JP2007168377A - Molding method of laminated sheet for thermoforming - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a molding method which enables the manufacture of a molded product having a three-dimensional shape and a concave-convex pattern on the surface. <P>SOLUTION: The laminated sheet for thermoforming is thermoformed comprising: a thermoplastic film layer; an adhesive layer; and a supporting substrate layer whose surface of the side contacting the adhesive layer is smooth and which keeps opposite surface of the side a concave-convex pattern transferred by an embossing roll, laminated in this order. When the thermoforming of the sheet is carried out to the three-dimensional shape using a usual smooth mold, the molded product in which the concave-convex pattern formed on the external surface (rear face) of the side of the supporting substrate layer of the laminated sheet for thermoforming is embossed on the external surface (front face) of the side of the thermoplastic film layer and the concave-convex pattern attached to the supporting substrate layer exists clearly on the side of the thermoplastic film layer can be manufactured. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a method for forming a laminated sheet for thermoforming, which can produce a molded product having a three-dimensional shape and an uneven pattern on the surface.

  Conventionally, as a secondary processed product of a sheet provided with a concavo-convex pattern using an embossing roll, a stationery file, a decorative board, and the like can be cited, but these are two-dimensional molded products having a beautiful design. On the other hand, there is a technology that vacuum-molds a sheet using embossing rolls on parts such as automobile interior materials, especially dashboards, into a three-dimensional shape, but there has never been a beautiful product with a high gloss design. It was.

In addition, there is a method of imparting a three-dimensional shape by providing irregularities on the surface of a mold (see, for example, Patent Document 1). However, even when molding a molded product with the same three-dimensional shape, if the concavo-convex pattern (for example, wood grain, leather texture, etc.) is different, prepare separate molds and attach the desired concavo-convex pattern to each mold. It is necessary and uneconomical. Many methods have been reported for incorporating a curable resin into a sheet to produce irregularities, but this is also expensive and uneconomical.
JP-A-5-301243

  The subject of this invention is providing the shaping | molding method of the laminated sheet for thermoforming which can manufacture the molded article which has a three-dimensional shape and an uneven | corrugated pattern on the surface.

  The method for forming a laminated sheet for thermoforming according to the present invention is such that the thermoplastic film layer, the adhesive layer, and the surface in contact with the adhesive layer are smooth, and an uneven pattern is transferred to the opposite surface by an embossing roll. The laminated sheet for thermoforming laminated with the support substrate layer thus formed is thermoformed.

According to the present invention, when a sheet is thermoformed into a three-dimensional shape using a normal smooth mold, a molded product in which the uneven pattern attached to the support base material layer clearly exists on the thermoplastic film layer side is obtained. Can be manufactured. As a result, a molded product having a three-dimensional shape and a concavo-convex pattern on the surface can be formed, and a molded product excellent in appearance and design can be obtained by combining the visual effect of the shape and the concavo-convex.
In addition, when molding molded products with the same three-dimensional shape and different concavo-convex patterns, by changing the thermoforming laminated sheet to one with the desired concavo-convex pattern, a variety of common molds can be used. It is possible to cope with the uneven pattern of this, and is excellent in economic efficiency and productivity.
The laminated sheet for thermoforming having a concavo-convex pattern used in the present invention can be easily provided with a concavo-convex pattern with an embossing roll, can be produced at low cost, and easily corresponds to different three-dimensional shapes by changing the mold. Because it is possible, it is excellent in economic efficiency.

Hereinafter, the molding method of the laminated sheet for thermoforming according to the present invention will be described in detail.
In the method for forming a laminated sheet for thermoforming according to the present invention, at least the thermoplastic film layer (A), the adhesive layer (D), and the surface in contact with the adhesive layer (D) are smooth. The opposite surface has a support base material layer (C) having a concavo-convex pattern transferred by an embossing roll, and a thermoforming laminated sheet in which these layers are laminated in this order is used. In the present invention, it is preferable to use a laminated sheet for thermoforming in which at least a decorative layer (B) is laminated between the thermoplastic film layer (A) and the adhesive layer (D).

[Thermoplastic film layer (A)]
The thermoplastic film layer (A) used in the laminated sheet for thermoforming in the present invention is a thermoplastic resin layer that has spreadability by heating. The thermoplastic film layer (A) is preferably a transparent or translucent single layer or multilayer film, and may contain a colorant.
Specifically, in order to perform thermoforming using a mold, a film mainly composed of a thermoplastic resin having a softening point in the range of 30 to 300 ° C is preferable, and a more preferable softening temperature is 50 to 250 ° C. . 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, silicon-acrylic resin, ionomer, polystyrene, Polyurethanes such as polyurethane, polyacrylonitrile, acrylonitrile-styrene resin, methyl methacrylate-styrene resin, nylon, ethylene-vinyl acetate resin, ethylene-acrylic acid resin, ethylene-ethyl acrylate resin, ethylene-vinyl alcohol resin, polychlorinated Chlorine resins such as vinyl and polyvinylidene chloride, fluorine resins such as polyvinyl fluoride and polyvinylidene fluoride, polycarbonate resins, Jo polyolefin resin, modified polyphenylene ether resins, methylpentene resins, cellulose resins are preferably used.

Among these thermoplastic resins, a film mainly composed of polyvinylidene fluoride, a polycarbonate resin, or an acrylic resin is preferable from the viewpoint of integral molding possibility and weather resistance. In addition, since the thermoformability and the sharpness of the decorative layer (B) are excellent, the film mainly contains one or more selected from the group of acrylic resins, polyester resins, polycarbonate resins, and cyclic polyolefin resins. Is preferred.
In addition, two or more of the exemplified resins may be mixed or multilayered as long as the transparency of the film is not impaired.
The thickness of the thermoplastic film layer (A) is not particularly limited, but the coating property when the decorative protective layer (described later) and the decorative layer (B) are spreading layers such as ink, and thermoformability are good. Therefore, the range of 30 to 2000 μm is preferable, and more preferably 50 to 500 μm.
The thermoplastic film layer (A) may also contain a colorant. Alternatively, additives such as a plasticizer, an antioxidant, an ultraviolet absorber, an antistatic agent, a flame retardant, and a lubricant may be blended as long as the impact strength and moldability are not impaired. Two or more types may be used in combination.

  In addition, for the purpose of improving impact resistance, the various resins exemplified above used as the thermoplastic film layer (A) may be modified with rubber within a range that does not impair transparency. There are no particular restrictions on the method of making a rubber-modified product, but a method in which a rubber component monomer such as butadiene is added and copolymerized at the time of polymerization of various resins, and the resin and synthetic rubber or thermoplastic elastomer are heat-melt blended. A method is mentioned. Further, the thermoplastic film layer (A) may contain various additives commonly used for film applications such as antioxidants, ultraviolet absorbers, lubricants and the like within a range not impairing transparency. Furthermore, from the viewpoint of designability, a colorant such as a pigment or a dye can be contained, and the transparency can be intentionally lowered. The method for producing the thermoplastic resin film is not particularly limited, and may be formed into a film by a conventional method. Further, the thermoplastic resin film may be stretched in a uniaxial direction or a biaxial direction within a range that does not impair the extensibility during thermoforming. good.

[Decoration layer (B)]
In the present invention, a decoration layer (B) is provided between the thermoplastic film layer (A) and the adhesive layer (D), and the decoration (metal tone, color, etc.) by the decoration layer (B) is passed through the thermoplastic film layer (A). ) Is preferably visible.
A decorative layer (B) that is an intermediate layer of the laminated sheet for thermoforming, in order to allow the thermoplastic film layer (A) side to be satisfactorily expressed by thermoforming a sheet having a concavo-convex pattern on the support base material layer (C) side. ) Is preferably composed of an ink layer containing a binder resin. A preferred example of the ink layer is an ink layer (hereinafter referred to as a foil ink layer) containing a metal thin film strip and a binder resin and having a metallic luster. In addition, metallic ink containing metal powder and binder resin, and pigment ink containing pigment and binder resin are also suitable. Moreover, it is good also considering what laminated | stacked the foil ink layer and the other ink layer as a decoration layer (B). A metal vapor deposition layer can be used as a decoration layer (B). However, it has poor expandability and stretchability, so it is not suitable for deep drawing forming with high expansion.

(Foil ink layer)
When a decorative layer (B) is formed as a foil ink layer using a metallic gloss ink (hereinafter referred to as foil ink) containing metal thin film strips, a molded product having a metallic gloss can be obtained. . In such a decorative layer (B), if the film thickness of the foil ink layer is too thin, the concealability tends to be inferior and the design properties tend to be impaired. If it is too thick, the orientation of the metal pieces is particularly affected when foil ink is used. May be disturbed. For this reason, as a film thickness of a foil ink layer, 5 micrometers or less are preferable, 0.05-5 micrometers is more preferable, Especially preferably, it is 0.5-3 micrometers.

(Foil ink)
The foil ink is an ink having a mirror-like metallic luster formed by dispersing metal thin film strips in a binder resin. The content of the metal thin film strip with respect to the nonvolatile content in the ink is preferably in the range of 3 to 60% by mass. Foil inks using thin metal strips can be obtained with metallic inks using conventional metal powder as a result of the thin metal strips being oriented parallel to the surface of the object when the ink is printed or applied. A high-brightness mirror-like metallic luster is obtained. In the molding method of the present invention, it is possible to realize a deep-drawn molded product having both a metallic luster and a concavo-convex pattern by thermoforming using the laminated sheet having the high brightness ink layer.

(Metal thin film strips in foil ink)
The metal of the metal thin film strip used for the foil ink is not particularly limited. For example, aluminum (Al), gold (Au), platinum (Pt), silver (Ag), copper (Cu), brass (Cu— Zn), titanium (Ti), chromium (Cr), nickel (Ni), indium (In), molybdenum (Mo), tungsten (W), palladium (Pd), iridium (Ir), silicon (Si), tantalum ( Ta), nickel chromium (Ni—Cr), stainless steel (SUS), chromium copper (Cr—Cu), aluminum silicon (Al—Si), and the like. As a method for forming the metal into a thin film, vapor deposition is performed in the case of a metal having a low melting point such as aluminum, and foil is formed in the case of a malleable metal such as aluminum, gold, silver, or copper, and the melting point is high and the malleability is poor. In the case of a metal, sputtering etc. can be mentioned. Especially, the metal thin film strip obtained from the vapor deposition metal thin film is used preferably.

  The thickness of the metal thin film is preferably 0.01 to 0.1 μm, more preferably 0.02 to 0.08 μm. The size in the surface direction of the thin metal thin film dispersed in the ink is preferably 5 to 25 μm, more preferably 10 to 15 μm. When the size of the metal thin film strip is less than 5 μm, the brightness of the foil ink coating film decreases, and when the ink is printed or applied by the gravure method or the screen printing method, the plate is clogged. Cause.

  Hereinafter, a method for producing a metal thin film strip will be described by way of an example in which a particularly preferable vapor deposition method is used. A polyolefin film, a polyester film, etc. can be used for the support body film which vapor-deposits a metal. First, a release layer is provided on the support film by coating or the like, and then a metal is deposited on the release layer to have a predetermined thickness. A top coat layer is applied to the surface of the deposited film to prevent oxidation. As the coating agent for forming the release layer and the topcoat layer, the same one can be used, or different ones can be used.

  Resin used for the said peeling layer or the said topcoat layer is not specifically limited. Specific examples include cellulose derivatives such as nitrocellulose, acrylic resins, vinyl resins, polyamides, polyesters, ethylene-vinyl alcohol (EVA) resins, chlorinated polyethylene, chlorinated EVA resins, petroleum resins, and the like. Can do. Solvents used for the release layer or topcoat layer include aromatic hydrocarbons such as toluene and xylene; aliphatic or alicyclic hydrocarbons such as n-hexane and cyclohexane; esters such as ethyl acetate and propyl acetate; Alcohols such as methanol, ethanol and isopropyl alcohol; ketones such as acetone and methyl ethyl ketone; alkylene glycol monoalkyl ethers such as ethylene glycol monoethyl ether and propylene glycol monomethyl ether are preferably used.

  The metal vapor deposition film is immersed in a solvent that dissolves the release layer and the top coat layer and stirred to separate the metal vapor deposition film. Further, the peeled metal vapor-deposited film is stirred in a solvent to form a metal thin film strip having a size in the plane direction of about 5 to 25 μm, filtered and dried. The solvent used for peeling is not particularly limited as long as it dissolves the peeling layer and the topcoat layer. Also when a metal thin film is produced by sputtering, it can be made into a metal thin film strip by the same method as described above. When using a metal foil, it may be immersed in a solvent and pulverized to a predetermined size with a stirrer.

  The metal thin film strip is preferably surface-treated in order to enhance dispersibility in the ink. Examples of the surface treatment agent include organic fatty acids such as stearic acid, oleic acid, and palmitic acid; isocyanates such as methylsilyl isocyanate; and cellulose derivatives such as nitrocellulose, cellulose acetate propionate, cellulose acetate butyrate, and ethyl cellulose. It is made to adsorb | suck to the surface of a metal thin film strip by a well-known and usual method.

(Binder resin in foil ink)
As the binder resin used for the foil ink, those conventionally used for conventional gravure ink, flexo ink, screen ink, paint, and the like can be used. Specific examples include acrylic resins for paints, vinyl chloride resins, vinylidene chloride resins, vinyl chloride-vinyl acetate resins, ethylene-vinyl acetate resins, polyolefin resins, chlorinated olefin resins, ethylene-acrylic resins and the like; or A polyurethane resin for coating, a polyamide resin, a urea resin, an epoxy resin, a polyester resin, a petroleum resin, a cellulose derivative resin and the like are preferably used. Further, those obtained by chemically bonding polar groups such as carboxylic acid group, phosphoric acid group, sulfonic acid group, amino group, quaternary ammonium base to these resins may be used or used in combination.

(Additive in foil ink)
If necessary, the foil ink has no defoaming, settling prevention, pigment dispersion, fluidity modification, blocking prevention, antistatic, antioxidation, light stability, as long as it does not impair the design and spreadability. Various additives used in conventional gravure inks, flexographic inks, screen inks, paints, etc. may be added for the purpose of ultraviolet absorption, internal crosslinking, and the like. Examples of such additives include coloring pigments, dyes, waxes, plasticizers, leveling agents, surfactants, dispersants, antifoaming agents, chelating agents, polyisocyanates, and the like.

(Solvent in foil ink)
As the solvent used in the foil ink, a known and commonly used solvent used in conventional gravure ink, flexo ink, screen ink, paint or the like can be used. Specifically, aromatic hydrocarbons such as toluene and xylene; aliphatic or alicyclic hydrocarbons such as n-hexane and cyclohexane; esters such as ethyl acetate and propyl acetate; methanol, ethanol and isopropyl alcohol Examples include alcohols; ketones such as acetone and methyl ethyl ketone; alkylene glycol alkyl ethers such as ethylene glycol monoethyl ether and propylene glycol monomethyl ether.

(Foil ink preparation method)
Generally, in order to stably disperse the ink blending raw material, the pigment and other additives are finely divided to submicron by kneading using a roll mill, ball mill, bead mill, or sand mill. However, in the above-described foil ink, the metal thin film strip to be blended for expressing the metallic luster is preferably 5 to 25 μm in size, and when the kneaded meat is formed, the metal thin film strip is finely divided, There is a risk that the metallic luster is extremely lowered. Therefore, when preparing foil ink, it is desirable not to perform kneading, but to simply mix the above-mentioned blending raw materials into an ink. For this purpose, for the purpose of improving dispersibility, it is preferable to surface-treat the metal thin film strip as described above.

(Ink layer printing or coating method)
The printing method of the foil ink layer, other ink layers, and the adhesive of the laminated sheet for thermoforming used in the present invention is a printing method such as gravure printing, flexographic printing, screen printing, etc .; gravure coater, gravure Coating methods such as reverse coater, flexo coater, blanket coater, roll coater, knife coater, air knife coater, kiss touch coater, kiss touch reverse coater, comma coater, comma reverse coater, and micro reverse coater can be used. If the film thickness of the ink is too thin, the concealability tends to be inferior and the design property tends to be impaired. If it is too thick, the orientation of the metal thin film strips tends to be uneven. For this reason, as a film thickness of a foil ink layer, 5 micrometers or less are preferable, 0.05-5 micrometers is more preferable, Especially preferably, it is 0.5-3 micrometers. The same applies to the case where another ink layer is laminated on the foil ink layer. The thickness of the other ink layer is preferably 5 μm or less, more preferably 0.05 to 5 μm, and particularly preferably 0.5 to 5 μm. 3 μm.
For the purpose of controlling the adhesion between the thermoplastic film layer (A) and the decorative layer (B), the surface of the thermoplastic film layer (A) may be subjected to a surface treatment such as corona treatment or primer coating. .

(Other ink layers)
When an ink layer such as metallic ink or pigment ink is provided as the decorative layer (B), the ink component used is not particularly limited. As the binder resin, those usually used in conventional gravure ink, flexo ink, screen ink, paint, or the like can be used.

[Supporting substrate layer (C)]
As the support base material layer (C) used in the present invention, since the sheet is thermoformed (match mold forming, vacuum forming, pressure forming, etc.) using a mold, the softening temperature is in the range of 30 to 300 ° C. A film mainly composed of a certain thermoplastic resin is preferable, and a more preferable softening temperature is 50 to 250 ° C.
Examples of the thermoplastic resin include acrylonitrile / butadiene / styrene (ABS) resin, acrylonitrile / acrylic rubber / styrene (AAS) resin, acrylonitrile / ethylene rubber / styrene (AES) resin, (meth) acrylic ester / styrene. (MS) resin, styrene / butadiene / styrene (SBS) resin, styrene / isoprene / butadiene / styrene (SIBS) resin, polyethylene (PE) resin, polypropylene (PP) resin, polyvinyl chloride (PVC) resin, etc. General-purpose resins, olefin elastomers (TPO), polyvinyl chloride elastomers (TPVC), styrene elastomers (SBC), urethane elastomers (TPU), polyester elastomers (TPEE), polyamide elastomers It can be used Sutoma (TPAE) a thermoplastic elastomer (TPE) such as. Further, two or more kinds of the exemplified resins may be mixed or multilayered. Among these, since the forming property is excellent even in a molded body having a complicated shape typified by automobile exterior parts, polypropylene resins, polyethylene resins, blends thereof, AAS resins, ABS resins, etc. More preferably used. These resins may contain rubber modifiers such as ethylene propylene rubber (EPR), SBS, SIBS, styrene / ethylene / butadiene / styrene (SEBS) for the purpose of improving impact strength and the like. . The thickness of the support base material layer (C) is not particularly limited, but is preferably, for example, 10 μm to 4000 μm, more preferably 50 to 1000 μm, and still more preferably 100 to 500 μm because it can give a clear texture pattern.

(Inorganic filler in support substrate layer (C))
The laminated sheet for thermoforming becomes a three-dimensional shaped body by thermoforming. At this time, if the molding shrinkage of the thermoplastic resin used for the supporting base material layer (C) and the thermoplastic film layer (A) is different, the molded body is deformed and it is difficult to maintain a good shape. In this case, when an inorganic filler is added to the resin of the support base material layer (C), the molding shrinkage can be finely controlled, and the support base material layer (C) and the thermoplastic film layer (A) are heated. Since the difference in molding shrinkage of the plastic resin can be reduced, deformation during and after molding can be prevented. The kind of inorganic filler that can be used in the present invention is not particularly limited, and examples thereof include talc, calcium carbonate, clay, diatomaceous earth, mica, magnesium silicate, and silica.

  The addition amount of the inorganic filler in the support base material layer (C) is 5 to 60% by mass in terms of the mass percentage with respect to the resin in the support base material layer (C) from the viewpoint of the balance between molding processability and molding shrinkage. preferable. The particle size of the inorganic filler is not particularly limited, but if the particle size is too large, irregularities occur on the surface of the support base material layer (C), and in the case of a decorative sheet having a decorative layer (B), the decorative sharpness is impaired. There is a risk of being. For this reason, since the support base material layer (C) which is the foundation | substrate of a decoration layer (B) requires smoothness, the average particle diameter of the inorganic filler added to a support base material layer (C) is 4 micrometers or less preferably More preferably, it is 2 μm or less.

(Colorant in support base material layer (C))
It is preferable to add a colorant to the support base material layer (C) because the concealability of the base color of the molded article is improved. The colorant used here is not particularly limited, and customary inorganic pigments, organic pigments, dyes and the like used for coloring general thermoplastic resins can be used in accordance with 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, diketopyrrolo Organic pigments such as pyrrole pigments; metal complex pigments and the like. Moreover, as a dye, it is preferable to use 1 type, or 2 or more types mainly selected from the group of oil-soluble dyes.

  The amount of the colorant added to the support base layer (C) varies depending on the type of the colorant, the thickness and color tone of the target thermoforming sheet, etc., but ensures the concealment of the hue and background color, And in order to maintain impact strength, the range of 0.1-20 mass% is preferable as a mass percentage with respect to resin which comprises a support base material layer (C), More preferably, it is the range of 0.5-15 mass%. It is. When the addition amount of the colorant exceeds 20% by mass with respect to the resin, the impact strength decreases, and when the addition amount of the colorant is less than 0.1% by mass, the hue and the background color are not sufficiently concealed. There is a tendency.

(Other additives in the supporting substrate layer (C))
Furthermore, additives such as a plasticizer, an antioxidant, an ultraviolet absorber, an antistatic agent, a flame retardant, and a lubricant are added to the support base layer (C) as long as the impact strength and moldability are not impaired. These additives may be used alone or in combination of two or more.

(Formation of uneven surface of support base material layer (C))
As the support substrate layer (C), a film having a smooth surface on one side and a concavo-convex surface provided with a concavo-convex pattern on the opposite surface is used. The concavo-convex pattern can be easily imparted by embossing one side of the high-temperature support base material layer (C) taken from the extrusion die with an embossing roll. The type of uneven pattern is not particularly limited. For example, hairline, wood grain, leather grain (leather-like pattern), carbon pattern, stone grain, rock grain, sand grain, marble tone, fiber Tones, satin, line texture, geometric patterns, letters, pictograms, various figures, etc.

[Adhesive layer (D)]
The adhesive layer (D) used in the present invention is bonded to the thermoplastic film layer (A) and the support base material layer (C) having an uneven pattern on one side. Between the thermoplastic film layer (A) and the adhesive layer (D), the above-described decorative layer (B) and other ink layers may be provided.
In the present invention, the surface of the supporting base material layer (C) having an uneven pattern (uneven surface) and the direction of the smooth surface are such that the smooth surface is in contact with the adhesive layer (D) and the uneven surface is the adhesive layer (D). The direction is the opposite side of. If an adhesive is applied to the concavo-convex surface of the support base layer (C), the adhesive of the adhesive layer (D) fills the concavo-convex, and uneven thickness of the adhesive occurs.
In this invention, the thickness nonuniformity of an adhesive bond layer (D) can be suppressed by applying an adhesive agent to the smooth surface without an unevenness | corrugation of a support base material layer (C). Moreover, since the uneven surface of the support base material layer (C) is exposed to the outer surface (back surface) of the thermoforming laminated sheet, the thickness of the entire laminated sheet has a thickness variation based on the uneven pattern of the uneven surface. Become. As a result, when the molding laminated sheet having a concavo-convex pattern on one side of the support base material layer (C) of the present invention is thermoformed with a mold having a smooth surface, the design surface side after molding (thermoplastic film layer (A It is possible to develop a concavo-convex pattern visible on the side).

  The adhesive constituting the adhesive layer (D) is a conventional phenol resin adhesive, resorcinol resin adhesive, phenol-resorcinol resin adhesive, epoxy resin adhesive, urea resin adhesive, polyurethane adhesive. Adhesives, thermosetting resin adhesives such as polyaromatic adhesives; reactive adhesives using ethylene-unsaturated carboxylic acid copolymers; vinyl acetate resins, acrylic resins, ethylene vinyl acetate resins, polyvinyl alcohol , Polyvinyl acetal, vinyl chloride resin, nylon, cyanoacrylate resin and other thermoplastic resin adhesives; chloroprene adhesives, nitrile rubber adhesives, SBR adhesives, rubber adhesives such as natural rubber adhesives, etc. Is mentioned. In particular, an acrylic urethane-based adhesive is preferable because the adhesiveness between the acrylic resin and the polypropylene-based resin is good and the followability of elongation at the time of match molding is good.

As a method for laminating the adhesive layer (D), it can be laminated by a dry lamination method, a wet lamination method, a hot melt lamination method or the like using a conventional solvent-type adhesive. These adhesive coating methods are gravure coater, gravure reverse coater, flexo coater, blanket coater, roll coater, knife coater, air knife coater, kiss touch coater, kiss touch reverse coater, comma coater, comma reverse coater, micro reverse coater. Etc. can be used. 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 . When the amount is less than 2 g / m ² , the adhesive strength is weakened. When the amount is more than 10 g / m ² , the drying property is lowered and the appearance tends to be poor. 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.

[Decorative protective layer (E)]
Between the thermoplastic film layer (A) and the decorative layer (B), it is composed of one or more semi-cured curable resin layers for the purpose of improving heat resistance, solvent resistance, design properties, weather resistance and the like. A decorative protective layer (E) may be provided. In particular, when the decorative layer (B) is made of foil ink, it is desirable to provide the following decorative protective layer (E) as the ink protective layer. The type of resin that can be used for the decorative protective layer (E) is not particularly limited as long as it does not impair the spreadability of the thermoforming sheet, but the ink solvent resistance and heat resistance during molding are good. An ink protective layer comprising a crosslinked layer comprising a thermosetting composition is preferred. Among these, acrylic resins are preferable from the viewpoints of easy adjustment of the crosslinking density, weather resistance, adhesiveness with the thermoplastic film layer (A), and the like. The crosslinking mechanism of the resin is not particularly limited, and in the case of an acrylic resin, UV curing, EB curing, hydroxyl group-containing copolymer / isocyanate curing, silanol / water curing, epoxy / amine curing, and the like can be used. Of these, hydroxyl group-containing copolymer / isocyanate curing is preferred from the viewpoints of easy adjustment of the crosslinking density, weather resistance, reaction rate, presence or absence of reaction byproducts, production cost, and the like. Semi-cured here means that it is not in a completely cured state, and the crosslinking density can be controlled according to the thermoforming temperature and the hardness of the sheet to be used.

  Further, in order to impart design properties to the decorative protective layer (E), a coloring agent may be added to the decorative protective layer (E) to form a colored layer. In this case, the amount of the colorant added varies depending on the type of the colorant, the target color tone, the thickness of the decorative protective layer (E), etc., but the decorative protective layer (E) does not conceal the decorative layer (B). The total light transmittance is preferably 20% or more, and more preferably 40% or more. As a colorant that can be added to the decorative protective layer (E), a pigment is preferable. The pigment used here is not particularly limited, and known and commonly used pigments such as colored pigments, metallic pigments, interference color pigments, fluorescent pigments, extender pigments, and antirust pigments can be used.

(Colored pigment in decorative protective layer (E))
Examples of the color pigment include organic pigments such as quinacridone pigments such as quinacridone red, azo pigments such as pigment red, phthalocyanine pigments such as phthalocyanine blue, phthalocyanine green, and perylene red; inorganic pigments such as titanium oxide and carbon black Is mentioned. Examples of metallic pigments include aluminum powder, nickel powder, copper powder, brass powder, and chromium powder. Examples of the interference color pigment include pearl luster-like pearl mica powder and pearl luster-like colored pearl mica powder.

  As fluorescent pigments, quinacridone pigments, anthraquinone pigments, perylene pigments, perinone pigments, diketopyrrolopyrrole pigments, isoindolinone pigments, condensed azo pigments, benzimidazolone pigments, monoazo pigments, Insoluble azo pigments, naphthol pigments, flavanthrone pigments, anthrapyrimidine pigments, quinophthalone pigments, pyranthrone pigments, pyrazolone pigments, thioindigo pigments, anthanthrone pigments, dioxazine pigments, phthalocyanine pigments, indones Organic pigments such as Ron-based pigments; Metal complexes such as nickel dioxin yellow and copper azomethine yellow; Metal oxides such as titanium oxide, iron oxide and zinc oxide; Metal salts such as barium sulfate and calcium carbonate; Carbon black, aluminum and mica Inorganic pigments such as It is.

[Surface protective layer]
A surface protective layer composed of one or more semi-cured curable resin layers can be provided on the surface of the thermoplastic film layer (A) (that is, the surface opposite to the surface on the decorative layer (B) side). The type of resin that can be used for the surface protective layer is not particularly limited as long as it does not impair the spreadability of the thermoforming sheet, but may be formed of the same paint as that used for the decorative protective layer (E). preferable. Since the ink solvent resistance and the heat resistance during molding are good, a surface protective layer comprising a crosslinked layer comprising a thermosetting composition is preferred. Among these, acrylic resins are preferable from the viewpoints of easy adjustment of the crosslinking density, weather resistance, adhesiveness with the thermoplastic film layer (A), and the like. The crosslinking mechanism of the resin is not particularly limited, and in the case of an acrylic resin, UV curing, EB curing, hydroxyl group-containing copolymer / isocyanate curing, silanol / water curing, epoxy / amine curing, and the like can be used. Of these, hydroxyl group-containing copolymer / isocyanate curing is preferred from the viewpoints of easy adjustment of the crosslinking density, weather resistance, reaction rate, presence or absence of reaction byproducts, production cost, and the like. Semi-cured here means that it is not in a completely cured state, and the crosslinking density can be controlled according to the thermoforming temperature and the hardness of the sheet to be used.

(Method for producing thermoformed laminated sheet)
The method and order of laminating the layers constituting the thermoforming laminated sheet used in the present invention are not particularly limited. For example, the layer structure of a thermoplastic film layer (A) having a surface protective layer / decorative protective layer (E) / decorative layer (B) / other ink layer / adhesive layer (D) / supporting substrate layer (C) As a method for producing a laminated sheet for thermoforming comprising: a surface protective layer on one side of the thermoplastic film layer (A), a decorative protective layer (E), a decorative layer (B), and another ink layer on the other side A method of laminating and bonding a support base material layer (C) coated with an adhesive layer (D) on the decorative layer (B) or other ink layer side is exemplified.
When the decorative layer (B) is made of a metal thin film layer, for example, a surface protective layer is applied to one surface of the thermoplastic film layer (A) by coating or the like, and the other surface is made of metal by vacuum deposition or the like. An example is a method of forming a thin film layer, laminating a support base material layer (C) coated with an adhesive layer (D) on the metal thin film layer side, and bonding them together.
In addition, as a layer structure of the laminated sheet | seat for thermoforming used by this invention, it is also possible to abbreviate | omit a surface protective layer, a decoration layer (B), another ink layer, etc.

  The layering method of the ink layer such as the surface protective layer and the decorative layer (B) may be performed by a known printing or coating method. For example, a printing method such as gravure printing, flexographic printing or screen printing, gravure coater, gravure reverse. Coating methods such as a coater, a flexo coater, a blanket coater, a roll coater, a knife coater, an air knife coater, a kiss touch coater, a kiss touch reverse coater and a comma coater, a comma reverse coater, and a micro gravure coater can be used.

  Further, the adhesive surface of the support base layer (C) is subjected to plasma treatment, corona treatment, flame treatment, electron beam irradiation treatment, roughening for the purpose of improving the affinity with the adhesive constituting the adhesive layer (D). Surface treatment such as surface treatment, ozone treatment, and the like, and dry plating treatment such as vacuum deposition, sputtering, and ion plating may be performed.

(Thermoforming method)
In the present invention, at least the thermoplastic film layer (A), the adhesive layer (D), and the surface in contact with the adhesive layer (D) are smooth, and the opposite surface is embossed by an embossing roll. The laminated sheet for thermoforming, in which the support base material layer (C) to which is transferred, is laminated in this order, is thermoformed. In the present invention, the laminated sheet may be formed by any method as long as one or both sides of the heated sheet are formed in contact with at least one mold surface. Match molding, vacuum forming, pressure forming, pressure vacuum There is no particular limitation such as molding.

In the present invention, it is preferable to use a mold having a smooth surface for thermoforming. However, since the sheet having the above-described configuration can be molded at a relatively low temperature, for example, an injection-molded product, for example, It is also possible to perform thermoforming using a mold formed of plastic or other materials.
In addition, after forming the molded body having a three-dimensional shape by thermoforming, a step of performing an insert injection molding method in which the molded body is inserted into the female mold side in the injection mold and integrated with the injection resin is added. be able to.

(Match mold molding)
Match molding (also referred to as press molding) is performed by matching a female mold (also referred to as a concave mold) and a male mold (also referred to as a convex mold) with a sheet heated in a heating zone interposed therebetween. The mold used here is usually provided with a vacuum port as an escape path for air in the mold, but vacuum suction may be performed supplementarily using this hole. By performing this match mold molding at a low temperature, it is possible to obtain a molded body that takes advantage of the high-brightness metallic luster of the sheet before molding.

(Match molding using clamp frame)
In the present invention, as a method of match molding, after heat plasticizing a part to be molded of the laminated sheet for thermoforming, the entire circumference of the part to be molded is double-sided using a pair of clamp frames. The at least part of one mold is pressed against the heat plasticized part inside the clamp frame, and the heat plasticized part is placed between the one mold and the clamp frame. It is possible to use a method of extending and then bringing the other mold into contact with the heat plasticized portion and sandwiching the heat plasticized portion between the one mold and the other mold. preferable.

  As a result, the entire circumference of the portion of the thermoforming sheet that is to be molded can be clamped with a frame-shaped clamp frame, and the thermoforming sheet inside the clamp frame can be firmly fixed. By pressing the mold onto the sheet, the tension of the thermoforming sheet immediately before molding can be optimized (uniformized). Thereby, the generation | occurrence | production of the wrinkles by sheet | seat drawing in in a pair of metal mold | die, and the fall of the designability by non-uniform extension can be suppressed. Since the clamp frame is movable, the tension of the sheet can be optimized by performing clamping with the clamp frame after heat plasticization. Moreover, since a desired shape can be imparted by sandwiching the thermoforming sheet between a pair of match mold forming molds, molding at a lower temperature is possible compared to vacuum forming, and the mold reproducibility is remarkably improved. Moreover, adverse effects on the design material (such as a decrease in gloss of the metal thin film strip-containing ink layer and cracks in the metal thin film layer) can be avoided.

(Match mold forming device with clamp frame)
1 and 2 are schematic cross-sectional views for explaining a first embodiment of a molding method and a molding apparatus using a clamp frame. Although the molding method differs between FIG. 1 and FIG. 2, the same molding apparatus is used. This molding apparatus is an apparatus for molding a sheet by heat-plasticizing at least a part of a thermoforming sheet and then bringing a pair of molds into contact with both sides of the plasticized part. A frame-like clamp frame that clamps the entire circumference of the part is provided around each mold, and the clamp frame is relatively movable with respect to the mold.

  In FIG. 1 and FIG. 2, the code | symbol 1 represents the laminated sheet for thermoforming. The molding apparatus used in the present invention includes a male mold 10 and a female mold 20 as one match mold molding mold, fixing plates 13 and 23 to which the respective molds 10 and 20 are fixed, and a thermoforming laminate. A pair of clamp frames 14 and 24 for clamping the entire periphery of the portion 2 of the sheet 1 to be molded from both sides, and cylinders 16 and 26 as driving means for driving the clamp frame with respect to the mold are provided.

As shown in FIG. 4, the male mold 10 includes a male main body 11 that contacts the thermoforming laminated sheet 1 and forms the shape of the concave portion of the molded body, and a box 12 that houses the male main body 11. A block 12 a (see FIGS. 1 and 2) is inserted between the rear surface of the male main body 11 and the bottom surface of the box 12, and the box 12 is fixed to the fixing plate 13. The male main body 11 has a horizontal surface 11a provided on the outer peripheral portion, a top surface 11c provided in the center of the male main body 11, and an inclined surface 11b connecting the horizontal surface 11a and the top surface 11c. 11b and the top surface 11c are in a position higher than the horizontal surface 11a. This male mold 10 is provided with a flow path (not shown) of a medium such as water or oil in order to adjust the temperature of the mold, and can be connected to a mold temperature controller. The temperature control method for the mold is not particularly limited, and other methods may be used.
An air vent hole or a vacuum hole (not shown) may be provided at the joint between the horizontal surface 11a and the slope 11b of the male mold 10 as necessary. These holes are preferably as small as possible so that no trace remains on the molded body. Specifically, the diameter of the hole is preferably in the range of 0.3 to 1.2 mm, more preferably in the range of 0.3 to 0.6 mm.

  A frame-shaped clamp frame 14 is provided around the male mold 10. A pair of overhanging portions 14a project outward from both sides of the clamp frame 14, and the tip of a drive shaft (rod) 16a of the cylinder 16 is fixed to the overhanging portion 14a. Accordingly, the clamp frame 14 is configured to be movable relative to the male mold 10. 4A shows a state in which the clamp frame 14 is lowered with respect to the male mold 10, and FIG. 4B shows a state in which the clamp frame 14 is raised with respect to the male mold 10. The cylinder 16 that drives the clamp frame 14 is fixed to a fixed plate 13 that is common to the box 12 of the male mold 10. For this reason, both the male mold 10 and the clamp frame 14 can be simultaneously approached and moved away from the thermoforming laminated sheet 1 by driving the fixing plate 13 by a driving means (not shown).

As shown in FIG. 5, the female mold 20 includes a female mold body 21 that contacts the thermoforming laminated sheet 1 to mold the shape of the convex portion side of the molded body, and a box 22 that houses the female mold body 21. . A block 22 a (see FIGS. 1 and 2) is inserted between the back surface of the female mold main body 21 and the bottom surface of the box 22, and the box 22 is fixed to the fixing plate 23. The female main body 21 has a horizontal surface 21a provided on the outer peripheral portion, a bottom surface 21c provided at the center of the female main body 21, and a slope 21b connecting the horizontal surface 21a and the bottom surface 21c. The bottom surface 21c is at a position lower than the horizontal surface 21a. In order to adjust the temperature of the mold, the female mold 20 is provided with a flow path (not shown) of a medium such as water or oil, and can be connected to a mold temperature controller. The temperature control method for the mold is not particularly limited, and other methods may be used.
An air vent hole or a vacuum hole (not shown) may be provided at the joint between the slope 21b and the bottom surface 21c of the female mold 20 as necessary. These holes are preferably as small as possible so that no trace remains on the molded body. Specifically, the diameter of the hole is preferably in the range of 0.3 to 1.2 mm, more preferably in the range of 0.3 to 0.6 mm.

  A frame-shaped clamp frame 24 is provided around the female mold 20. A pair of overhanging portions 24a are provided on both sides of the clamp frame 24 so as to protrude outwardly. A tip of a drive shaft (rod) 26a of the cylinder 26 is fixed to the overhanging portion 24a. Thereby, the clamp frame 24 is configured to be movable relative to the female mold 20. FIG. 5A shows a state where the clamp frame 24 is lowered with respect to the female die 20, and FIG. 5B shows a state where the clamp frame 24 is raised with respect to the female die 20. A cylinder 26 for driving the clamp frame 24 is fixed to a fixed plate 23 common to the box 22 of the female mold 20. For this reason, by driving the fixing plate 23 with a driving means (not shown), both the female mold 20 and the clamp frame 24 can be simultaneously approached and moved away from the thermoforming laminated sheet 1.

In the match mold molding, the surface shape of the male mold 10 and the surface shape of the female mold 20 are the same. However, the clearance between both molds when the male mold 10 and the female mold 20 are combined needs to be appropriately adjusted in consideration of the thickness of the laminated sheet 1 for thermoforming and the expansion rate during thermoforming. . Specifically, the clearance between the male mold 10 and the female mold 20 is preferably within a range of −50 to + 30% with respect to the thickness distribution of the actually obtained three-dimensional molded body, and more preferably − It is good to design within the range of 30 to + 10%. If the clearance between the molds is too large, the sheet cannot be sandwiched between the two molds at the time of thermoforming, the mold reproducibility of the resulting molded body is deteriorated, and deformation of the molded body is increased due to cooling unevenness. Conversely, if the clearance is too small, compression marks and vacuum hole marks are likely to remain on the molded body. In particular, when a decorative sheet having design properties is used as the laminated sheet 1 for thermoforming, by making the clearance appropriate, a change in design properties at the time of molding is reduced, and a molded product having the desired design properties is obtained. It becomes easy to obtain.
Further, when the mold is heated and used, it is necessary to perform mold design (particularly clearance adjustment) in consideration of the coefficient of thermal expansion of the mold.

  In the present invention, the specific shapes and dimensions of the molds 10 and 20 can be appropriately designed according to the shape and dimensions of the molded body, and depend on the thermoformability of the thermoformed laminated sheet 1, and thus are particularly limited. However, in order to obtain a three-dimensional molded body having sufficient mold reproducibility, the R value of the corner of the mold is 0.2 mm or more, the development rate is within 500%, and the maximum drawing ratio (maximum The height / minimum length of the bottom is preferably 1.5 or less and the maximum inclination angle is within 87 °. More preferably, the R value of the corner portion is 0.5 mm or more, the development rate is within 350%, the maximum aperture ratio is 1.0 or less, and the maximum inclination angle is within 85 °.

  In the present invention, in addition to the male mold 10 and the female mold 20 for forming the thermoformed laminated sheet 1, the movable clamp frames 14 and 24 are used in combination, so that the molding mold is a problem peculiar to match molding. (This is caused by drawing the sheet into the mold) can be effectively suppressed. Moreover, generation | occurrence | production of the molding flaw by the sheet slack at the time of low temperature shaping | molding can also be suppressed simultaneously.

Since the movable clamp frames 14 and 24 are movable and can clamp the sheet 1 after heating, the laminated sheet 1 for thermoforming can be strongly fixed, and the sheet 1 into the molds 10 and 20 can be fixed. It is possible to remarkably suppress molding wrinkles due to pulling in. In general-purpose continuous molding machines, there are few cases where a frame clamp is used as a sheet fixing method at the time of heating, and even when a frame clamp is used, the sheet is clamped before heating. It was insufficient. In addition, the sheet 1 made of a thermoplastic resin generally has a problem that the sheet is likely to be loosened due to thermal expansion below the glass transition temperature, and there is a problem that molding wrinkles occur due to this loosening, but the movable element that is a characteristic element of the present invention. If the clamp frames 14 and 24 are used, the heated thermoformed laminated sheet 1 is pressed against the male mold 10 or the female mold 20 while being held by the clamp frames 14 and 24, so that before molding (the female mold 20 and the male mold 20). The wrinkles before the mold 10 is fitted can be removed.
As the structure of the movable clamp frames 14 and 24, a shape that can fix the sheet 1 after heating and does not collide with the male mold 10 and the female mold 20 when moving is preferable. Specifically, the distance between the movable clamp frames 14 and 24 and the boxes 12 and 22 (the male mold 10 and the female mold 20 when there is no box) depends on the properties and thickness of the sheet, but is not limited. Since the previous wrinkles can be effectively suppressed, it is preferably within the range of 20 mm or less than the sheet thickness.

The clamp frames 14 and 24 have a combination of a convex portion 31 and a concave portion 32 that are fitted to each other on the surface of the sheet fixing portions 15 and 25 that clamp the laminated sheet 1 for thermoforming, for example, as shown in FIG. It is preferable. Thereby, when the laminated sheet 1 for thermoforming is clamped between the clamp frames 14 and 24, the convex portion 31 protruding from one clamp frame is inserted into the concave portion 32 recessed from the other clamp frame. The laminated sheet 1 for thermoforming can be fixed more strongly. As a method of combining the convex portion 31 and the concave portion 32, the male-side clamp frame 14 may be provided with the convex portion 31 and the female-side clamp frame 24 may be provided with the concave portion 32. 32, the convex part 31 may be provided in the female side clamp frame 24, and these may be used together.
The shape of the convex part 31 and the recessed part 32 is not specifically limited, As the convex part 31, various shapes, such as pin shape, rib shape, serrated shape, mountain shape, triangular shape, column shape, are employable. Further, as the recess 32, various shapes such as a groove, a hole having a bottom, and a through hole can be adopted. At the time of clamping, a form in which the thermoforming laminated sheet 1 is sandwiched between the convex part 31 and the concave part 32 may be used, or a form in which a hole is formed by breaking through the thermoforming laminated sheet 1 may be used.

  The movable direction of the clamp frames 14 and 24 is not particularly limited, but the vertical direction perpendicular to the horizontal surfaces 11a and 21a of the molds 10 and 20 is adjusted by the pressure with which the tension of the sheet 1 is brought into contact with the molds. This is preferable because molding wrinkles can be effectively suppressed and cost is advantageous. Further, the power for moving the clamp frames 14 and 24 is not particularly limited, but a method using the cylinders 16 and 26 using pneumatic pressure or hydraulic pressure is preferable because it is simple, and in particular, a pneumatic cylinder (hereinafter referred to as an air cylinder). Is more preferable because the execution speed is faster. Moreover, when using a cylinder, since the clamping force of a sheet | seat becomes uniform, it is preferable to use 2 or more cylinders, and 4 or more uses are more preferable.

Clamping force for fixing the molding sheet using the clamp frames 14 and 24 is not limited because it depends on the properties of the thermoforming laminated sheet 1 and the shape of the clamp frame, but by drawing the sheet into the mold during match molding. 5 kgf {about 50 N} or more is preferable because defects of wrinkles can be satisfactorily suppressed. Further, the clamping stress is preferably 0.05 kgf / cm ² {about 5 kPa} or more.

  The materials of the molds 10 and 20 and the movable clamp frames 14 and 24 of the present invention are not particularly limited, and various metals used in conventional molds for match mold molding can be used. Specific examples include aluminum-based steel materials, iron-based steel materials, thermosetting resins, and the like. In particular, a hard aluminum steel material is preferable as a material for the mold. If necessary, surface treatment such as polishing treatment, fluororesin treatment, alumite treatment, nitriding treatment, boriding treatment, plating treatment, etc. can be performed.

The match mold molding die and molding method according to the present invention can be used in various molding machines equipped with a sheet heating device, a lower mold movable device, and an upper mold movable device. A molding machine (with a plug mechanism) or a vacuum / pressure forming machine is preferred. As the sheet heating device, an indirect heating method from one side or both sides of the sheet is preferable because no trace of the heating device remains on the sheet surface. Moreover, since various molding methods are possible, it is preferable that a vacuum mechanism is provided in at least one of the lower mold movable device and the upper mold movable device. One of the movable devices having a vacuum mechanism may be provided with a pressure air mechanism. Moreover, the drive system of a lower mold | type movable apparatus and an upper mold | type movable apparatus is not specifically limited, An air cylinder type, a hydraulic cylinder type, a servo motor type, etc. can be used. However, the mold closing force of the lower mold and the upper mold is not limited because it depends on the properties of the thermoforming laminated sheet 1 and the mold shape, but 10 kgf {about 100 N} or more is necessary, and the mold reproducibility is good. Therefore, it is more preferable that it is 100 kgf or more {about 1 kN or more}. The mold closing stress is preferably 0.05 kgf / cm ² {about 5 kPa} or more. In addition, the mold closing force said here shows the maximum compressive force at the time of fitting a female type | mold and a male type | mold. Specifically, the thrust obtained by subtracting the larger maximum thrust of the movable clamp frame for the female mold and the male mold from the smaller maximum thrust of the lower mold movable apparatus and the upper mold movable apparatus is shown.

  That is, if the molding apparatus having the clamp frame of the present invention is used, the clamping force of the sheet is adjusted by adjusting the thrust of the lower mold movable apparatus, the upper mold movable apparatus, the female mold movable clamp frame, and the male mold movable clamp frame. The molding speed and the mold closing force can be freely selected. For example, if the thrust of the movable clamp frame is increased, the clamping force of the sheet is high, the forming speed is slow, and the mold closing force is low. Conversely, if the thrust of the movable clamp frame is low, the clamping force of the sheet is low. The molding speed is fast and the mold closing force is high.

As the molding method according to the present invention, it is preferable to use match mold molding according to the following procedures (1) to (9).
(1) The laminated sheet 1 for thermoforming is fixed with a clamp (not shown) attached to the molding machine.
(2) The heater (not shown) is moved to a position above and / or below the sheet 1.
(3) The sheet 1 is heated with the heater until a predetermined temperature is reached.
(4) The heater is moved out of the molding machine.
(4 ′) When the heating position and the molding position are different, the heated sheet is moved to the mold position.
(5) The female mold 20 arranged on the upper side of the sheet 1 is lowered, and the male mold 10 arranged on the lower side of the sheet 1 is raised.
(6) After the laminated sheet 1 for thermoforming is clamped from both sides by the clamp frames 14 and 24, the sheet 1 is moved between the female mold 20 and the male mold 10 by using the lowering of the female mold 20 and the raising of the male mold 10. Make it a three-dimensional shape by sandwiching it,
(7) Hold the sheet 1 between the female mold 20 and the male mold 10 for a predetermined time.
(8) The female mold 20 is raised, the male mold 10 is lowered, and the molded body having a three-dimensional shape is separated from the molds 10, 20 and the clamp frames 14, 24, and then the molded body is predetermined with air or the like. Cool for hours.
(9) Open the clamp attached to the molding machine.

In (6), when the sheet is clamped, it is preferable that the sheet is not in contact with the mold because the sheet elongation tends to be uniform.
In (2) to (4), the heights of the clamp frames 14 and 24 are adjusted manually or by operating the solenoid valves to move the cylinders 16 and 26 up and down, and the clamp frames 14 and 24 and the heater during operation Can be avoided.
Instead of the procedure (2), the sheet 1 may be retracted from between the molds 10 and 20 and moved to the position of a heater (not shown) installed outside the molding machine. In this case, instead of the procedure (4), the sheet 1 is moved from the outside of the molding machine to a position between the molds 10 and 20.
In (8), when the release speed between the molded body and the male mold is inferior due to the operation of the cylinder 16, the cylinder 16 is opened manually or by solenoid valve operation. The mold should be lowered.
It is also possible to arrange the male mold 10 on the upper side of the sheet 1 and the female mold 20 on the lower side of the sheet 1. In this case, the male mold 10 is lowered and the female mold 20 is raised in the procedures (5) and (6), and the male mold 10 is raised and the female mold 20 is lowered in the procedure (8).

  In step (6), the following two molding methods A and B can be selected by selecting the shape of the movable clamp frames 14 and 24 and adjusting the thrust. Any molding method can be applied, and it is desirable to select a more appropriate method in consideration of a mold design, a sheet configuration, and the like.

(Forming method A)
As shown in FIG. 1A, after the thermoforming laminated sheet 1 is clamped from both sides by the clamp frames 14 and 24, the downward thrust of the female-side clamp frame 24 is increased as shown in FIG. By making it smaller than the upward thrust of the mold side clamp frame 14, the thermoforming laminated sheet 1 fixed by the movable clamp frames 14 and 24 after heating is pressed against the female mold 20 first. That is, the horizontal surface 21a of the female mold 20 is pressed against the central portion of the thermoforming laminated sheet 1, and the portion 2 of the thermoforming laminated sheet 1 to be molded is projected to the male mold 10 side. Thereby, in the laminated sheet 1 for thermoforming, a step is generated between the portion that is in contact with the horizontal surface 21a of the female mold 20 and the portion that is clamped by the clamp frames 14 and 24, thereby extending the wrinkles of the sheet 1. Can do. Thereafter, as shown in FIG. 1C, the sheet 1 is sandwiched between the male mold 10 and the female mold 20 to form a three-dimensional shape.

In FIG. 1B, the difference in height between the horizontal surface 21a of the female mold 20 and the surface 25 on which the female mold-side clamp frame 24 clamps the sheet 1 is due to the properties of the thermoforming laminated sheet 1 and the mold shape. Therefore, it is not particularly limited, but is preferably in the range of 2 to 30 mm because sheet loosening during low temperature molding can be effectively removed. The sign of the height difference is positive when the horizontal surface 21a of the female mold 20 protrudes from the clamp surface 25 of the female clamp frame 24 to the male mold 10 side.
According to this forming method A, when a decorative sheet having a decorative layer is used, it is easy to obtain a molded article with good decorative sharpness by directing the design surface on which the decorative layer becomes visible toward the female mold 20 side. Furthermore, when using a decorative sheet having a printed pattern as a decorative layer and partially decorating the resulting molded body, it is easy to align the pattern position, and uneven thickness during molding is less likely to occur. Non-uniform deformation is also reduced.
The same applies to the female mold 20 on the lower side and the male mold 10 on the upper side.

(Forming method B)
As shown in FIG. 2A, after the thermoforming laminated sheet 1 is clamped from both sides by the clamp frames 14 and 24, the downward thrust of the female-side clamp frame 24 is increased as shown in FIG. By making it larger than the upward thrust of the mold side clamp frame 14, the thermoforming laminated sheet 1 fixed by the movable clamp frames 14 and 24 after heating is pressed against the male mold 10 first. That is, the top surface 11c of the male mold 10 is pressed against the central portion of the thermoforming laminated sheet 1, and the portion 2 of the thermoforming laminated sheet 1 to be molded is protruded to the female mold 20 side. Thereby, in the laminated sheet 1 for thermoforming, a step is generated between the portion 2a in contact with the top surface 11c of the male mold 10 and the portions clamped by the clamp frames 14 and 24, and the sheet 1 is wrinkled. Can be stretched. Thereafter, as shown in FIG. 2 (c), the sheet 1 is sandwiched between the male mold 10 and the female mold 20 and formed into a three-dimensional shape.

  In FIG. 2B, the difference in height between the horizontal surface 11a of the male mold 10 and the surface 15 on which the male mold clamping frame 14 clamps the sheet 1 is due to the properties of the thermoforming laminated sheet 1 and the mold shape. Although it is not particularly limited because it depends, it is preferably in the range of −30 to 15 mm because sheet loosening during low-temperature molding can be effectively removed. The sign of the height difference is positive when the horizontal surface 11a of the male mold 10 protrudes toward the female mold 20 from the clamp surface 15 of the male clamp frame 14, and the horizontal plane 11a is lower than the clamp surface 15. Negative when in position. In the example shown in FIG. 2B, the horizontal surface 11a of the male mold 10 and the clamp surface 15 of the male clamp frame 14 are substantially on the same plane, and the height difference is approximately 0 mm. Further, the height difference between the male mold side clamp frame 14 and the surface 15 for clamping the sheet 1 is set to less than 0 mm, and the mold reproducibility is further improved by vacuum suction from the vacuum hole provided in the male mold. There is a case.

  According to this forming method B, the sheet 1 (part 2b not in contact with the mold) between the top surface 11c of the male mold 10 and the clamp frames 14, 24 is placed on the inclined surface 11b of the male mold 10 on the horizontal surface 11a. Since the sheet can be extended without being contacted, a sheet having a larger area can be distributed to the gradient portion (portion formed by the inclined surfaces 11b and 21b of the molds 10 and 20) of the molded body. Therefore, when a mold having a shape with a high development rate or a portion with a large gradient is used, a molded product with good mold reproducibility is easily obtained. The same applies to the female mold 20 on the lower side and the male mold 10 on the upper side.

Next, a second embodiment of the molding method and molding apparatus of the present invention will be described.
FIG. 3 is a schematic cross-sectional view for explaining a second embodiment of the molding method and molding apparatus of the present invention. FIG. 6 is a perspective view showing a female mold provided with a clamp frame used in FIG. 3.
In the present embodiment, the male mold 10 and the male clamp frame 14 may be those shown in FIG. 4 as in the first embodiment. As shown in FIGS. 3 and 6, the female mold side clamp frame 24 has a flange portion 27 extending to the inner peripheral edge portion of the clamp frame 24, and the flange portion 27 is an inner peripheral edge portion of the male mold side clamp frame 14. Use the clamp frame inside. In this case, the female mold 20 </ b> A is such that the height of the horizontal surface 21 a of the female mold main body 21 exceeds the thickness of the flange portion 27 and protrudes from the edge of the box 22. As a method of adjusting the height of the female mold body 21, there is a method of inserting a height adjusting plate 22b on the back side of the female mold body 21, and according to this method, the box 22 of the female mold 20 in FIG. The female mold 20A shown in FIG. 6 can be configured simply by adding the plate 22b.

  The clamp frames 14 and 24 in the present embodiment are projections that fit together on the surfaces of the sheet fixing portions 15 and 25 that clamp the thermoformed laminated sheet 1 in the same manner as described in the molding apparatus of the first embodiment. It is preferable to have a combination of the portion 31 and the recessed portion 32 (see FIGS. 8 and 9). Thereby, when the laminated sheet 1 for thermoforming is clamped between the clamp frames 14 and 24, the convex portion 31 protruding from one clamp frame is inserted into the concave portion 32 recessed from the other clamp frame. The laminated sheet 1 for thermoforming can be fixed more strongly. As a method for combining the convex portion 31 and the concave portion 32, the male-side clamp frame 14 may be provided with the convex portion 31, and the female-side clamp frame 24 may be provided with the concave portion 32. The convex portion 31 may be provided on the mold side clamp frame 24, or these may be used in combination.

  In this embodiment, the sheet 1 can be formed by the same method as the above-described forming method B (male is first pressed against the sheet). That is, as shown in FIG. 3 (a), the thermoforming laminated sheet 1 is clamped from both sides by the clamp frames 14, 24, and then the clamping pressure of the female-side clamp frame 24 is shown in FIG. 3 (b). Is made larger than the clamping pressure of the male mold side clamp frame 14, the thermoformed laminated sheet 1 fixed by the movable clamp frames 14 and 24 after heating is pressed against the male mold 10 first. That is, the top surface 11c of the male mold 10 is pressed against the center portion of the thermoforming laminated sheet 1, and the portion 2 of the thermoforming laminated sheet 1 to be molded is protruded toward the female mold 20A. Thereby, in the laminated sheet 1 for thermoforming, it is possible to create a step between the portion 2a in contact with the top surface 11c of the male mold 10 and the portion clamped by the clamp frames 14 and 24 to extend the wrinkles. it can. Thereafter, as shown in FIG. 3 (c), the sheet 1 is sandwiched between the male mold 10 and the female mold 20A and formed into a three-dimensional shape.

3B, when the thermoformed laminated sheet 1 fixed by the movable clamp frames 14 and 24 after heating is pressed against the male mold 10 at the stage, the female-side clamp frame 24 The thermoformed laminated sheet 1 is clamped between the flange portion 27 of the inner peripheral edge portion and the outer peripheral edge portion 17 (here, the edge of the box 12) of the male mold 10, and further, the hem portion (horizontal plane 11a) of the male mold 10 From the vacuum hole 18 (see FIG. 3B) provided in the joint portion of the slope 11b), the heat-plasticized portion 2 of the thermoforming laminated sheet 1 is vacuum-sucked from the male mold 10 side.
According to this configuration, since the vacuum on the male mold side can be used effectively, it is easy to obtain a molded article with better mold reproducibility. At the time of vacuum suction, the distance between the convex part of the male mold 10 and the flange part 27 (horizontal direction in FIG. 3B) can suppress wrinkling and further improve the mold reproducibility. 5-50 mm is preferable. Further, the shape of the flange portion 27 is not necessarily uniform between the convex portion of the male mold 10 and the flange portion 27, and the interval between the portions having a high development rate is intentionally increased or a bridging failure occurs. The design retention and mold reproducibility can be further improved by intentionally shortening the interval between the easy-to-do portions.

  Note that the thermoforming apparatus and method are not limited to the above-described match mold molding, and pressure-vacuum vacuum molding, pressure-air molding, vacuum molding, and the like can also be used. In the case of pressure forming or vacuum forming, the mold can be formed using only one of a male mold and a female mold.

(Temperature conditions for thermoforming)
The temperature of the laminated sheet for thermoforming at the time of molding is not particularly limited because it depends on the thermoformability and mold shape of the laminated sheet for thermoforming used as a raw fabric, but when using a decorative sheet having design properties, As the molding is performed at a lower temperature, the change in the design property is less, and a molded article having excellent decorative sharpness can be easily obtained. In particular, a highly glossy molded article is obtained in the case of a metallic glossy decorative sheet. Furthermore, it is preferable because it is easy to match the pattern in the case of a decorative sheet having a printed pattern for the purpose of partial decoration of the molded body as a decorative layer.

Specifically, at least the thermoplastic film layer (A), the adhesive layer (D), and the surface in contact with the adhesive layer (D) are smooth, and the opposite surface is uneven by an embossing roll. The molding temperature in the case of thermoforming the laminated sheet for thermoforming in which the support base material layer (C) to which the pattern is transferred is laminated in this order is in a temperature range of (T1-20) ° C. or more and (T2) ° C. or less. Preferably there is.
However, T1 is the softening temperature of the laminated sheet which integrated the thermoplastic film layer (A) and the support base material layer (C), and T2 is the softening temperature of the support base material layer (C). However, the softening temperature here refers to a storage elastic modulus measured under measurement conditions of a frequency of 1 Hz and a heating rate of 3 ° C./min using dynamic viscoelasticity measurement measured in accordance with JIS K7244-1 method. The temperature at the intersection of the straight line obtained by extending the base line on the low temperature side of the temperature dependence curve to the high temperature side and the tangent line drawn at the point where the slope of the step-like change portion becomes the maximum.
Further, in order to satisfy both the conditions where the molding temperature is (T1-20) ° C. or higher and the conditions (T2) ° C. or lower, the relationship of T1 and T2 is (T1-20) ° C. ≦ (T2) ° C. It is necessary to become.

That is, in the present invention, by thermoforming in a temperature range in which the temperature at which the thermoplastic film is sufficiently spread (T1-20) ° C. is the lower limit and the temperature at which the embossed pattern does not disappear (T2) ° C. is the upper limit, The uneven | corrugated pattern of a support base material layer (C) can float on the thermoplastic film layer (A) side (design surface side), and the molded object which can recognize a concavo-convex pattern from the design surface side can be manufactured. That is, it is preferable to perform thermoforming at a molding temperature in the above-described temperature range because a molded product having both good mold reproducibility and design can be manufactured.
A more preferable molding temperature range is (T1-15) ° C. or more and (T2-5) ° C. or less, and a more preferable molding temperature range is (T1-10) ° C. or more and (T2-10) ° C. or less. It is a range.

  More specifically, when a far-infrared heater is used, the heater temperature is preferably 200 to 500 ° C., the indirect heating time is 5 to 30 seconds, and the temperature at which the sheet can be thermoformed is preferable. Further, the mold temperature needs to be determined while confirming the appearance and molding shrinkage of the molded body to be obtained. This is set to 20 to 200 ° C., and the time for sandwiching the sheet between the male mold and the female mold (described above) The step (7) corresponds to 10 seconds to 5 minutes. The mold temperature is not particularly limited because it depends on the properties of the thermoformed laminated sheet 1, and may be appropriately adjusted depending on the appearance, mold reproducibility, molding shrinkage, and deformation of the resulting molded body. For example, a temperature gradient may be provided between the two molds as necessary. Moreover, it is preferable to cool the obtained molded object with air etc. after completion | finish of thermoforming.

  In the laminated sheet having the decorative layer described above, there is no particular limitation as to which surface is brought into contact with the mold, but from the thermoplastic film layer (A) (the side of the design surface where the decorative layer (B) is visible). When brought into contact with the mold, the state in which the orientation of the metal thin film strips of the decoration layer (B) is aligned can be easily maintained by the mold, so that a molded article with good decoration sharpness can be easily obtained. Moreover, when it deform | transforms from the support base material layer (C) side, a deformation | transformation of a decoration layer (B) becomes mild and it is thought that the designability holding effect is high. On the other hand, from the viewpoint of mold reproducibility, it may be better to deform from the one that is less likely to be deformed (for example, the transition temperature is higher). Therefore, it is desirable to select a more appropriate method in consideration of the mold design and the sheet configuration.

[Decorated molded body]
(Insert injection molding)
A high-gloss laminate sheet is formed into a molded body according to the method for forming a thermoformed laminate sheet of the present invention, and the molded body and resin having high gloss are obtained by integrally molding the obtained molded body and resin ( Hereinafter, it is referred to as a decorative molded body.).
The decorative molded body is a method of integrally molding the molded body by placing the molded body so that the thermoplastic resin film side is in contact with the female mold of the injection mold, and filling the injection resin on the back side of the molded body, or injection After thermoforming in the mold, it can be produced by a method of integrating with the injection resin in the injection mold as it is. Any of them can provide a decorative molded article having high gloss, no breakage, and excellent mold reproducibility.

  If the shape of the target injection-molded body is a two-dimensional shape or a simple three-dimensional shape with a maximum development rate of less than 120%, the sheet is not used as a molded body, and a hairline or the like is formed by match molding. It is possible to obtain an insert injection molded body by inserting it into an injection mold while keeping the sheet shape with the above pattern.

  The injection resin is preferably a resin of the same system as the support base material layer (C) from the viewpoint of adhesion to the support base material layer (C). Specifically, when the support base layer (C) is a polypropylene resin, the polypropylene resin is preferably 40% by mass or more, more preferably 50% by mass or more, and 60% by mass or more in the injection resin. More preferably. When the injection resin contains a polypropylene resin as a main component, other resins that can be blended together with the polypropylene resin include various thermoplastic resins exemplified above as constituting the support base material layer (C) of the present invention. A thermoplastic elastomer or the like can be preferably used. In this case, the injection resin contains 40% by mass or more of the polypropylene resin, and in addition, various resins that can generally be melt-mixed with the polypropylene resin may be contained.

  Examples of resins that can be melt-mixed with polypropylene resins include high-density polyethylene, low-density polyethylene, linear low-density polyethylene, styrene-ethylene-butadiene-styrene copolymers, and styrene-ethylene-propylene-styrene copolymers. And olefin elastomers such as ethylene propylene rubber represented by ethylene elastomer, ethylene-propylene copolymer and ethylene-propylene-diene copolymer. When the supporting base layer (C) is an ABS resin, it is preferable that the injection resin contains 40% by mass or more of ABS resin, but the supporting base layer (C) should have sufficient adhesion to the resin. Main components are acrylonitrile / butadiene / styrene (ABS) resin, acrylonitrile / acrylic rubber / styrene (AAS) resin, acrylonitrile / ethylene rubber / styrene (AES) resin, (meth) acrylic ester / styrene (MS) resin It may be used as a resin.

  An inorganic filler can be added to the injection resin for the purpose of preventing deformation of the injection molded body. The inorganic filler is not particularly limited, and examples thereof include talc, calcium carbonate, clay, diatomaceous earth, mica, magnesium silicate, and silica.

  Further, in the injection resin, additives such as a colorant, a plasticizer, an antioxidant, an ultraviolet absorber, an antistatic agent, a flame retardant, and a lubricant are added as long as the low temperature impact property and the in-mold formability are not impaired. These additives may be used alone or in combination of two or more.

  The filling temperature of the injection resin is not particularly limited, but if the resin temperature is too low, the supporting base layer (C) and the injection resin are easily peeled off, and if the resin temperature is too high, the injection molded body warps as a sink. Is likely to occur. For this reason, in the case of polypropylene resin, the filling temperature of the injection resin is preferably 180 to 270 ° C, and more preferably 200 to 260 ° C. In the case of an ABS resin, 200 to 290 ° C is preferable, and 210 to 260 ° C is more preferable. The injection mold temperature is preferably 20 to 100 ° C. for both the male mold and the female mold. However, when warpage or the like occurs in the injection molded body, it is necessary to provide a temperature gradient to the male mold and the female mold. In addition, the injection delay time (time from mold closing to injection) is set within the range of 1 to 100 seconds in order to heat the molded body inserted into the injection mold to the mold temperature before filling with the injection resin. You may do it.

  As described above, according to the molding method of this embodiment, when the sheet is thermoformed into a three-dimensional shape using a normal smooth mold, the support base material layer (C) side of the thermoformed laminated sheet is used. Molding in which the concavo-convex pattern formed on the outer surface (back surface) of the film is raised on the outer surface (front surface) on the thermoplastic film layer (A) side, and the concavo-convex pattern attached to the support base layer is clearly present on the thermoplastic film layer side Product can be manufactured. As a result, a molded product having a three-dimensional shape and a concavo-convex pattern on the surface can be formed, and a molded product excellent in appearance and design can be obtained by combining the visual and tactile effects of the shape and the concavo-convex. When the decorative layer (B) is combined with an ink layer having a metallic luster such as a metal thin film strip, it is more effective because even a minute pattern (unevenness) can be recognized by reflection of light.

  By providing the transparent thermoplastic film layer (A) on the surface (design surface) side of the thermoformed laminated sheet, a high gloss and beautiful design can be realized. Prior to thermoforming, the surface of the thermoplastic film layer (A) is smooth, so that the thermoplastic film layer (A) can be subjected to desired printing such as grain or stone. Combining this printed pattern with a concavo-convex pattern that floats from the support base material layer (C) side to the thermoplastic film layer (A) side gives a more realistic tactile feel and design expression close to natural wood grain or stone grain. It can also be granted.

  Hereinafter, the present invention will be described with specific examples, but the present invention is not limited thereto. In addition, the physical-property evaluation in an Example and a comparative example was performed with the following measuring method or test method. In the examples, “part” and “%” are both based on mass.

(Evaluation mold)
Low surface 183 × 204mm, top surface 51 × 66mm, height 50mm, slope slope gradient is 35, 55, 60, 70 °, respectively, the top and slope joints are 0.5, 1, 5, 3mmR, slope A trapezoidal male die 10 having a joint portion of 5 mmR and a joint portion between the slope and the lower surface of 1 mmR was used. In addition, a female mold having a clearance of 400 μm when combined with the male mold was used. Further, a vacuum hole with a diameter of 0.5 mm was provided at the joint between the male horizontal surface (low surface) and the slope, and an air vent hole with a diameter of 0.5 mm was provided at the joint between the bottom and the slope of the female mold. The mold has a movable clamp mechanism for preventing sheet slippage during molding.

(Softening temperature measurement method)
The softening temperature used in the present invention is a storage elasticity measured under dynamic viscoelasticity measurement measured in accordance with JIS K7244-1 method under a measurement condition of a frequency of 1 Hz and a heating rate of 3 ° C./min. The softening temperature was defined as the temperature at the intersection of the straight line obtained by extending the low-temperature base line of the temperature-dependent curve of the rate to the high-temperature side and the tangent line drawn at the point where the slope of the step-like change portion becomes the maximum.

(Appearance evaluation method for molded products)
Using the molded body produced using the evaluation mold, the state of unevenness derived from the support base material layer (C) and the presence or absence of breakage of the base material body on the 180% development rate surface were observed. evaluated. Note that the break was regarded as a break when there was a crack in a part of the molded body.
A: No breakage, good gloss and clear irregularities.
○: No breakage, good gloss, and sufficient unevenness as a product.
Δ: No breakage and good gloss, but uneven and thin and insufficient.
X: An occurrence of breakage, apparently low gloss, or almost no unevenness.

(Method for evaluating the specularity of molded products)
The specularity of the molded body was evaluated based on the following criteria by observing the reflection of the top face of the trapezoidal molded body by the thermoforming method.
A: A sheet that can feel the original specularity of the sheet.
○: Face is visible but mirror surface is not sufficient.
Δ: Slightly specular but slightly scary.
X: Silver tone, no face and no specularity.

(Production of laminated sheet for thermoforming with excellent specularity)
(A) Thermoplastic film layer As a transparent or translucent thermoplastic film layer A-1, a rubber-modified PMMA film having a haze of 0.1% and a thickness of 125 μm (trade name “Technoloy S-001”, Sumitomo Chemical Co., Ltd.) Manufactured, Tg = 125 ° C.). The softening temperature of this sheet was 112 ° C.

(E) Decorative protective layer In order to improve the adhesion between the thermoplastic film layer (A) and the decorative layer (B), an acrylic polyol resin “6KW-032E” (trade name, manufactured by Dainippon Ink and Chemicals, solid content 38 % (Solvent: ethyl acetate), hydroxyl value 30 KOH mg / g) in a mixed solution of 46 parts and 4-methyl-2-pentanone 46 parts, isocyanurate ring-containing polyisocyanate “BURNOCK DN-981” (trade name, Dainippon 8 parts of Ink Chemical Industries, Ltd., solid content 75% (solvent: ethyl acetate), number of functional groups 3, NCO concentration 14%) were mixed (100 parts in total) to prepare a decorative protective layer solution. This decorative protective layer solution is also used for the following surface protective layer.

(F) Surface protective layer A transparent or semi-coated surface having a surface protective layer having a thickness of 5 μm is applied on the opposite surface of the thermoplastic film layer A-1 from which the decorative protective layer is laminated. It was set as the transparent thermoplastic film layer A-2. The softening temperature of this sheet was 111 ° C.

(B) Decoration layer 10 parts of aluminum thin film strip (thickness 0.04 μm, size in the surface direction 5 to 25 μm), 37.25 parts of ethyl acetate, 30 parts of methyl ethyl ketone, 31.5 parts of isopropyl alcohol, nitrocellulose 1 25 parts were mixed (a total of 110 parts) to prepare an aluminum thin film strip slurry.

  30 parts of the obtained aluminum thin-film strip slurry, 3 parts of carboxylic acid-containing vinyl chloride-vinyl acetate resin ("Vinylite VMCH" manufactured by UCC) as a binder resin, urethane resin ("Polyurethane 2593" manufactured by Arakawa Chemical) non-volatile content 32%), 8 parts of ethyl acetate, 23 parts of ethyl acetate, 26 parts of 4-methyl-2-pentanone, and 10 parts of isopropyl alcohol are mixed (a total of 100 parts), and the aluminum thin film strip concentration in the non-volatile content is 35% by mass. Ink B-1 was prepared.

  25 parts of aluminum paste (non-volatile content: 13%) (Hiprint TD-200T: manufactured by Toyo Aluminum Co., Ltd.), 20 parts of urethane resin (“Polyurethane 2593” manufactured by Arakawa Chemical Co., Ltd.), 27 parts of ethyl acetate, 18 parts of methyl ethyl ketone, isopropyl alcohol 10 The ink B-2 whose aluminum paste density | concentration in a non volatile matter is 35 mass% was prepared.

  Moreover, although different from ink, the aluminum for laminating | stacking a 0.04 micrometer aluminum thin film by the vacuum evaporation method was prepared for the thermoplastic film layer A-1 (as B-3).

(D) Adhesive layer In order to adhere the thermoplastic film layer (A) having the decorative layer (B) and the support base layer (C), as a main agent, an aromatic polyester polyol resin “LX-703VL” (trade name, 15 parts by Dainippon Ink and Chemicals), 1 part of aliphatic polyisocyanate “KR-90” (trade name, manufactured by Dainippon Ink and Chemicals) as a curing agent and 18 parts of ethyl acetate as a diluent ( 34 parts in total) to prepare a polyester urethane adhesive.

(C) Support base material layer Low crystalline polypropylene resin (Excellen SP7834) manufactured by Sumitomo Chemical Co., Ltd., linear low density polyethylene “FV403” manufactured by Sumitomo Chemical Co., Ltd., ethylene propylene rubber manufactured by Mitsui Chemicals (Tuffmer P0480) ) Is dry blended at a ratio of 70/10/20, then fed from an extruder hopper, extruded from a T die at a processing temperature of 200 ° C., passed through a cast roll heated to 40 ° C., and wound up An unstretched original fabric sheet C-1 having a thickness of 300 μm was produced. The softening temperature (T2) of this sheet C-1 was 116 ° C.

  After dry blending Sumitomo Chemical's block PP (Noblen AD571) / Sumitomo Chemical's low density polyethylene (Sumikasen F101-1) and Mitsui Chemicals' ethylene propylene rubber (Tuffmer P0480) at a ratio of 65/15/20, After feeding from an extruder hopper, extruded from a T-die at a processing temperature of 230 ° C., passed through a cast roll heated to 40 ° C., wound up, and a 300 μm unstretched original sheet C-2 was produced. The softening temperature (T2) of this sheet C-2 was 156 ° C.

(Sheet stacking method)
The thermoplastic protective layer (A) was coated and dried with a microgravure coater so that the decorative protective layer solution had a dry film thickness of 2.0 μm, and then subjected to an aging treatment at 50 ° C. for 3 days. Next, in the case of the ink as the decoration layer (B), it is coated and dried on the decoration protective layer (E) using a gravure coater so as to have a dry film thickness of 2.0 μm. Vapor deposition was performed to a thickness of 0.04 μm by a vapor deposition method.

  Furthermore, after the corona treatment was performed so that the supporting base layer (C) had a wetting index of 40 dyne / cm on the adhesive surface of the sheet, the adhesive was applied to the supporting base layer (C) side using a micro gravure coater. The adhesive layer (D) obtained by applying and drying to a dry film thickness of 5 μm is bonded to the ink-coated or vapor-deposited surface of the rubber-modified PMMA film and subjected to aging treatment at 50 ° C. for 3 days. A laminated sheet for thermoforming was obtained.

(Molding method)
(Match mold molding)
For the match mold molding of this example, a small vacuum / pressure forming machine FK-0431-10 manufactured by Asano Laboratory Co., Ltd. having a clamping force of 10 ton was used. Attach the female and female movable clamp frames to the plug movable device (upper side) and the male and male movable clamp frames to the mold movable device (lower side). Carried out.

(1) The laminated sheet for thermoforming is fixed with a clamp attached to the molding machine so that the thermoplastic film layer (A) side is on the upper side.
(2) The upper heater is moved above the thermoforming laminated sheet (the lower heater is not used).
(3) The laminated sheet for thermoforming is heated to a predetermined temperature.
(4) Retract the heater.
(5) Lower the female mold and raise the male mold.
(6) Utilizing the lowering of the female mold and the raising of the male mold, the laminated sheet for thermoforming is sandwiched by the movable clamp frame of the mold, and then the sheet is sandwiched between the female mold and the male mold as it is. Use original shape. At this time, vacuum suction from the female mold side is performed for the purpose of releasing air between the female mold and the sheet.
(7) Hold the sheet between the female mold and the male mold for 1 minute.
(8) After raising the female mold and lowering the male mold, the molded body having a three-dimensional shape is cooled with air for 5 seconds.
(9) Open the clamp attached to the molding machine.
A molded body was obtained by the match mold molding method through the above steps (1) to (9).

  For heating, the heater temperature on the upper surface was set to 400 ° C., and the sheet was heated to the sheet temperature shown in each Example and Comparative Example by adjusting the heating time, and then molded. The heater-sheet distance was 130 mm, the mold temperature was 95 ° C. for the female mold, 75 ° C. for the male mold, and the vacuum / cooling time was 60 seconds.

(Pressurized vacuum forming, vacuum forming)
A compact vacuum / pressure forming machine FK-0431-10 manufactured by Asano Laboratories Co., Ltd. having a clamping force of 10 tons was used for the vacuum forming and vacuum forming of this example. The female mold cavity of the match mold was removed so that the compressed air was successfully transmitted to the mold, and the compressed air vacuum forming and vacuum forming were performed in the same manner as the match mold forming except for the box covering the cavity.
In both cases, vacuum suction is performed from the male mold side, but unless otherwise specified, the pressure from the female box side is set to 0.4 MPa, and molding is performed with the atmosphere open during vacuum molding. .

(Insert molding)
A molded body produced by thermoforming of the present invention using a laminated sheet for thermoforming is brought into close contact so that the surface protective layer of the sheet having the ink layer is in contact with the female mold of the injection mold. After heating, a molten resin made of Novatec polypropylene resin (trade name “TX1868H5”) heated to 230 ° C. as a main raw material was injected into the mold and integrally molded to prepare a decorative molded body. The injection molding machine used was Auto-shot 50D manufactured by FANUC, and the injection mold used was 90 mm × 100 mm × thickness 3 mm.

(Examples 1-8, Comparative Examples 1-4)
The layer structure was thermoplastic film layer (A) / decorative protective layer (E) / decorative layer (B) / adhesive layer (D) / support base layer (C). Among these, the supporting base layer (C) (described as “(C) layer” in Table 1) and the thermoplastic film layer (A) (described as “(A) layer” in Table 1) are shown in Table 1. The laminated sheet was formed into a 425 μm molding sheet. The obtained laminated sheet for molding was subjected to the match molding method (described as “Match” in Table 1), the pressure vacuum forming method (described as “Pressure” in Table 1), and the vacuum forming method (Table 1) under the above conditions. Then, it was described as “vacuum”.) The molded body was evaluated for appearance and specularity. In addition, the temperature of the sheet | seat was measured with Keyence Corporation radiation thermometer IT2-80. The evaluation results are shown in Table 1.

  Example 8 is an example in which a metal vapor deposition layer was used as a decorative layer, but the low development part up to about 130% of the development rate showed good specularity, but the development part above it was slightly cloudy. And good mirror surface was not maintained.

Example 9
The top surface portion of the molded body obtained in Example 1 was cut out and integral injection molding was performed by the method shown in the above-described insert molding method. As a result, it was found that the integrally injection-molded product also showed a good leather texture.

(Example 10)
A laminated sheet for thermoforming similar to that of Example 6 was used at 115 ° C. and a pressure of 0.2 MPa using an injection molded product for a design sample including a 230 × 110 × 50 (height) curve instead of a mold. Compressed air vacuum forming was performed. As a result, it was possible to obtain a molded article having a good uneven texture pattern.

(Comparative Example 5)
Only the PP sheet (C-2) used in Example 1 and the like was indexed with a molded body using a compressed air vacuum forming method. As a result, although uneven texture remained, sufficient gloss and specularity were not obtained.

As shown in the evaluation of Examples 1 to 8 shown in Table 1, the molded body molded in a temperature range of (T1-20) ° C. or higher and (T2) ° C. or lower is cracked at a highly developed portion of 180%. In addition, it can be seen that the unevenness derived from the texture pattern of the support base material layer (C) remains in the molded body in a good state. In Example 7, the ink had an aluminum paste specification, so it was not specular, but the high glossiness of the acrylic resin on the surface was maintained.
Moreover, it turns out that sufficient unevenness | corrugation is maintained after insert injection molding from Example 9. Furthermore, it was found from Example 10 that when the thermoforming method was performed using the injection molded body instead of the mold, the molded body in the final form having a good wrinkle pattern was obtained as in the molded body obtained by insert molding. .

On the other hand, it can be seen that when the molding is performed at a temperature exceeding T2 as in Comparative Examples 1 to 3, sufficient unevenness cannot be obtained. It was also found that when the molding temperature of the laminated sheet for thermoforming at the time of molding was lower than (T1-20) ° C. as in Comparative Example 4, the molded body was broken and became defective.
In Comparative Example 5, although no crack was generated, there was no sufficient glossiness and specularity.

  From the above results, it can be seen that the method for forming a laminated sheet for thermoforming according to the present invention is an excellent forming method capable of providing a molded body having good formability and an uneven texture pattern.

  The molded body produced by the molding method of the present invention is useful in fields requiring high design without requiring exterior coating, which is used for applications such as automobile-related members, building material members, and home appliances.

It is typical sectional drawing explaining the shaping | molding method A of the 1st form example of the shaping | molding method of this invention, (a) is the state which clamped the sheet | seat with the clamp frame, (b) is the clamped sheet | seat on one metal mold | die. The state of contact, (c) shows the state where the clamped sheet is clamped with both molds. It is typical sectional drawing explaining the shaping | molding method B of the 1st form example of the shaping | molding method of this invention, (a) is the state which clamped the sheet | seat with the clamp frame, (b) is the clamped sheet | seat on one metal mold | die. The state of contact, (c) shows the state where the clamped sheet is clamped with both molds. It is typical sectional drawing explaining the 2nd form example of the shaping | molding method of this invention, (a) is the state which clamped the sheet | seat with the clamp frame, (b) is the state which made the clamped sheet | seat contact one mold , (C) shows a state where the clamped sheet is clamped by both molds. It is a perspective view which shows an example of the male type | mold which provided the clamp frame, (a) shows the state which lowered | hung the clamp frame with respect to the metal mold | die, (b) shows the state which raised the clamp frame with respect to the metal mold | die. It is a perspective view which shows an example of the female type | mold which provided the clamp frame, (a) shows the state which lowered | hung the clamp frame with respect to the metal mold | die, (b) shows the state which raised the clamp frame with respect to the metal mold | die. It is a perspective view which shows the other example of the female type | mold which provided the clamp frame, (a) is the state which lowered | hung the clamp frame (it is noting and showing partially) with respect to a metal mold | die, (b) is The state where the clamp frame is raised with respect to the mold is shown. It is the schematic which shows an example in case the clamp frame has a recessed part and a convex part which mutually fit in the shaping | molding apparatus used with the match mold shaping | molding method of a 1st form example. It is the schematic which shows an example in case the clamp frame has a recessed part and a convex part which mutually fit in the shaping | molding apparatus used with the match mold shaping | molding method of the 2nd form example. It is the schematic which shows the other example in case a clamp frame has a recessed part and a convex part which mutually fit in the shaping | molding apparatus used with the match mold shaping | molding method of a 2nd form example.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Laminated sheet for thermoforming, 2 ... Part which should be mold-molded, 10 ... Male type, 11 ... Male main body, 12 ... Box, 13 ... Fixed plate, 14 ... Clamp frame, 15 ... Clamp surface, 17 ... Male Outer peripheral edge of mold, 18 ... vacuum hole, 20 ... female mold, 21 ... female body, 22 ... box, 23 ... fixing plate, 24 ... clamp frame, 25 ... clamp surface, 27 ... flange, 31 ... convex , 32 ... concave portion.

Claims (9)

  A thermoplastic film layer, an adhesive layer, and a support base material layer on which the concave and convex pattern was transferred by an embossing roll were laminated in this order on the surface that was in contact with the adhesive layer was smooth. A method for forming a thermoformed laminate sheet, comprising thermoforming the thermoformed laminate sheet.   The method for forming a laminated sheet for thermoforming according to claim 1, wherein the laminated sheet for thermoforming has a decoration layer between the thermoplastic film layer and the adhesive layer.   The method for forming a laminated sheet for thermoforming according to claim 2, wherein the decorative layer is an ink layer containing a metal thin film strip and a binder resin and having a metallic luster.   The said decoration layer is a metal vapor deposition layer, The shaping | molding method of the laminated sheet for thermoforming of Claim 2. The method for forming a laminated sheet for thermoforming according to claim 1, wherein a forming temperature by the thermoforming is in a temperature range of (T1-20) ° C. or more and (T2) ° C. or less.
However, T1 is the softening temperature of the laminated sheet which integrated the thermoplastic film layer and the support base material layer, and T2 is the softening temperature of the support base material layer. However, the softening temperature here refers to a storage elastic modulus measured under measurement conditions of a frequency of 1 Hz and a heating rate of 3 ° C./min using dynamic viscoelasticity measurement measured in accordance with JIS K7244-1 method. The temperature at the intersection of the straight line obtained by extending the base line on the low temperature side of the temperature dependence curve to the high temperature side and the tangent line drawn at the point where the slope of the step-like change portion becomes the maximum.   The thermoforming heat-plasticizes the part to be molded of the laminated sheet for thermoforming, and then clamps the entire periphery of the part to be molded from both sides using a pair of clamp frames. At least a part of the mold is pressed against the heat plasticized part inside the clamp frame to extend the heat plasticized part between the one mold and the clamp frame, and then 6. The method according to claim 1, wherein the other mold is brought into contact with the heat-plasticized part, and the heat-plasticized part is sandwiched between the one mold and the other mold. A method for forming a laminated sheet for thermoforming described in 1.   The method for forming a laminated sheet for thermoforming according to claim 6, wherein the one mold is a male mold and the other mold is a female mold.   The method for forming a laminated sheet for thermoforming according to claim 6, wherein the one mold is a female mold and the other mold is a male mold.   A clamp frame is used in which the inner peripheral edge of the female-side clamp frame is on the inner side of the inner peripheral edge of the male-side clamp frame, and at least part of one mold is heated and plasticized inside the clamp frame. When the heat plasticized part is extended between the one mold and the clamp frame by pressing against the formed part, the inner peripheral edge part of the clamp frame on the female mold side and the outer peripheral edge part of the male mold The method for forming a laminated sheet for thermoforming according to claim 7, wherein the heat-plasticized portion is sucked from the male mold side using a vacuum while the laminated sheet for thermoforming is clamped between them. .

Images