C. for 30 minutes, the masking film was removed, and the coating material in which the trifunctional isocyanate was mixed with the curable resin of Production Example 2 was spray-coated, and the solid content was applied to the entire transfer body. A coating film having a thickness of about 20 μm was formed and heated at 80 ° C. for 30 minutes to dry the activator and cure the thermosetting resin layer. As a result, a hydraulic transfer body having a wood grain decorative layer on the portion not subjected to the metal design was obtained.

(Example 2 hydraulic transfer)
Hot water of 28 ° C. was put in a water tank, and the hydraulic transfer film C2 was floated on the water surface with the PVA side facing down. An activator (xylene: MIBK: butyl acetate: isopropanol, 5: 2: 2: 1) is sprayed at 40 g / m ² , and a masking film is provided on a part of the transferred surface as the outermost layer, An ABS transfer object having a decorative layer providing a metallic design, including a metallic glossy ink layer containing a binder resin, was inserted from the ink surface toward the water and hydraulically transferred. After PVA was washed away with water, it was dried at 80 ° C. for 30 minutes. Subsequently, after removing the masking film, UV irradiation was performed at an irradiation amount of 1200 mJ / cm ² to completely cure the curable resin phase. As a result, a hydraulic transfer body having a wood grain decorative layer on the portion not subjected to the metal design was obtained.

(Example 3 water pressure transfer)
Hot water of 28 ° C. was put in a water tank, and the peelable film of the hydraulic transfer film C3 was peeled off, and then the hydraulic transfer film C3 was floated on the water surface with the PVA side down. An activator (xylene: MIBK: butyl acetate: isopropanol, 5: 2: 2: 1) is sprayed at 40 g / m ² , and a masking film is provided on a part of the transferred surface as the outermost layer, An ABS transfer object having a decorative layer providing a metallic design, including a metallic glossy ink layer containing a binder resin, was inserted from the ink surface toward the water and hydraulically transferred. After PVA was washed away with water, it was dried at 80 ° C. for 30 minutes. Subsequently, after removing the masking film, UV irradiation was performed at an irradiation amount of 1200 mJ / cm ² to completely cure the curable resin phase. As a result, a hydraulic transfer body having a wood grain decorative layer on the portion not subjected to the metal design was obtained.

(Example 4 water pressure transfer)
Hot water of 28 ° C. was put in a water tank, and the PVA side of the hydraulic transfer film C4 from which the peelable film was peeled was floated on the water surface. An activator (xylene: MIBK: butyl acetate: isopropanol, 5: 2: 2: 1) is sprayed at 40 g / m ² , and a masking film is provided on a part of the transferred surface as the outermost layer, An ABS transfer object having a decorative layer providing a metallic design, including a metallic glossy ink layer containing a binder resin, was inserted from the ink surface toward the water and hydraulically transferred. PVA was removed by washing with water. Subsequently, after removing the masking film, heating was performed at 80 ° C. for 60 minutes to dry the activator and cure the thermosetting resin layer. As a result, a hydraulic transfer body having a wood grain decorative layer on the portion not subjected to the metal design was obtained.

(Comparative Example 1)
Hot water of 28 ° C. was put in a water tank, and the water pressure transfer film C5 was floated on the water surface with the water pressure transfer film C5 facing downward. An activator (xylene: MIBK: butyl acetate: Solfit acetate, 5: 2: 2: 1) is sprayed at 20 g / m ^2, and an ABS transfer object (having no metal design) is sprayed from the ink surface into water. It was inserted toward the water and was hydraulically transferred. After the PVA was washed away with water and dried at 80 ° C. for 30 minutes, the masking film was removed, and the coating material in which the trifunctional isocyanate was mixed with the curable resin of Production Example 2 was spray-coated, and the solid content was applied to the entire transfer body. A coating film having a thickness of about 20 μm was formed and heated at 80 ° C. for 30 minutes to dry the activator and cure the thermosetting resin layer. Although a metallic ink layer was transferred, only a metallic water pressure transfer body with low brightness was obtained.

(Comparative Example 2)
A metal hydrostatic transfer body was obtained in the same manner as in Example 2 except that the transfer body in Example 2 was changed to the transfer body obtained in Comparative Production Example 2. Since the metal portion of the transferred body obtained in Comparative Production Example 2 directly becomes the transferred surface, the obtained hydraulic transfer body has an appearance defect that the transfer pattern is missing. Easily peeled off.

The results of the present invention are shown in Table 3.

Here, the surface gloss of the metallic design was determined by a 20-degree gloss measurement method with an incident angle of 20 degrees and a light-receiving angle of 20 degrees in accordance with JIS-K7105. In addition, Nippon Denshoku VGS-300A was used for the gloss meter.
The cross cut test was in accordance with JIS K5400 cross cut tape method.

  The hydraulic transfer body obtained by the production method of the present invention has a design similar to that of a metal-like design or a complicated design combining a metal-like luster pattern and a general-purpose printed pattern. Of course, it can be widely used for molded products having curved surfaces and requiring design. For example, home appliances such as TVs, videos, air conditioners, radio cassettes, mobile phones, refrigerators; OA equipment such as personal computers, fax machines and printers; housing parts of household products such as fan heaters and cameras; tables, chests, pillars, etc. Furniture parts; Building parts such as bathtubs, system kitchens, doors and window frames; Miscellaneous goods such as calculators and electronic notebooks; Car interior panels, automobile and motorcycle skins, wheel caps, ski carriers, automobile carrier bags, etc. Exterior items; sports equipment such as golf clubs, skis, snowboards, helmets, goggles; three-dimensional images for advertising, signboards, monuments, etc.

It is the figure which showed the manufacturing method of this invention typically. It is a schematic diagram of the to-be-transferred body which provided the masking film of the same shape as the decoration layer which provides the metal design which covers all the decoration layers which provide the metal design used by this invention. It is a schematic diagram of the to-be-transferred body which provided the masking film so that a part of decoration layer which provides the metallic design used in this invention may be covered.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Molded body based on resin 2 Decorative layer providing metal design 3 Masking film 4 Transfer object 5 Hydraulic transfer film 6 Water tank

Claims (8)

A hydraulic transfer film having a support film made of a water-soluble or water-swellable resin and a transfer layer soluble in an organic solvent provided on the support film was floated on water with the support film down. A method for producing a hydraulic transfer body, comprising: a step 1 for activating the transfer layer in a state; a step 2 for transferring the transfer layer to a transfer target; and a step 3 for removing the support film. The transferred body has a decorative layer providing a metallic design covered with a transparent resin layer on a part of the transferred surface, and a resin having a masking film attached to a part or all of the outermost surface of the decorative layer. A molded body as a base material,
A method for producing a hydraulic transfer body, comprising the step 3 of removing the masking film in the step 3 or after the step 3. The manufacturing method of the hydraulic transfer body of Claim 1 with which the decoration layer which provides the said metallic design has a metallic gloss ink layer containing a metal thin film strip and binder resin. The transferred body is a molded body having a three-dimensional shape obtained by an insert molding method, and a decorative sheet to be mounted in a mold at the time of insert molding is a transparent resin film layer, a metallic glossy ink layer, and a supporting substrate. The hydraulic transfer body according to claim 1, which is a decorative sheet obtained by thermoforming a laminated sheet obtained by laminating a masking film on the thermoplastic resin film layer of a laminated sheet for thermoforming laminated with a resin layer in this order. Production method. Between the step 3 for removing the support film and the step 4 for removing the masking film, there is a step 5 of forming a curable resin composition curable by active energy rays or heat on the transfer surface, The method for producing a hydraulic transfer body according to claim 1, further comprising a step 6 of curing the curable resin layer by active energy rays or heat after the step 4. After passing through the step 4 for removing the masking film, a step 5 for forming a curable resin layer curable with active energy rays or heat on the transfer surface, and a step 6 for curing the curable resin layer with active energy rays or heat. The method for producing a hydraulic transfer member according to claim 1, comprising: The transfer layer of the hydraulic transfer film is a transfer layer having a curable resin layer and a decorative layer that can be cured by active energy rays or heat, and after passing through the step 4 of removing the masking film, The manufacturing method of the hydraulic transfer body of Claim 1 which has the process 6 which hardens a curable resin layer. The method for producing a hydraulic transfer member according to claim 1, wherein the masking film is a water-soluble or water-swellable resin. The hydraulic transfer body obtained by the manufacturing method in any one of Claims 1-7.

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