JP2019171782A - Laminate for metallic decoration and molded body of the same - Google Patents

Abstract

To provide a laminate for metallic decoration in which lowering of image clarity after molding is suppressed.SOLUTION: A laminate for metallic decoration has an acrylic film, a primer layer, an indium layer, an adhesive layer and a resin substrate in this order, in which the primer layer contains (A) acrylic polyol as a main agent and (B) a reaction product with an isocyanate compound as a curing agent, and a molar ratio of the isocyanate group of the isocyanate compound to 1 mol of a hydroxyl group of the acrylic polyol is 0.25/1 to 2.0/1.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a laminate for metallic decoration and a molded body thereof.

  Conventionally, in order to improve the designability of a molded body, a metallic luster has been imparted to the surface of the molded body. As a means for imparting metallic luster, metal plating has been performed for a long time. However, metal plating has problems such as complicated processes and high production costs, and generation of waste liquid and environmental load. Moreover, when the surface of the molded body has an uneven shape, it has been difficult to apply a uniform and clean plating film.

As an alternative to metal plating, means for decorating the surface of an adherend such as a resin molded body using a decorative sheet having a metallic luster has been proposed.
In patent document 1, what has a metal film on a transparent substrate is used as a molding sheet having a metallic luster, and the acrylic film is used as the transparent substrate from the viewpoint of flexibility and followability of the film itself. Is used, and from the viewpoint of improving the adhesion strength between the acrylic film and the metal film, a primer layer is used as a two-component curable resin in which an isocyanate is added to a mixture of a urethane resin and a ketone resin, Further, ABS resin is used as an adherend through an adhesive layer made of acrylic resin or the like.
In the above configuration, the surface of the acrylic film may be uneven as a result of the expansion of moisture generated from the ABS resin at the temperature in the heating process at the time of molding. In order to remove moisture in the adherend, for example, heat drying may be performed at a temperature of 70 to 90 ° C. for several tens of hours.

Japanese Patent No. 5809768

  However, when the heat-drying is performed, unevenness on the surface of the acrylic film due to moisture from the ABS resin is eliminated, but the acrylic film heat shrinks in the first place due to heat during drying. The image clarity of the resin molding may be reduced.

  This invention is made | formed in view of such a situation, and makes it a subject to provide the laminated body for metal tone decoration in which the fall of the image clarity after shaping | molding was suppressed.

In order to solve the above problems, the present invention provides the following (1) and (2).
(1) A laminate for metallic decoration having an acrylic film, a primer layer, an indium layer, an adhesive layer and a resin substrate in this order, wherein the primer layer is (A) an acrylic polyol as a main agent, and a curing agent. (B) a metal product comprising a reaction product with an isocyanate compound, wherein the molar ratio of the isocyanate group of the isocyanate compound to 1 mol of the hydroxyl group of the acrylic polyol is 0.3 / 1 to 2.5 / 1. Laminated body for decoration.
(2) A metal-decorated molded article using the laminate for metallic decorating according to (1) above.

  ADVANTAGE OF THE INVENTION According to this invention, the laminated body for metallic decorations by which the fall of the image clarity after shaping | molding was suppressed can be provided.

It is sectional drawing which shows embodiment of the laminated body for metallic decorations of this invention.

[Metallic decorative laminate]
The laminate for metallic decoration of the present invention is a laminated body for metallic decoration having an acrylic film, a primer layer, an indium layer, an adhesive layer and a resin substrate in this order, and the primer layer is used as a main agent. (A) A reaction product of acrylic polyol and (B) isocyanate compound as a curing agent, wherein the molar ratio of the hydroxyl group of the acrylic polyol to 1 mol of the isocyanate group of the isocyanate compound is 0.3 / 1 to 2 .5 / 1.

  Drawing 1 is a sectional view showing an embodiment of a layered product for metallic decoration of the present invention. 1 has an indium layer 4 via a primer layer 3 and a resin substrate 6 via an adhesive layer 5 on an acrylic film 2.

  The laminate for metallic decoration includes an acrylic film, a primer layer, an indium layer, an adhesive layer, and a resin substrate in this order. Moreover, the laminated body for metallic decoration should just have an acrylic film, a primer layer, an indium layer, an adhesive layer, and a resin base material in this order, and between these layers or the surface, a protective layer, an adhesion layer, You may have other layers, such as a colored layer.

  First, the primer layer which is the characteristic of the laminated body for metallic decorations of this invention is demonstrated.

(Primer layer)
A primer layer is provided between the acrylic film and the indium layer. The primer layer used in the present invention improves the moldability and adhesion of the laminate for metallic decorating, and suppresses the thermal shrinkage of the acrylic film that occurs during heat drying of the resin substrate of the laminated laminate for metallic decorating. This makes it easy to suppress a decrease in the image clarity of the molded metallic decorative article after molding.
The primer layer contains a reaction product of (A) an acrylic polyol as a main agent and (B) an isocyanate compound as a curing agent.

(A) The acrylic polyol is not particularly limited as long as it is an acrylic polymer having two or more hydroxyl groups in the molecule. (A) The acrylic polyol is preferably a copolymer obtained by copolymerizing a hydroxyl group-containing acrylate and a copolymerizable vinyl monomer copolymerizable with the hydroxyl group-containing acrylate.
Examples of the hydroxyl group-containing acrylate include 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, 2,2-dihydroxymethylbutyl (meth) acrylate, polyhydroxyalkyl maleate, poly And hydroxyalkyl fumarate. Preferably, 2-hydroxyethyl (meth) acrylate etc. are mentioned.
Examples of the copolymerizable vinyl monomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, and s-butyl ( Examples include alkyl (meth) acrylates such as (meth) acrylate, t-butyl (meth) acrylate, and pentyl (meth) acrylate. Also, for example, aromatic vinyl such as styrene, vinyl toluene, α-methyl styrene, etc., vinyl cyanide such as (meth) acrylonitrile, carboxyl such as (meth) acrylic acid, fumaric acid, maleic acid, itaconic acid, etc. Vinyl monomer containing a group, or an alkyl ester thereof, such as ethylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, hexanediol di (meth) acrylate, oligoethylene glycol di (meth) acrylate, trimethylolpropane Examples include alkane polyol poly (meth) acrylates such as di (meth) acrylate and trimethylolpropane tri (meth) acrylate.
The acrylic polyol can be obtained by copolymerizing these hydroxyl group-containing acrylate and copolymerizable vinyl monomer in the presence of a suitable solvent and polymerization initiator.
The number average molecular weight of the acrylic polyol is preferably 5,000 to 50,000, and more preferably 10,000 to 30,000. The number average molecular weight of the acrylic polyol is a molecular weight in terms of polystyrene measured by a gel permeation chromatography (GPC) method.

  (B) As an isocyanate compound, various aromatic and aliphatic isocyanate compounds can be used. It is preferably at least one selected from tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), xylylene diisocyanate (XDI), hexamethylene diisocyanate (HDI), and isophorone diisocyanate (IPDI). Of these, TDI is more preferable.

The molar ratio (isocyanate group / hydroxyl group) of the isocyanate group of the isocyanate compound to 1 mol of the hydroxyl group of the acrylic polyol is 0.25 / 1 to 2.0 / 1. When the molar ratio of the isocyanate group to 1 mol of the hydroxyl group is less than 0.25, the heat resistance in the molding process is lowered. When the molar ratio is more than 2.0, the moldability tends to decrease. The molar ratio is preferably 0.4 / 1 to 2.0 / 1, and more preferably 0.5 / 1 to 1.2 / 1.
When the molar ratio of the isocyanate group of the isocyanate compound to 1 mol of the hydroxyl group of the acrylic polyol is in the above range, the thermal shrinkage of the acrylic film that occurs when the resin substrate of the laminate for metallic decoration is heated and dried is easily suppressed. And it leads to suppression of the fall of the image clarity of the metal tone decoration molded object after shaping | molding.

The thickness of a primer layer is not specifically limited, Preferably it is 0.05-20 micrometers, More preferably, it is 0.1-10 micrometers.
The primer layer may contain additives such as an ultraviolet absorber and a light stabilizer.

  Examples of the primer layer forming method include known methods such as gravure coating, bar coating, roll coating, reverse roll coating, and comma coating.

(Acrylic film)
An acrylic film has a role as a support body of the laminated body for metal decoration, for example, and a role which protects an indium layer.
As the acrylic film used in the present invention, it is preferable to use an acrylic film having a small heat shrinkage rate from the viewpoint of suppressing a decrease in image clarity.

The acrylic film is made of an acrylic resin. Examples of the acrylic resin include polymethyl (meth) acrylate, polybutyl (meth) acrylate, and the like. One kind may be used alone, or two or more kinds may be used in combination. Moreover, copolymers, such as a methyl (meth) acrylate-butyl (meth) acrylate copolymer and a methyl (meth) acrylate-styrene copolymer, may be sufficient.
In the present invention, (meth) acrylate means acrylate or methacrylate.
The acrylic film is excellent in transparency and light resistance.

The acrylic film preferably has a haze of JIS K7136: 2000 of 5% or less, more preferably 3% or less, and even more preferably 1% or less.
The acrylic film preferably has a total light transmittance of JIS K7361-1: 1997 of 85% or more, and more preferably 90% or more.

The thickness of the acrylic film is not particularly limited, but is preferably 50 to 250 μm, more preferably 60 to 200 μm, and further preferably 70 to 150 μm from the viewpoint of the balance between moldability and protection of the indium layer. preferable.
The acrylic film may contain additives such as an ultraviolet absorber and a light stabilizer.

  As a commercial product of an acrylic film, for example, an acrylic film (manufactured by Kaneka Corporation, product names: Sandulen SD009, SD010) can be used.

(Indium layer)
The laminate for metallic decoration of the present invention uses an indium layer from the viewpoint of excellent weather resistance, whitening suppression, and metallic luster balance.

  Examples of the method for forming the indium film include a vacuum deposition method, a sputtering method, and an ion plating method. Among these, the vapor deposition method which can process to all the materials is preferable.

  The thickness of the indium layer is preferably 10 to 300 nm, more preferably 30 to 150 nm, and even more preferably 30 to 100 nm from the viewpoint of metallic gloss.

[Resin substrate]
The laminate for metallic decoration of the present invention includes a resin substrate.
Examples of the resin for the resin substrate include polyethylene, polypropylene, polybutene, polymethylpentene, ethylene-propylene copolymer, ethylene-propylene-butene copolymer, polyolefin resin such as olefin thermoplastic elastomer, ABS (acrylonitrile-butadiene- Styrene copolymer) resins, styrene resins, vinyl chloride resins, acrylic resins, polycarbonate resins and other thermoplastic resins, two-component curable urethane resins, unsaturated polyester resins, epoxy resins and other curable resins.
Although the thickness of a resin substrate is not specifically limited, Usually, it is 0.3 mm or more, and it is preferable that it is 1-10 mm from a viewpoint of a moldability and mechanical strength.

(Adhesive layer)
The laminate for metallic decoration includes an adhesive layer on the surface of the indium layer opposite to the primer layer. The adhesive layer is used, for example, for bonding the resin substrate and the indium layer.
The adhesive layer is preferably a pressure-sensitive adhesive layer or a heat seal layer.

The pressure-sensitive adhesive layer is preferably used because of the simplicity of the bonding process. The resin used for the pressure-sensitive adhesive layer may be a general-purpose acrylic resin, urethane resin, polyester resin, silicone resin, vinyl chloride resin or vinyl acetate resin, or a mixture or copolymer of two or more thereof. Can be used.
The thickness of the pressure-sensitive adhesive layer is preferably 1 to 100 μm, and more preferably 10 to 50 μm.

  A heat seal layer expresses adhesiveness in addition to adhesiveness by heating and pressurization. Examples of the resin used for the heat seal layer include acrylic resins, vinyl chloride resins, vinyl acetate resins, vinyl chloride-vinyl acetate copolymer resins, styrene-acrylic copolymer resins, polyester resins, and polyamide resins. The at least 1 sort (s) of resin chosen from resin etc. can be mentioned. Applying one or two or more resins selected from the above resins into a form that can be applied such as a solution or an emulsion by a gravure printing method, a screen printing method or a reverse coating method using a gravure plate, It can be formed by drying. The thickness of the heat seal layer is preferably 0.1 to 6 μm, and more preferably 0.5 to 4 μm.

(Adhesion layer)
The laminate for metallic decoration may have an adhesion layer further on the surface of the indium layer opposite to the primer layer and on the resin substrate side of the adhesive layer. The adhesion layer is formed, for example, to improve adhesion to the resin substrate.

The adhesion layer is preferably composed of a heat-sensitive or pressure-sensitive resin. In other words, the adhesion layer is preferably a so-called heat-sensitive adhesive layer or pressure-sensitive adhesive layer (adhesive layer). A pressure-sensitive adhesive layer (adhesive layer) is more preferable because of the simplicity of the bonding process.
Examples of heat-sensitive or pressure-sensitive resins include general-purpose acrylic resins, urethane resins, polyester resins, silicone resins, vinyl chloride resins or vinyl acetate resins, or a mixture or copolymer of two or more of these. Can be used.
Further, if the adhesion layer is made of the same kind of thermoplastic resin as the resin substrate, the adhesion to the adherend can be improved even if the adhesion layer is inferior in heat sensitivity or pressure sensitivity.

The thickness of the adhesion layer is preferably 1 to 100 μm, and more preferably 10 to 50 μm.
The adhesion layer can also serve as a backer layer described later. When the adhesion layer also serves as the backer layer, the adhesion layer is composed of a plastic film made of the same kind of thermoplastic resin as the resin base material (for example, the same kind of injection resin used for in-mold molding described later). Is preferred. The thickness of the plastic film before molding is preferably 100 μm or more and less than 1000 μm, and more preferably 150 μm or more and 500 μm or less.

(Backer layer)
The laminated body for metallic decoration may have a backer layer between the adhesive layer and the indium layer. A backer layer has a role which raises the intensity | strength of the laminated body for metal tone decoration and a metal tone decoration molded object, or keeps the shape of a molded object, for example.

  The backer layer is preferably composed of a plastic film. As a plastic film of a backer layer, the plastic film formed from the same kind of thermoplastic resin as the injection resin used for the in-mold shaping | molding mentioned later is mentioned, for example.

The thickness of the backer layer before molding is preferably 100 μm or more and less than 1000 μm, and more preferably 150 to 500 μm.
In addition, when the laminated body for metallic decorations has a backer layer between an adhesive bond layer and an indium layer, it is preferable to have an adhesive layer between a backer layer and an indium layer. A general-purpose adhesive can be used as the adhesive constituting the adhesive layer.

<Protective layer>
A protective layer may be formed on the surface of the acrylic film opposite to the indium layer, for example, in order to improve scratch resistance.

  The protective layer preferably contains a cured product of the curable resin composition. Examples of the cured product of the curable resin composition include a cured product of the thermosetting resin composition and a cured product of the ionizing radiation curable resin composition, and among these, a cured product of the ionizing radiation curable resin composition is preferable.

  The thermosetting resin composition is a composition containing at least a thermosetting resin, and is a resin composition that is cured by heating. Examples of the thermosetting resin include acrylic resin, urethane resin, phenol resin, urea melamine resin, epoxy resin, unsaturated polyester resin, and silicone resin. In the thermosetting resin composition, a curing agent is added to these curable resins as necessary.

The ionizing radiation curable resin composition is a composition containing a compound having an ionizing radiation curable functional group (hereinafter also referred to as “ionizing radiation curable compound”). Examples of the ionizing radiation curable functional group include an ethylenically unsaturated bond group such as a (meth) acryloyl group, a vinyl group, and an allyl group, an epoxy group, and an oxetanyl group.
As the ionizing radiation curable resin, a compound having an ethylenically unsaturated bond group is preferable. In addition, from the viewpoint of suppressing damage to the resin layer in the process of producing a metallic decorative molded body, the ionizing radiation curable resin is more preferably a compound having two or more ethylenically unsaturated bond groups. More preferred are polyfunctional (meth) acrylate compounds having two or more ethylenically unsaturated bond groups. As the polyfunctional (meth) acrylate compound, any of a monomer and an oligomer can be used.
The ionizing radiation means an electromagnetic wave or a charged particle beam having an energy quantum capable of polymerizing or cross-linking molecules, and usually ultraviolet (UV) or electron beam (EB) is used. Electromagnetic waves such as X-rays and γ-rays, and charged particle beams such as α-rays and ion beams can also be used.

  The thickness of the protective layer is preferably 0.5 to 30 μm, more preferably 1 to 20 μm, and further preferably 3 to 10 μm.

[Example of layer structure of laminated body for metallic decoration]
Specific examples of the laminate for metallic decoration include the following configurations (1) to (3) in addition to the configuration shown in FIG. Note that “/” means the boundary of each layer.
(1) Acrylic film / primer layer / indium layer / adhesive layer / adhesive layer (backer layer combined adhesive layer) / resin substrate (2) acrylic film / primer layer / indium layer / adhesive layer / backer layer / adhesive layer ( Heat-sensitive adhesive layer or pressure-sensitive adhesive layer) / resin substrate (3) protective layer / acrylic film / primer layer / indium layer / adhesive layer / backer layer / adhesion layer (heat-sensitive adhesive layer or pressure-sensitive adhesive) Layer) / resin substrate

  In this invention, image clarity can be evaluated as an optical characteristic of the indium layer surface of the laminated body for metallic decorations and a metallic decoration molding. The image clarity is an index indicating whether or not the image is clearly reflected on the surface of the decorative material. It can be evaluated by measuring the used DOI (Distinctness of Image) value.

  The laminate for metallic decoration according to the present invention can maintain the excellent image clarity of the indium layer, since deterioration of the image clarity after molding is suppressed. For this reason, it is preferably used for the exterior of a vehicle body. Here, the vehicle body is not particularly limited, and examples thereof include automobiles, bicycles, trains, trucks, buses, airplanes, and the like that accompany movement on roads, airways, and the like.

<Manufacturing method of laminated body for metallic decoration>
The method for producing a laminate for metallic decoration of the present invention includes a step of forming a primer layer on an acrylic film, a step of forming an indium layer on the primer layer, and a step of forming an adhesive layer on the indium layer. And a step of bonding a resin substrate to the adhesive layer.

(Primer layer formation process)
The primer layer forming step is a step of forming a primer layer on the acrylic film. The method for forming the primer layer is as described above.

(Indium formation process)
The indium forming step is a step of forming an indium layer on the primer layer obtained in the primer forming step. The method for forming the indium layer is as described above.

(Adhesive layer forming process)
The method for producing a metallic decorative sheet includes an adhesive layer forming step. The adhesive layer forming step is a step of forming an adhesive layer on the indium layer obtained in the indium layer forming step. The adhesive layer can be formed by a known method.

(Resin substrate forming process)
The manufacturing method of the laminated body for metallic decoration further includes a resin substrate forming step. The resin substrate forming step is a step of bonding a resin substrate to the adhesive layer obtained in the adhesive layer forming step to form a laminate for metallic decoration. The adhesive layer forming method and the bonding method can be performed by known methods.

<Metallic decorative molded body>
It is preferable to shape | mold the metal-tone decoration molded object of this invention using the laminated body for metal-tone decoration of this invention.

(Manufacturing method of metal-like decorative molded body)
A metal decoration decoration body can be manufactured by shape | molding using the laminated body for metal decoration decoration of this invention.

For example, a metallic decorative molded body can be produced by vacuum forming having the following steps (y1) to (y3).
(Y1) The resin substrate of the laminate for metallic decoration is heat-dried at a predetermined temperature to remove moisture in the resin substrate before molding. The heating and drying temperature is usually 70 to 90 ° C.
(Y2) After setting the laminated body for metallic decoration on a mold having a molding surface of a predetermined shape, the laminated body for metallic decoration is heated and softened. Although heating temperature is based on the resin substrate material to be used, it is 120-180 degreeC normally. When the mold is a male mold, the metal substrate is placed so that the resin substrate side of the laminate for metal decoration faces the mold (male mold) side. When the mold is a female mold, the laminate for metal decoration It arrange | positions so that the acrylic film side may face the shaping | molding die (female type | mold) side.
(Y3) Vacuum-suction is performed from the side of the mold, and the softened laminate for metal decoration is brought into close contact with the molding surface of the mold to form the laminate for metal decoration.

Alternatively, a metallic decorative molded body can be produced by in-mold molding having the following steps (z1) to (z2).
(Z1) The laminate for metallic decoration is placed in an in-mold mold. At this time, of the pair of molds (male mold and female mold) constituting the in-mold mold, the inside of the mold on the resin injection side and the indium layer of the metallic decoration laminate are used as a reference. The laminate for metallic decoration is arranged so that the surface on the agent layer side faces. Note that the inside of the mold refers to the gap side formed between a pair of molds.
(Z2) A resin is injected and injected into an in-mold molding die to mold a resin molded body to be an adherend, and the molded body and the laminate for metallic decoration are brought into close contact with each other.
In the case of in-mold molding, it is preferable to use a thermoplastic resin as the injection resin. Examples of such thermoplastic resins include polystyrene resins, polyolefin resins, ABS resins (including heat-resistant ABS resins), AS resins, AN resins, polyphenylene oxide resins, polycarbonate resins, polyacetal resins, acrylic resins, Examples thereof include polyethylene terephthalate resin, polybutylene terephthalate resin, polysulfone resin, and polyphenylene sulfide resin.

  Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. In addition, this invention is not limited to the form as described in an Example.

1. Evaluation and Measurement Various characteristics (image clarity before and after molding and moldability) of the laminate for metallic decoration and the metallic decorative molded body obtained in Examples and Comparative Examples were evaluated according to the following procedures. The results are shown in Table 1.
In addition, before shaping | molding means before heat drying of the laminated body for metallic decorations, and after heat drying.

1-1. Image clarity The image clarity of the laminate for metal decoration (before molding) and the metal decoration decoration (after molding) is measured using a wave scan device (by brand name: Wave Scan Dual AW-4840). Using, it measured from the decoration surface side of a decoration laminated body and a decoration molded object. In addition, the display item of the mapping clarity on the measurement apparatus is “DOI (Distinctness of Image)”. The evaluation criteria for image clarity are as follows.
<Evaluation criteria>
○: The decrease in the DOI value is less than 10 before and after molding (contrast between before drying and after molding), and the DOI value after molding is 70 or more.
(Triangle | delta): The fall of the value of DOI is 10 or more and less than 15 before and behind shaping | molding (before drying and after shaping | molding), and the value of DOI after shaping | molding is 70 or more.
X: The decrease in the DOI value is 15 or more and / or the DOI value after molding is less than 70 before and after molding (contrast between before drying and after molding).

1-2. Formability The appearance of the metal-like decorative molded body was visually observed. The evaluation criteria are as follows.
<Evaluation criteria>
○: There are no defects such as cracks in the appearance.
X: There are defects such as cracks in the appearance.

2. [Example 1] Production of laminated body for metallic decoration and molded metallic decoration body
On a 125 μm thick acrylic film (manufactured by Kaneka Corporation, grade: SD009), the following primer layer forming coating solution having a molar ratio of isocyanate group of the isocyanate compound to 1 mol of hydroxyl group of the acrylic polyol is 0.25, The primer layer was dried to form a 2 μm thick primer layer.
<Primer layer forming coating solution>
・ Acrylic polyol (Arakawa Chemical Industries, trade name: Aracoat DA105)
100 parts by mass / isocyanate compound (Arakawa Chemical Industries, trade name: Alacoat CL102H)
10 parts by mass / solvent: methyl ethyl ketone 25 parts by mass butyl acetate 20 parts by mass

  Next, an indium layer having a thickness of 50 nm was formed on the primer layer by vacuum deposition.

Subsequently, the decorative laminate used in Example 1 was obtained by sticking the indium layer as an adhesive layer to a plate-like ABS having a thickness of 3 mm via an adhesive layer formed as follows.
To 100 parts by mass of an acrylic pressure-sensitive adhesive (manufactured by Soken Chemical Co., Ltd., trade name: SK Dyne 2094, solid content 25% by mass), an epoxy-based cross-linking agent (manufactured by Soken Chemical Co., Ltd., trade name: E-AX, solid content 5) (Mass%) 0.27 parts by mass was mixed to obtain an adhesive layer composition. The pressure-sensitive adhesive layer composition was applied to a release-treated surface of a 38 μm-thick polyester film (trade name: E7304, manufactured by Toyobo Co., Ltd.) and dried so that the thickness after drying was 40 μm. Pressure-sensitive adhesive layer) was formed.

  Next, the laminate for metallic decoration is heated and dried at 75 ° C. for 3 days, and then a mold having a desired molding shape is used, and the ABS side surface of the laminated body for metallic decoration is arranged toward the mold. Then, vacuum forming (ABS plate arrival temperature 150 ° C.) was performed to obtain a metallic decorative molded body of Example 1.

[Example 2]
A metallic decorative molded article of Example 2 was obtained in the same manner as Example 1 except that the isocyanate group / hydroxyl ratio was changed to 1.0.

[Example 3]
A metallic decorative molded body of Example 3 was obtained in the same manner as Example 1 except that the isocyanate group / hydroxyl molar ratio was changed to 2.0.

[Comparative Example 1]
In Example 1, a metallic decorative molded body of Comparative Example 1 was obtained in the same manner as in Example 1 except that the primer layer was not laminated.

[Comparative Example 2]
A metallic decorative molded body of Comparative Example 2 was obtained in the same manner as in Example 1 except that the hydroxyl ratio / isocyanate group molar ratio was changed to 0.1.

[Comparative Example 3]
A metallic decorative molded body of Comparative Example 3 was obtained in the same manner as in Example 1 except that the molar ratio of hydroxyl group / isocyanate group was changed to 2.5.

[Comparative Example 4]
In Example 1, the metal layer of Comparative Example 4 was prepared in the same manner as in Example 1 except that the primer layer-forming coating solution was applied and dried as a primer layer, and the primer layer was formed to have a thickness of 2 μm. A decorative molded body was obtained.
<Primer layer forming coating solution>
・ Polyester resin (made by Showa Ink, trade name: HS for SIVM)
100 parts by mass / isocyanate compound (product name: OP No. 81, manufactured by Showa Ink Co., Ltd.)
10 parts by mass / solvent: 50 parts by mass of methyl ethyl ketone 50 parts by mass of ethyl acetate

  From the results in Table 1, the image clarity before and after molding of the molded body composed of the laminate for metallic decoration of Examples 1 to 3 using the acrylic film of the present invention and the specific primer layer (before heat drying and molding) It can be seen that the comparison with the latter is suppressed as compared with Comparative Examples 2 to 4 having no specific primer layer. Furthermore, it turns out that the comparative example 1 which does not have a primer layer is inferior in image clarity and moldability.

  Since the laminate for metallic decoration of the present invention has excellent image clarity, it is used for exteriors of vehicle bodies such as automobiles, and various molded bodies requiring high design properties (for example, interior and exterior of automobiles, It can be suitably used for members such as home appliances and furniture.

1: laminate for metallic decoration 2: acrylic film 3: primer layer 4: indium layer 5: adhesive layer 6: resin substrate

Claims (7)

  A laminate for metal decoration having an acrylic film, a primer layer, an indium layer, an adhesive layer and a resin substrate in this order, wherein the primer layer comprises (A) an acrylic polyol as a main agent, and ( B) For metal decoration, including a reaction product with an isocyanate compound, wherein the molar ratio of the isocyanate group of the isocyanate compound to 1 mol of the hydroxyl group of the acrylic polyol is 0.25 / 1 to 2.0 / 1. Laminated body.   2. The isocyanate compound is at least one selected from tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), xylylene diisocyanate (XDI), hexamethylene diisocyanate (HDI), and isophorone diisocyanate (IPDI). The laminated body for metallic decorations described in 1.   The metallic acrylic decoration according to claim 1, wherein the acrylic polyol is a copolymer obtained by copolymerizing a hydroxyl group-containing acrylate and a copolymerizable vinyl monomer copolymerizable with the hydroxyl group-containing acrylate. Laminated body.   The laminated body for metallic decorations according to claim 1, wherein the adhesive layer is a pressure-sensitive adhesive layer or a heat seal layer.   The laminated body for metallic decorations according to claim 1, wherein the resin substrate is an ABS resin.   The laminated body for metallic decorations according to any one of claims 1 to 5, which is used for a vehicle body exterior.   The metal decoration decoration molded object which uses the laminated body for metal decorations of any one of Claims 1-6.