JP2007118350A - Molded laminated sheet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a laminated sheet for molding which suppresses a deterioration in designability during thermoforming by the water absorption of a resin, is capable of in-mold injection molding using a styrene resin represented by an ABS resin, and has a metallic gloss layer. <P>SOLUTION: In the laminated sheet for molding, a thermoplastic resin film layer, the metallic gloss layer, a support substrate layer (1), and a support substrate layer (2) are laminated in turn. The support substrate layer (1) is made of a resin with a water content of 0.15 mass% or below when the resin is dried at 60°C for 30 min after being saturated with water under the conditions of an ambient temperature of 23°C and a humidity of 50%, and the support substrate layer (2) contains an ABS resin as a main component. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a laminated sheet for thermoforming having a metallic luster layer. The present invention also relates to a three-dimensional molded body obtained by thermoforming the molding laminated sheet, and an injection molded body obtained by in-mold injection molding the molded body.

  As a method for decorating the resin molded member, there are a method in which a pigment is kneaded in a resin and the resin itself is colored and injection molded, and a method of spray coating after molding is available. In particular, when a metallic design is required, the design is often applied by a coating method or a plating method after molding because it is difficult to uniformly disperse the metal pigment in the resin. However, from the viewpoint of protection of the working environment against the discharge of chemical substances and protection of the external environment, a method that replaces the coating method and the plating method is required, and the use of water-based paints and powder paints has been attempted. The expression of the design is difficult at present. On the other hand, a method is known in which a colored sheet on which a moldable support resin layer is laminated is integrally molded during injection molding. According to this method, it is possible to produce a resin-molded member having a metal design without solvent.

As a sheet having a metallic design, a laminated sheet in which a film mainly composed of polyethylene terephthalate (hereinafter referred to as PET) deposited with aluminum and a film mainly composed of polypropylene (hereinafter referred to as PP) is laminated by a dry laminating method is known. It has been. In addition, a laminated sheet having an acrylate emulsion layer containing scaly and smooth aluminum particles as a decoration layer is known (see, for example, Patent Document 1). Further, it has been proposed to use a laminated sheet having an ink film in which metal thin film strips are dispersed in a binder resin varnish as a decorative layer (see, for example, Patent Document 2).

The laminated sheet having these decorative layers is composed of a transparent thermoplastic resin layer, a decorative layer, and a support base material layer. After thermoforming using a vacuum forming method or the like, it is in-mold injection-molded, and is an automobile member or household appliance member. Used for building materials. Therefore, when the injection resin is filled from the back side of the decorative visible surface of the laminated sheet, the support base material layer needs to be heat-fusible with the injection resin. The main component is the same resin as the injection resin.

Resins used for in-mold injection molding vary depending on each application. For example, olefin resins such as polypropylene, styrene resins such as ABS resin (acrylonitrile-styrene-butadiene copolymer), polycarbonate resins, and acrylic resins. Examples thereof include resins.

JP-A-5-111991 JP 2002-46230 A

When using the same resin as the main component of the support base layer when the ABS resin, polycarbonate resin, and blended resins thereof are used as the injection resin, the inventors foamed during thermoforming due to water absorption of the support base layer. And found that the appearance of the decorative layer is significantly impaired. In that case, it is sufficient to dry the sheet in advance before thermoforming. However, it takes time to completely remove the moisture, so that productivity is remarkably lowered and the drying temperature is high, so that the decoration layer is sharp. There was a problem of detracting from sex. In particular, this problem is remarkable when the decorative layer has metallic gloss.

An object of the present invention is to provide a molding laminate having a metallic luster layer capable of suppressing a decrease in designability during thermoforming due to water absorption of the resin and capable of in-mold injection molding using a styrene resin typified by ABS resin. To provide a sheet.

The inventors have introduced a resin layer mainly composed of a resin having low water absorption or high water release on the proximity surface of the metallic luster layer in the support base material layer of the laminated sheet for molding, The present inventors have found that a laminated sheet for thermoforming that suppresses a decrease in decorative sharpness during thermoforming can be obtained even under conditions where the entire sheet absorbs water, and the present invention has been completed.

  That is, the present invention is a laminated sheet for molding in which a thermoplastic resin film layer, a metallic luster layer, a supporting substrate layer (1), and a supporting substrate layer (2) are laminated in this order, The base material layer (1) is a layer made of a resin having a moisture content of 0.15% by mass or less when the substrate layer (1) is saturated with moisture under conditions of an environmental temperature of 23 ° C. and a humidity of 50% and then dried at 60 ° C. for 30 minutes The support base material layer (2) is a layer mainly composed of ABS resin, and provides a laminated sheet for molding.

The present invention also provides a three-dimensional shaped product obtained by thermoforming the molded laminated sheet of the present invention, and a decorative molded product obtained by integrally molding a resin to the molded product.

  The laminated sheet for molding of the present invention has high luster and good thermoformability, and even when it absorbs water during storage, there is little decrease in gloss at the time of thermoforming, and there is no appearance defect due to foaming. It is characterized by.

The laminated sheet for molding of the present invention is described in detail below.
(Laminated sheet for molding)
The laminated sheet for molding of the present invention is a laminated sheet in which a transparent or translucent thermoplastic resin film layer (A), a metallic luster layer (B), and a supporting base material layer (C) are laminated in this order. It is. In this laminated sheet, the thermoplastic resin film layer side is the surface layer, and the metallic luster layer (B) is visible through the transparent or translucent thermoplastic resin film layer (A). Between the thermoplastic resin film layer (A) and the metallic luster layer (B), one or more protective layers for metallic luster layers, adhesive layers, etc. are provided as long as the metallic luster of the sheet is not significantly impaired. May be. One or more other ink layers, adhesive layers, and the like may be provided between the metallic gloss layer (B) and the support base material layer (C). On the thermoplastic resin film layer, one or more surface protective layers (topcoat layers) may be provided on the side that becomes the surface layer during molding.

(Thermoplastic resin film)
As the thermoplastic resin film layer (A) that can be used for the laminated sheet for molding of the present invention, a film that has spreadability by heating is used. The thermoplastic resin film is preferably a transparent or translucent single layer or multilayer film, and may contain a colorant. In order to perform the molding process by heat, a film mainly composed of a thermoplastic resin having a softening temperature 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, polyethylene terephthalate, saturated polyester resins such as polybutylene terephthalate and polyethylene naphthalate, acrylic resins such as polymethyl methacrylate and polyethyl methacrylate, ionomer resins and polystyrene. , Polyacrylonitrile, acrylonitrile-styrene resin, methyl methacrylate-styrene resin, polyamide resin such as nylon, ethylene-vinyl acetate resin, ethylene-acrylic acid resin, ethylene-ethyl acrylate resin, ethylene-vinyl alcohol resin, polyvinyl chloride And chlorinated resins such as polyvinylidene chloride, fluororesins such as polyvinyl fluoride and polyvinylidene fluoride, polycarbonate resins, cyclic Li olefin resins, modified polyphenylene ether resins, methylpentene resins, cellulose resins are preferably used. Among these thermoplastic resins, one or two or more selected from the group of acrylic resins, saturated polyester resins, polycarbonate resins, and cyclic polyolefin resins are used because of their excellent thermoformability and sharpness of the metallic luster layer. A film containing the main component 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.
Further, for the purpose of improving the impact resistance, the various resins exemplified above used as the thermoplastic resin film may be modified with rubber within a range that does not impair the 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. In addition, the thermoplastic resin film may contain various additives that are commonly used for film applications such as an antioxidant, an ultraviolet absorber, and a lubricant as long as the transparency is not impaired. 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.

  The thickness of the thermoplastic resin film is not particularly limited, but is preferably in the range of 30 to 2000 μm, more preferably 50 to 500 μm, since the coating property of the protective layer (described later) of the metallic luster layer is good.

(Glossy metallic layer)
The metallic luster layer (B) is not particularly limited, and ink or paint may be spread on a thermoplastic resin film by a conventional method, or a metal thin film may be formed by a vacuum deposition method, a sputtering method, a plating method, or the like. Examples of the method for spreading ink or paint on the thermoplastic resin film layer (A) include, for example, gravure printing, flexographic printing, screen printing, and other printing methods, gravure coaters, gravure reverse coaters, flexographic coaters, blanket coaters, roll coaters. Coating methods such as knife coater, air knife coater, kiss touch coater, kiss touch reverse coater, comma coater, comma reverse coater, and micro gravure coater can be used.

  In addition, when forming a metal thin film, there are a method of spreading on the thermoplastic film layer (A) and a method of spreading on the support base material layer (C). From the viewpoint of design, the film is spread on the thermoplastic film layer. A method of wearing is preferred. The component of the metal thin film 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 chrome (Ni- Cr), stainless steel (SUS), chromium copper (Cr—Cu), aluminum silicon (Al—Si), and the like.

  If the metallic gloss layer is too thin, the concealability may be inferior and the design may be impaired.If the thickness is too thick, gloss unevenness is likely to occur during thermoforming. Is preferably 0.1 to 5 μm, more preferably 0.5 to 3 μm. When a metal thin film is used, 0.01 to 0.1 μm is preferable, and 0.02 to 0.08 μm is more preferable. In addition, for the purpose of controlling the adhesion between the thermoplastic resin film layer and the metallic luster layer, the surface of the thermoplastic resin film may be subjected to a surface treatment such as corona treatment or primer coating.

(High gloss ink)
When a metal thin film layer or the like by vacuum deposition or the like is used as the metal gloss layer (B), gloss reduction due to cracks occurs in the metal thin film layer in the high extension portion. In that case, the use of a high-brightness ink layer made of high-brightness ink can effectively suppress the above-described reduction in gloss. Here, the high gloss ink is an ink having a mirror-like metallic luster that is obtained 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. High-gloss inks using metal thin film strips are aligned with the metal thin film strips in a direction parallel to the surface of the object when the ink is printed or applied. An unobtainable, high-brightness mirror-like metallic luster is obtained.

(Metal thin film strips in high brightness ink)
As the metal of the metal thin film strip used for the high-brightness ink, various metals exemplified above as the components of the metal thin film can be preferably used. As a method of 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, foil is formed in the case of a malleable metal such as aluminum, gold, silver, copper, and indium. In the case of a poor metal, sputtering or the like 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. If the size of the metal thin strip is less than 5 μm, the brightness of the coating film of high-brightness ink will decrease, and clogging of the plate will occur when the ink is printed or applied by gravure or screen printing. 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, methyl ethyl ketone and methyl isobutyl 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 high brightness ink)
As the binder resin used for the high gloss ink, those conventionally used in 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 high gloss ink)
If necessary, the high-brightness ink has no defoaming, settling prevention, pigment dispersion, fluidity modification, anti-blocking, antistatic, antioxidation, light stability in the ink as long as it does not impair the design and spreadability. Various additives used in conventional gravure inks, flexo inks, screen inks, paints, etc. may be added for the purpose of properties, 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 high brightness ink)
As the solvent used in the high gloss ink, known conventional solvents used in conventional gravure ink, flexo ink, screen ink, paint, and 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, methyl ethyl ketone, and methyl isobutyl ketone; alkylene glycol alkyl ethers such as ethylene glycol monoethyl ether and propylene glycol monomethyl ether.

(Preparation method of high brightness ink)
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-mentioned high-brightness ink, the metal thin film strip to be blended for expressing the metallic luster is preferably 5 to 25 μm, and when the above-mentioned kneaded meat is formed, the metal thin film strip becomes fine particles. In addition, the metallic luster may be extremely lowered. Therefore, it is desirable not to perform kneading when preparing a high-brightness ink, but to simply mix the above blended raw materials to obtain 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 high-brightness ink layer of the thermoforming sheet used in the present invention, other ink layers that may be further laminated on the ink layer, and the printing or coating method of the adhesive include gravure printing, flexographic printing, screen Printing method such as printing: 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. A construction method 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 an ink layer, 5 micrometers or less are preferable, 0.1-5 micrometers is more preferable, Especially preferably, it is 0.5-3 micrometers.

(Supporting substrate layer)
The supporting base material layer (C) of the forming laminated sheet of the present invention is a forming laminated sheet in which a supporting base material layer (1) and a supporting base material layer (2) are laminated, wherein the supporting base material layer (1) is the proximity layer of the metallic luster layer, and after moisture saturation under the conditions of an environmental temperature of 23 ° C. and a humidity of 50%, the moisture content when dried at 60 ° C. for 30 minutes is 0.15% by mass or less The support base material layer (2) is a layer mainly composed of ABS resin. However, a main component means containing 50 mass% or more with respect to the whole resin which forms a layer.

  The resin constituting the support base layer (1) preferably has a heat-fusibility with the support base layer (2). However, when it does not have heat-fusibility, a layer using a hot melt adhesive may be introduced between the support base material layer (1) and the support base material layer (2). Examples of the resin having a moisture content of 0.15% by mass or less when dried at 60 ° C. for 30 minutes after being saturated with water under conditions of an environmental temperature of 23 ° C. and a humidity of 50% include methyl methacrylate, ethyl methacrylate, Polymer having at least one selected from butyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate as a monomer, styrene, methyl methacrylate, ethyl methacrylate, butyl methacrylate, methyl acrylate, acrylic acid Copolymer with at least one monomer selected from ethyl and butyl acrylate, vinyl chloride polymer, vinylidene chloride polymer, vinyl chloride-vinylidene chloride copolymer, polyethylene terephthalate, polybutylene terephthalate, polyethylene terephthalate, These rubber-modified products are listed. Rukoto can. The rubber-modified product is a method in which a diene compound such as butadiene or isoprene is copolymerized during the polymerization of the resin, or a styrene-butadiene copolymer, a styrene-isoprene copolymer, a styrene-isoprene-butadiene copolymer, or styrene. -Styrene elastomer such as ethylene-butylene copolymer, styrene-ethylene-propylene copolymer, styrene- (meth) acrylic acid alkyl ester-butadiene copolymer, olefin elastomer such as ethylene propylene rubber, and silicon- What was obtained by the method of melt-mixing synthetic rubber powders, such as acrylic rubber, is mentioned. These may be used alone or in combination.

The resin constituting the support base material layer (2) is a layer mainly composed of ABS resin. However, a main component means containing 50 mass% or more with respect to the whole resin which forms a layer. Components other than the ABS resin contained in the support base layer (2) are not particularly limited, but from the viewpoint of compatibility with the ABS resin, polycarbonate resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyamide resin, acrylic resin Examples thereof include resins, saturated polyester resins, styrene-acrylonitrile copolymers, and styrene-butadiene copolymers.

The ratio of the supporting substrate layer (1) and the supporting substrate layer (2) is not particularly limited, but the gloss of the present invention due to water absorption is reduced when the thickness of the supporting substrate layer (1) is 0.005 mm or more. It is preferable that the thickness of the support base material layer (2) is 0.01 mm or more from the viewpoint of good adhesion to the injection resin at the time of in-mold injection molding.

The total thickness of the supporting substrate layer (1) and the supporting substrate layer (2) is preferably 0.03 mm to 3.0 mm, more preferably 0.05 mm to 1.0 mm because thermoformability is improved.

  The lamination method of the supporting substrate layer (1) and the supporting substrate layer (2) uses a co-extrusion method by heat melting because the film forming cost is low, and an efficient sheet with less thickness unevenness is obtained. Is preferred. The extrusion conditions of the sheet for the supporting base material layer (C) by the coextrusion molding method are not particularly limited because they vary depending on the resin composition constituting each supporting base material layer, but generally a resin temperature of 150 to 300 ° C. Then, the resin composition kneaded and melted by each extruder is laminated in a feed block which is a resin merging apparatus, and melt-extruded by a T-die to form a sheet. The melt-extruded sheet is formed into a sheet shape having a predetermined thickness distribution by adjusting the lip opening of the T die, and then cooled as necessary. Although the cooling method is not particularly limited, a method of cooling while winding with a temperature-adjustable roll is preferable because a sheet with less thickness unevenness is obtained, and a touch roll, an air knife, or the like is used as an auxiliary cooling device. I can do it.

  When the supporting substrate layer (1) and the supporting substrate layer (2) do not have heat-fusibility, an adhesive layer is provided between the layers, and the supporting substrate layer ( C) may be obtained. Moreover, the support base material layer (C) which introduce | transduced the adhesive bond layer similarly to the above can also be obtained also by combined use of a coextrusion molding method and an extrusion lamination method.

  The laminated sheet for molding of the present invention is thermoformed into a three-dimensional shaped product, and is a thermoplastic resin film layer (A) laminated via a supporting base layer (C) and a metallic luster layer (B). When the resin composition used has a different molding shrinkage ratio, the molded body is deformed and a good shape cannot be maintained. The molding shrinkage rate of the supporting base material layer (C) and the thermoplastic resin film layer (A) is not particularly limited as long as deformation of the laminated sheet for molding of the present invention does not occur, but the supporting base material layer (C) The difference in molding shrinkage between the thermoplastic resin film layer (A) and the thermoplastic resin film layer is preferably 0.7% or less, and more preferably 0.4% or less.

It is preferable to add a colorant to the support base material layer because the concealability of the base color of the molded article is improved. The colorant to be used is not particularly limited, and conventional inorganic pigments, organic pigments and dyes used for coloring general thermoplastic resins can be used according to the intended design. For example, inorganic pigments such as titanium oxide, titanium yellow, iron oxide, complex oxide pigments, ultramarine, cobalt blue, chromium oxide, bismuth vanadate, carbon black, zinc oxide, calcium carbonate, barium sulfate, silica, talc; azo Pigments, phthalocyanine pigments, quinacridone pigments, dioxazine pigments, anthraquinone pigments, isoindolinone pigments, isoindoline pigments, perylene pigments, perinone pigments, quinophthalone pigments, thioindigo pigments and diketopyrrolo Organic pigments such as pyrrole pigments; metal complex pigments and the like. Moreover, it is preferable to use 1 type or 2 types mainly chosen from the group of an oil-soluble dye as a dye.

The amount of colorant added to the support base layer varies depending on the type of colorant and the desired thickness and color tone of the sheet, but in order to ensure the concealment of the hue and background color and maintain the impact strength. Furthermore, it is preferable that it is the range of 0.1-20 mass% with respect to resin which comprises a colored layer, More preferably, it is the range of 0.5-15 mass%. When the colorant is added in excess of 20% by mass, the impact strength is lowered, and when the amount of the colorant added is less than 0.1%, there is a tendency that the hiding property of the hue and the background color is not sufficient. In addition, additives such as plasticizers, antioxidants, ultraviolet absorbers, antistatic agents, flame retardants and lubricants may be blended as long as the impact strength and moldability are not impaired. It may be used alone or in combination of two or more.

The laminated sheet for molding of the present invention has a solvent resistance, heat resistance, and weather resistance when the adhesive and high gloss ink layer is spread between the thermoplastic resin film layer (A) and the metallic luster layer (B). One or more protective layers of the metallic luster layer (B) may be provided for the purpose of improving the properties and design properties. The type of resin that can be used for the protective layer is not particularly limited as long as it does not hinder transparency and spreadability during thermoforming, but is preferably an acrylic cross-linked resin from the viewpoint of adhesiveness with a transparent thermoplastic resin film. . The crosslinking mechanism is not particularly limited, and in the case of acrylic resins, UV curing, EB curing, hydroxyl group-containing copolymer / isocyanate curing, silanol / water curing, epoxy / amine curing, etc. can be used. From the viewpoints of ease, weather resistance, reaction rate, presence or absence of reaction byproducts, production cost, etc., a hydroxyl group-containing copolymer / isocyanate curing is preferred.

As a laminate of the thermoplastic resin film layer (A) and the protective layer, the haze (cloudiness value) is preferably less than 5%, but from the viewpoint of design, colorants such as pigments and dyes are added to the protective layer. In addition, the transparency can be intentionally lowered. In this case, the amount of the colorant added varies depending on the type of colorant, the target color tone, and the thickness of the protective layer. However, the thermoplastic resin film layer (A) and the protective layer are protected so as not to conceal the metallic gloss layer (B). It is preferable that the haze (cloudiness value) of the layered laminate is less than 20%.

The colorant is preferably a pigment from the viewpoint of weather resistance. The pigment to be used is not particularly limited, and known and commonly used pigments such as colored pigments, metallic pigments, interference color pigments, fluorescent pigments, extender pigments and rust preventive pigments can be used.

Examples of the color pigment include quinacridone series such as quinacridone red, azo series such as pigment red, phthalocyanine series organic pigments such as phthalocyanine blue, phthalocyanine green, and perylene red; and inorganic pigments such as titanium oxide and carbon black. Examples of the metallic pigment 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-colored pearl mica powder. Examples of the fluorescent pigment include quinacridone, anthraquinone, perylene, perinone, and diketopyrrolopyrrole. , Isoindolinone, condensed azo, benzimidazolone, monoazo, insoluble azo, naphthol, flavanthrone, anthrapyrimidine, quinophthalone, pyranthrone, pyrazolone, thioindigo, anthanthrone, dioxazine , Organic pigments such as phthalocyanine and indanthrone, metal complexes such as nickel dioxin yellow and copper azomethine yellow, metal oxides such as titanium oxide, iron oxide and zinc oxide, barium sulfate and calcium carbonate Metal salt, carbon black, aluminum Inorganic pigments fine mica.

(Lamination method)
The metallic gloss layer (B) and the support base material layer (C) can be laminated via an adhesive layer. As a bonding method, a laminated sheet can be formed by a dry lamination method, a wet lamination method, a hot melt lamination method, etc. using a conventional solvent-type adhesive, but the high gloss of the laminated sheet for molding of the present invention can be obtained. Is preferable because the dry lamination method is preferable.

The adhesive which comprises the said adhesive bond layer is not specifically limited, A normal adhesive can be used. For example, conventional phenol resin adhesives, resorcinol resin adhesives, phenol-resorcinol resin adhesives, epoxy resin adhesives, urea resin adhesives, polyurethane adhesives and polyaromatic adhesives, etc. Curable resin adhesive; reactive adhesive using ethylene-unsaturated carboxylic acid copolymer; vinyl acetate resin, acrylic resin, ethylene-vinyl acetate resin, polyvinyl alcohol, polyvinyl acetal, vinyl chloride, nylon and cyanoacrylate Examples include thermoplastic resin adhesives such as resins; rubber adhesives such as chloroprene adhesives, nitrile rubber adhesives, styrene-butadiene rubber adhesives, and natural rubber adhesives. Of these, various urethane-based adhesives are preferable because they have good followability of elongation during thermoforming such as vacuum forming.

As for the coating method of these adhesives, gravure coater, gravure reverse coater, flexo coater, blanket coater, roll coater, knife coater, air knife coater, kiss touch coater, comma coater, etc. can be used, and metallic gloss layer (B) Or it apply | coats on the surface of the support base material layer (1) which comprises a support base material layer (C).

The application amount of the adhesive is preferably in the range of 0.1 to 30 g / m ² and particularly preferably ² to 10 g / m ^{2 in} order that the adhesive force is sufficient and the solvent drying property is good. If it is less than 2 g / m ² , the adhesive strength is weakened, and if it is more than 10 g / m ² , the solvent drying property is lowered. The thickness of the adhesive layer is preferably in the range of 0.1 to 30 μm, more preferably 1 to 20 μm, and particularly preferably 2 to 10 μm.

In addition, plasma is applied to the sheet surface of the support base material layer (1), which is an adhesive surface between the thermoplastic resin film layer (A) and the support base material layer (C), in order to improve the affinity with the adhesive. It is preferable to perform surface treatment such as treatment, corona treatment, frame treatment, electron beam irradiation treatment, surface roughening treatment, ozone treatment, and the like so that the wetting index is 35 dyne / cm or more. Furthermore, a dry plating process such as vacuum deposition, sputtering, or ion plating may be performed.

Moreover, it can replace with the said adhesive bond layer and can also provide an adhesive layer. As the adhesive, acrylic, rubber, polyalkyl silicon, urethane, polyester, and the like are preferably used.

(Sheet molding)
The laminated sheet for molding of the present invention can be thermoformed by a conventional method, and the molded body can be inserted into an injection mold and in-mold injection molded. Specifically, the sheet is formed using a vacuum forming method (including a plug-assisted vacuum forming method), a vacuum / pressure forming method (including a plug-assisted vacuum / pressure forming method), a hot plate / pressure forming method, a press forming method, or the like. After forming the three-dimensional molded body, the molded body is inserted into the mold so that the thermoplastic resin film layer side is in contact with the concave mold side of the injection mold, the mold is closed, and the injection resin is injected from the back side of the molded body. An injection-molded body is obtained by an in-mold injection molding method for filling.

The forming conditions of the vacuum forming method are not particularly limited. When a far infrared heater is used, the heater temperature is 200 to 500 ° C., the indirect heating time is 5 to 30 seconds, and the sheet can be formed. For example, the storage elastic modulus (E ′) of dynamic viscoelasticity measurement (hereinafter referred to as “DMA”) determined by JIS K7244-1 is a measurement condition with a frequency of 1 Hz and a heating rate of 3 ° C./min. The temperature is preferably 0.1 to 50 MPa. The mold temperature needs to be determined while confirming the appearance and the degree of shrinkage of the molded article to be obtained, but it is preferably 20 to 80 ° C. and the cooling time by the mold is preferably 1 to 60 seconds.

The forming conditions of the vacuum / pressure forming method are not particularly limited, but when a far infrared heater is used, the heater temperature is 200 to 500 ° C., the indirect heating time is 5 to 30 seconds, and the sheet can be formed. The temperature at which the storage elastic modulus (E ′) of DMA is from 1 to 250 MPa is preferred. The mold temperature is the same as in the vacuum forming method.

When the hot plate pressure forming method is used, the hot plate temperature is preferably set to a temperature at which the storage elastic modulus (E ′) of DMA becomes 0.1 MPa to 100 MPa as in the vacuum pressure forming method. The heating time by the hot plate varies depending on the thickness of the sheet, but is 1 to 20 seconds, and the molding pressure is preferably 1 to 250 MPa.

Furthermore, the laminated sheet for molding according to the present invention provides a molded article with excellent decorative sharpness as it is molded at a low temperature, and in particular, in the case of a metallic luster design, a highly glossy molded article is obtained. It is preferable to apply a press molding method (also called a match mold molding method) which is a mechanical molding method. Here, the press molding method refers to a method in which a heated sheet is sandwiched between a concave mold and a convex mold to form a molded body. In this case, by setting the sheet temperature at the time of molding to (the glass transition temperature of the thermoplastic resin film + 20 ° C.) or less, a molded article having excellent decorative sharpness can be obtained. The glass transition temperature referred to here is the peak temperature of tan δ when measured at a frequency of 1 Hz and a heating rate of 3 ° C./min using DMA. More specifically, when a far infrared heater is used, the heater temperature is 200 to 500 ° C., the indirect heating time is 5 to 30 seconds, the temperature at which the sheet can be formed, and the DMA storage elastic modulus (E ′). Is preferably set to a temperature of 10 to 500 MPa. In addition, the mold temperature needs to be determined while confirming the appearance and the degree of shrinkage of the obtained molded body, but is set to 20 to 200 ° C., and the pressing time between the concave mold and the convex mold is set to 10 seconds to 5 minutes. It is preferable. Further, after the press molding is completed, the obtained molded body may be cooled with air or the like.

(In-mold injection molding)
Next, the three-dimensional molded body (preform) obtained by thermoforming the sheet is placed so that the thermoplastic resin film side is in contact with the concave mold (cavity) of the injection mold, and the back surface of the molded body An injection molded body can be formed by integral molding by filling the side with an injection resin. However, if the shape of the target injection-molded body is a two-dimensional shape or a simple three-dimensional shape with a maximum expansion rate of less than 120%, the sheet is not used as a molded body and remains in the sheet shape. By inserting into an injection mold, an in-mold injection molded body can be obtained. That is, the three-dimensional molded body of this sheet used for in-mold injection molding does not necessarily have the same shape as the concave mold of the injection mold, but the preform R reproducibility with respect to the concave mold of the injection mold is 50%. The above is preferable.

As the injection resin, it is preferable that the ABS resin is a main component from the viewpoint of adhesion with the support base material layer, and specifically, the ABS resin is preferably 30% by mass or more in the injection resin. 50% by mass or more is more preferable, and 70% by mass or more is still more preferable.

Components other than ABS resin contained in the injection resin are not particularly limited, but from the viewpoint of compatibility with ABS resin, polycarbonate resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyamide resin, acrylic resin, saturated polyester resin Styrene-acrylonitrile copolymer, styrene-butadiene copolymer and the like.

A high gloss molded laminate sheet is formed by thermoforming, and then the resulting molded body and resin are integrally molded to form a molded body of resin having high gloss (hereinafter referred to as a decorative molded body). Say.) Can be obtained. 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 concave mold of the injection mold, and filling the injection resin on the back side of the molded body, or the injection mold 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.

Furthermore, the injection resin may contain additives such as colorants, plasticizers, antioxidants, ultraviolet absorbers, antistatic agents, flame retardants and lubricants, and these additives are used alone. Or you may use 2 or more types together.

The filling temperature of the injection resin is not particularly limited, but if the resin temperature is too low, the adhesiveness between the support base layer and the injection resin becomes insufficient, and if the resin temperature is too high, the injection molded body warps as a sink. In the case of an ABS resin, 200 to 280 ° C. is preferable and 210 to 270 ° C. is more preferable because defects are likely to occur. The injection mold temperature is preferably 30 to 100 ° C. for both the concave mold and the convex mold. However, when warping or the like occurs in the injection molded body, it is necessary to provide a temperature gradient to the concave mold and the convex 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.

  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.

Example 1
A method for producing a laminated sheet is shown below.
(Thermoplastic resin film layer (A))
As the thermoplastic resin film layer, a rubber-modified PMMA film (trade name “Technoloy S-001”, manufactured by Sumitomo Chemical Co., Ltd.) having a haze of 0.1% and a thickness of 75 μm was used.
(Protective layer solution)
In order to improve the adhesion between the thermoplastic resin film layer (A) and the metallic luster layer (B), an acrylic polyol resin “6KW-032E” (trade name, manufactured by Dainippon Ink & Chemicals, Inc., solid content 38% (solvent) : Ethyl acetate), hydroxyl value 30 KOH mg / g) In a mixed solution of 46 parts and 46 parts of 4-methyl-2-pentanone, an isocyanurate ring-containing polyisocyanate “BURNOCK DN-981” (trade name, Dainippon Ink and Chemicals, Inc.) 8 parts of solid content 75% (solvent: ethyl acetate), functional group number 3, NCO concentration 14%) were mixed (100 parts in total) to prepare a protective layer solution (primer).

(Solution for metallic luster layer (B) (high gloss ink))
Mix 10 parts of aluminum thin film strip (thickness 0.04 μm, size 5-25 μm in the plane direction), 37.25 parts of ethyl acetate, 30 parts of methyl ethyl ketone, 31.5 parts of isopropyl alcohol, and 1.25 parts of nitrocellulose. (110 parts in total) to prepare an aluminum thin film 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 parts) is mixed with 8 parts of ethyl acetate, 23 parts of ethyl acetate, 26 parts of 4-methyl-2-pentanone and 10 parts of isopropyl alcohol (100 parts in total), and the aluminum film thin film concentration in the nonvolatile content is 35% by mass. Ink was prepared.

(Adhesive layer solution (between layer (A) and layer (B))
Aromatic polyester polyol resin “LX-703VL” (trade name, Dainippon Ink & Chemicals, Inc.) is used as the main agent for bonding the thermoplastic resin film layer (A) having the metallic gloss layer (B) and the supporting base material layer (C). 15 parts by industry, 1 part aliphatic polyisocyanate “KR-90” (trade name, manufactured by Dainippon Ink & Chemicals, Inc.) as a curing agent and 18 parts ethyl acetate as a diluent (total 34 parts) A polyester urethane-based adhesive was prepared.

(Supporting substrate layer (C))
(Supporting substrate layer (1))
As the supporting substrate layer (1) constituting the supporting substrate layer, a styrene-methyl methacrylate-butyl acrylate terpolymer (hereinafter referred to as MS resin) “Cry assist TS-10” (trade name, Dainippon Ink and Chemicals, Inc.) (Resin 1-1) was used alone.

(Supporting substrate layer (2))
As the support base material layer (2) constituting the support base material layer, a transparent ABS resin “Clarastic SXH-290” (trade name, manufactured by Nippon A & L Co., Ltd.) (resin 2-1) was used alone.

(Preparation of sheet for supporting substrate layer (C))
Using two single-screw extruders, the resin (1-1) and the resin (2-1) were 210 ° C., respectively, as the two types of support base material layers (1) and support base material layers (2). It is melted at 240 ° C., laminated with a feed block so that the layer composition ratio (thickness ratio) of resin (1-1) / resin (2-1) = 10/90, and extruded into a sheet through a T-die. After that, it was immediately cooled with a metal roll whose temperature was adjusted to 80 ° C. to obtain a sheet for supporting base material layer having a thickness of 0.20 mm.

(Sheet stacking method)
The protective layer solution was applied to the rubber-modified PMMA film using a micro gravure coater so as to have a dry film thickness of 1.5 μm, and then subjected to aging treatment at 50 ° C. for 3 days. Next, the high gloss ink as a metallic luster layer (B) was applied to the protective layer using a micro gravure coater so as to have a dry film thickness of 1.5 μm, and then subjected to an aging treatment at 50 ° C. for 3 days. Furthermore, after the corona treatment was applied to the adhesive surface (supporting base material layer (1)) of the sheet for supporting base material layer so as to have a wetness index of 40 dyne / cm, the adhesive was applied to the high gloss ink coated surface with a microbravia coater. Was applied and dried so as to have a dry film thickness of 5 μm, bonded to the sheet for supporting base material layer, and subjected to aging treatment at 50 ° C. for 3 days to obtain a laminated sheet for molding (I). The 20 ° gloss value (measurement angle: 20 °) of the sheet was 890%. Here, the 20 ° gloss value was measured according to JIS Z8741 using “Micro-TRI-gloss” manufactured by BYK Gardner.

(Moisture content measurement)
The moisture content of the resin for supporting substrate layer (1-1) and the resin (2-1) is measured using a Karl Fischer moisture meter (MKC-201, manufactured by Kyoto Electronics Industry Co., Ltd.) using each single-layer sheet or pellet. Used and measured according to JIS K7521. The monolayer sheet or pellet is left in a constant temperature part at a temperature of 23 ° C. and a humidity of 50% RH for 1 week or longer to saturate water content (hereinafter referred to as saturated water content) and hot air at 60 ° C. The moisture content immediately after being left in the dryer for 30 minutes (hereinafter referred to as the moisture content after drying) was measured. A resin having a large difference between the saturated moisture content and the moisture content after drying can be said to be a resin having high water release. The saturated water content of the resin (1-1) was 0.12%, and the water content after drying was 0.10%. Moreover, the saturated water content of the resin (2-1) was 0.23%, and the water content after drying was 0.17%.

(Vacuum forming)
The laminated sheet (I) is indirectly heated from the thermoplastic resin film side using a Hermis FE38PH small vacuum forming machine, and immediately after the heater is retracted, the mold is raised from the opposite side to form a vacuum formed body. Produced. The heating time was 15 seconds, the sheet temperature was 130 ° C., the heater temperature was 370 ° C., the distance between the sheet and the heater was 130 mm, the mold temperature was 60 ° C., and the vacuum / cooling time was 8 seconds. In addition, sheet temperature uses the infrared radiation thermometer IT2-80 (emissivity (epsilon) = 0.95) by Keyence Corporation, and lowers the sheet | seat temperature near the upper part of a metal mold | die center (support base material layer side). Measured from Moreover, the average expansion ratio of the bottom part of the obtained vacuum formed body was 150%.
Vacuum forming mold: 154 x 160 x 30mm (concave, corner: 15mmR)

(Condition 1)
As a result of vacuum forming under the above conditions within 1 hour after completion of the production of the laminated sheet (I) for molding (after the aging treatment), the 20 ° gloss value of the 150% developed portion was 460%.
(Condition 2)
The laminated sheet (I) for molding was allowed to stand for 3 days in the state of a single wafer under conditions of a temperature of 23 ° C. and a humidity of 50% RH, and then vacuum-formed under the above conditions. Was 425%, and the gloss retention of Condition 1 and Condition 2 was 92%. Moreover, the appearance defect by foaming was not recognized by the metal glossy surface of this vacuum forming body.

(Example 2)
Molded in the same manner as in Example 1 except that the supporting substrate layer (2) in the supporting substrate layer is composed of a general-purpose ABS resin “Clarastic SRE” (trade name, manufactured by Nippon A & L Co., Ltd.) (2-2). A laminated sheet (II) was obtained. The 20 ° gloss value of the sheet was 880%, the 20 ° gloss value of the developed part of the 150% vacuum formed body was 440% under Condition 1, 410% under Condition 2, and the gloss retention was 93%. Moreover, the appearance defect by foaming was not recognized by the metal glossy surface of this vacuum forming body. Moreover, the saturated water content of the above (2-2) was 0.28%, and the water content after drying was 0.23%.

(Example 3)
A laminated laminate sheet for molding in the same manner as in Example 1 except that the support base material layer (1) of the support base material layer is made of PMMA resin “SUMIPEX LG” (trade name, manufactured by Sumitomo Chemical Co., Ltd.) (1-2). III) was obtained. The 20 ° gloss value of the sheet was 760%, and the 20 ° gloss value of the developed portion of the 150% vacuum formed body was 460% under Condition 1, 445% under Condition 2, and the gloss retention was 97%. Moreover, the appearance defect by foaming was not recognized by the metal glossy surface of this vacuum forming body. The saturated water content of (1-2) was 0.63%, and the water content after drying was 0.14% by mass. PMMA is a highly hygroscopic resin with high moisture absorption, but has a moisture content of 0.15% or less after drying.

(Comparative Example 1)
A comparative laminated sheet (I ′) was obtained in the same manner as in Example 1 except that the supporting base material layer was a single layer sheet made of a transparent ABS resin (2-1). The 20 ° gloss value of the sheet was 885%, the 20 ° gloss value of the 150% developed portion of the vacuum formed body was 440% under condition 1, 360% under condition 2, and the gloss retention was 82%. Further, appearance defects due to fine foaming occurred on the metallic gloss surface of the vacuum formed body.

(Comparative Example 2)
A comparative laminated sheet (II ′) was obtained in the same manner as in Example 1 except that the supporting base material layer was a single layer sheet made of a general-purpose ABS resin (2-1). The 20 ° gloss value of the sheet was 880%, and the 20 ° gloss value of the 150% developed portion of the vacuum formed body was 390% under Condition 1, 325% under Condition 2, and the gloss retention was 83%. In addition, many appearance defects due to foaming occurred on the metallic gloss surface of the vacuum formed body.

The results of Examples 1 to 3 and Comparative Examples 1 and 2 are shown in Table 1. From the results of Table 1, the gloss value of the vacuum formed body is improved by arranging a resin layer mainly composed of a resin having low water absorption or high water release on the metallic luster layer side of the support base material layer. It was found that the gloss reduction due to moisture absorption of the support base material layer can be suppressed. Furthermore, it can be inferred that the effect of the present invention becomes remarkable under high temperature and high humidity.

  The laminated sheet for molding of the present invention can be used for automobile members, home appliance members, building members and the like as plastic molded bodies decorated by in-mold injection molding after thermoforming.

The schematic diagram of the lamination sheet for shaping | molding in which the thermoplastic resin film layer in this invention, the metallic luster layer, the support base material layer which consists of a support base material layer (1) and a support base material layer (2) were laminated | stacked in this order. It is.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Thermoplastic resin film layer 2 Metal luster layer 3 Support base material layer (1)
4 Support base material layer (2)
5 Support base material layer

Claims (7)

A thermoplastic laminated film layer, a metallic luster layer, a supporting base material layer (1), and a supporting base material layer (2) are laminated sheets in this order, wherein the supporting base material layer (1 ) Is a layer made of a resin having a moisture content of 0.15% by mass or less when dried at 60 ° C. for 30 minutes after being saturated with water under conditions of an environmental temperature of 23 ° C. and a humidity of 50%, A layered sheet for molding, wherein the base material layer (2) is a layer mainly composed of ABS resin. The laminated sheet for molding according to claim 1, wherein the metallic luster layer is a high-gloss ink layer containing a metallic thin film layer or a metallic thin film strip and a binder resin and having a metallic luster. The support base layer (1) is a (meth) acrylic acid alkyl ester polymer, a styrene- (meth) acrylic acid alkyl ester copolymer, a vinyl chloride polymer, a vinylidene chloride polymer, a saturated polyester resin, or a rubber thereof. The laminated sheet for molding according to claim 1 or 2, which contains at least one resin selected from the group consisting of modified products. The laminated sheet for molding according to claim 1, further comprising an adhesive layer between the metallic luster layer and the supporting base material layer (1). A three-dimensional shaped product obtained by thermoforming the forming laminated sheet according to any one of claims 1 to 4. A decorative molded body obtained by integrally molding a resin with the molded body according to claim 5. The decorative molded body according to claim 6, wherein the integrally molded resin contains 30% by mass or more of ABS resin.

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