JP2019034484A - Metal-tone laminate - Google Patents

Abstract

To provide a metal-tone laminate having excellent various performances suitable for decoration or the like.SOLUTION: There is provided a metal-tone laminate 10 having a primer layer 2 containing a urethane resin (I) and an isocyanate crosslinking agent (II), and a metal layer 3 formed on the primer layer 2 and containing a metal, in which the urethane resin (I) contained in the primer layer 2 contains an urethane resin containing a silyl group, and contains an ether-based urethane resin and an ester-based or polycarbonate-based urethane resin.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a metallic laminate.

  A laminate having a metallic appearance may be attached to the surface of an interior or exterior product of a vehicle such as an automobile or a home appliance for the purpose of decoration or the like. Such a metal-like laminate may be attached as it is through an adhesive layer or an adhesive layer, or a molded body formed into a predetermined shape may be attached.

  Therefore, the metal-like laminate is required to have various performances in addition to formability so that it can withstand long-term use.

  As the metal-like laminate as described above, for example, in Patent Document 1 below, a base material, a two-layer anchor coat layer capable of imparting an adhesive force between the solvent barrier property and the base material, and a metal vapor deposition layer are laminated. A molding sheet having a metallic luster is disclosed.

  Patent Document 2 listed below has a high heat-resistant metallic luster formed by laminating a base material, an anchor coat layer made of a urethane resin, a ketone resin, and an isocyanate, a metal vapor deposition layer, and an adhesive layer. Is disclosed.

Japanese Patent Laying-Open No. 2005-305786 JP 2016-153210 A

  In the molding sheet described in Patent Document 1, it is necessary to laminate two anchor coat layers in order to improve the adhesion and solvent resistance between the substrate and the anchor coat layer. For this reason, such a sheet for molding tends to increase the manufacturing cost and the labor of manufacturing.

  In addition, when the second anchor coat layer is made only of a water-based urethane resin as in the molding sheet described in Patent Document 1, the fuel resistance required when affixing to an exterior product such as an automobile can be satisfied. It can be difficult.

  In the molding sheet described in Patent Document 2, a ketone-based resin is used for the anchor coat layer. Ketone resins are excellent in various physical properties such as heat resistance and chemical resistance, but tend to have poor adhesion to metals. Therefore, while improving the heat resistance and chemical resistance of the anchor coat layer, the adhesion between the anchor coat layer and the metal vapor deposition layer is reduced, the chemical resistance of the molding sheet, the fuel resistance, etc. are reduced. There is a concern that the metal vapor-deposited layer may be whitened when used for an automobile exterior or the like.

  Therefore, the present invention solves the above-mentioned problems and is used for decoration such as flexible emblems, badges, emblems, stickers, seals, labels, nameplates, ribbons, etc. excellent in moldability, chemical resistance, and fuel resistance. An object is to provide a suitable metallic laminate.

  The metallic laminate of the present invention comprises a primer layer containing a urethane resin (I) and an isocyanate crosslinking agent (II), and a metal layer formed on the primer layer and containing a metal, and the urethane resin (I) contains a urethane resin containing a silyl group, and the urethane resin (I) contains an ether urethane resin and an ester or polycarbonate urethane resin.

  Further, a surface layer is laminated on the surface of the primer layer opposite to the metal layer, and the surface layer includes a thermoplastic resin (A), a polycaprolactone polyol (B), and an isocyanate crosslinking agent (C). It is preferable to contain.

  The metal layer preferably contains indium.

  Moreover, it is preferable that a back surface layer is laminated | stacked on the surface on the opposite side to the said primer layer of the said metal layer, and the said back surface layer contains urethane resin (i) and isocyanate crosslinking agent (ii).

  Moreover, it is preferable that the laminated body provided with the said primer layer and the said metal layer is shape | molded so that it may have at least 1 recessed part, and it fills with the urethane resin in the said recessed part.

  As described above, according to the present invention, a metal texture suitable for decoration such as a flexible emblem, emblem, emblem, sticker, seal, label, nameplate, ribbon, etc. excellent in moldability, chemical resistance and fuel resistance. A laminate is provided.

It is a figure showing roughly the section of the layered product concerning a 1st embodiment of the present invention. It is a figure which shows roughly the cross section of the laminated body which concerns on 2nd Embodiment of this invention.

  The embodiments exemplified below are intended to facilitate understanding of the present invention, and are not intended to limit the present invention. The present invention can be modified and improved from the following embodiments without departing from the spirit of the present invention.

  In this specification, a silyl group means any one of a silyl hydride group, a silyl ether group (alkoxysilyl group) and a silanol group, and (meth) acryl means one or both of acryl and methacryl.

[Laminate]
FIG. 1 is a diagram schematically showing a cross section of the laminate according to the first embodiment of the present invention. The laminate 10 of this embodiment includes a surface layer 1, a primer layer 2, a metal layer 3, and a back layer 4.

[Surface layer 1]
The surface layer 1 in the present embodiment is not particularly limited as long as it is a layer made of a moldable thermoplastic resin. Examples of the thermoplastic resin include (meth) acrylic resin, urethane resin, polyester resin, and polycarbonate resin. And resins such as polyolefin resin, vinyl chloride resin, acrylonitrile-butadiene-styrene (ABS) resin. In particular, from the viewpoint of adhesion with the primer layer 2, (meth) acrylic resin, urethane resin, polyester resin, polycarbonate resin, and vinyl chloride resin are preferable. From the viewpoint of weather resistance, fuel resistance, and heat resistance, (meth) acrylic resins, urethane resins, and vinyl chloride resins are more preferable.

  In particular, the surface layer 1 includes a thermoplastic resin (A) having a hydroxyl value of 0 mgKOH / g or more and 20 mgKOH / g or less, and a polycaprolactone polyol (B) from the viewpoint of fuel resistance, abrasion resistance, and moldability. It is preferable that the layer contains an isocyanate cross-linking agent (C), and the thermoplastic resin (A) particularly suppresses a decrease in thermoplasticity due to curing with the isocyanate cross-linking agent (C). A resin not containing a functional group such as a hydroxyl group or a carboxyl group is more preferable. Here, “substantially not containing a functional group” means that no functional group exists in the molecular structure or a functional group exists only at the terminal.

  Examples of the thermoplastic resin (A) that substantially does not contain a functional group include, for example, an acrylic resin or a diol formed by copolymerizing one or a plurality of (meth) acrylic acid ester monomers having no functional group. Examples thereof include a urethane resin composed of diisocyanate or a urethane resin chain-extended with an amine, and one kind may be used alone, or two or more kinds may be used in combination.

  Moreover, you may use a commercial item as a thermoplastic resin (A). Examples of commercially available (meth) acrylic resins that contain substantially no functional groups include Dianal BR-90, Dianal BR-95, and Dianal MB-2593 manufactured by Mitsubishi Rayon Co., Ltd. .

  Examples of commercially available urethane resins include Resamine ME-88NFLP, Resamine ME-3612NFLP, Resamine ME-8105LP, Resamine ME-8115LP, Resamine ME-8210LP, Resamine ME-8210LP, Resamine SP-630LP, manufactured by Dainichi Seika Kogyo Co., Ltd. NE-302HV, resamine NE-308, resamine NE-8811, resamine NE-8836, resamine NE-8850, resamine NE-8880, resamine NES-9950-3, and the like.

  The polycaprolactone polyol (B) is obtained, for example, by reacting a caprolactone with a compound having a plurality of hydroxyl groups in the molecule, and one kind may be used alone, or two or more kinds may be used in combination.

  Or you may use a commercial item as a polycaprolactone polyol (B). As a commercial product of polycaprolactone polyol, Placel 208 manufactured by Daicel Corporation (molecular weight 830, number of hydroxyl groups 2), Plaxel 210 (molecular weight 1000, number of hydroxyl groups 2), Plaxel 212 (molecular weight 1250, number of hydroxyl groups 2) ), Plaxel 220 (molecular weight 2000, number of hydroxyl groups 2), Plaxel 303 (molecular weight 300, number of hydroxyl groups 3), Plaxel 305 (molecular weight 550, number of hydroxyl groups 3), Plaxel 308 (molecular weight 850, hydroxyl group number) 3), Plaxel 309 (molecular weight 900, hydroxyl group number 3), Plaxel 312 (molecular weight 1250, hydroxyl group number 3), Plaxel 320 (molecular weight 2000, hydroxyl group number 3) and Plaxel 410 (molecular weight 1000, Number of hydroxyl groups 4) and CA made by Perstorp Japan A2085 (molecular weight 830, number of hydroxyl groups 2), CAPA2100 (molecular weight 1000, number of hydroxyl groups 2), CAPA2121 (molecular weight 1250, number of hydroxyl groups 2), CAPA2125 (molecular weight 1250, number of hydroxyl groups 2), CAPA2200 ( Molecular weight 2000, number of hydroxyl groups 2), CAPA2201 (molecular weight 2000, number of hydroxyl groups 2), CAPA2205 (molecular weight 2000, number of hydroxyl groups 2), CAPA2209 (molecular weight 2000, number of hydroxyl groups 2), CAPA3091 (molecular weight 900) , 3 hydroxyl groups), CAPA 3121J (molecular weight 1200, 3 hydroxyl groups), CAPA 3201 (2000 molecular weight, 3 hydroxyl groups) and CAPA 4101 (1000 molecular weight, 4 hydroxyl groups).

  The content of the polycaprolactone polyol (B) is preferably 100 parts by mass or more and 280 parts by mass or less with respect to 100 parts by mass of the thermoplastic resin (A). When the content of the polycaprolactone polyol (B) is 100 parts by mass or more, the fuel resistance, water resistance, and abrasion resistance of the surface layer 1 can be further improved. Further, when the content of the polycaprolactone polyol (B) is 280 parts by mass or less, curing proceeds sufficiently only by the drying step, and thus the blocking resistance of the surface layer 1 is improved. Furthermore, when the content of the polycaprolactone polyol (B) is 280 parts by mass or less, the elastic modulus after curing of the surface layer 1 does not become too high, and the laminate 10 is formed when thermoformed. It becomes easy to follow the surface shape of the adherend, and after the laminated body 10 is thermoformed, the surface layer 1 contracts during cooling and the surface layer 1 peels off, or the laminated body 10 peels off the adherend. Can be suppressed.

  The isocyanate crosslinking agent (C) forms a crosslinked structure by reacting at least the crosslinkable group with the hydroxyl group of the polycaprolactone polyol (B), and contains an isocyanate crosslinking agent having at least an alicyclic ring. Is preferred.

As an isocyanate crosslinking agent having an alicyclic ring, for example, an isocyanate crosslinking agent derived from hydrogenated xylylene diisocyanate (H ₆ XDI), an isocyanate crosslinking agent derived from hydrogenated diphenylmethane diisocyanate (H ₁₂ MDI), or an isophorone diisocyanate (IPDI) derived. An isocyanate crosslinking agent is mentioned. Among the isocyanate crosslinking agents having an alicyclic ring, it is particularly preferable to use an isocyanate crosslinking agent derived from hydrogenated xylylene diisocyanate from the viewpoint of improving the wear resistance.

  From the viewpoint of flexibility, it is preferable that an isocyanate crosslinking agent having an alicyclic ring and an isocyanate crosslinking agent derived from hexamethylene diisocyanate (HDI) are used in combination.

  However, the isocyanate crosslinking agent (C) may contain other crosslinking agents other than the crosslinking agent. Examples of the other crosslinking agent include an isocyanate crosslinking agent containing at least one of tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), and xylylene diisocyanate (XDI).

  The content of the isocyanate crosslinking agent (C) is preferably such that the isocyanate group in the crosslinking agent is 0.5 equivalents or more and 2.0 equivalents or less with respect to the hydroxyl value of the polycaprolactone polyol, and 0.7 equivalents or more. It is more preferably 1.5 equivalents or less, and further preferably 0.8 equivalents or more and 1.2 equivalents or less. By setting the content of the isocyanate crosslinking agent (C) to 0.5 equivalent or more as described above, the fuel resistance and water resistance of the laminate 10 can be improved. Moreover, the blocking resistance of the surface layer 1, a weather resistance, and heat resistance can be improved by content of an isocyanate crosslinking agent (C) being 2.0 equivalent or less.

  The surface layer 1 may contain other components as necessary. Examples of other components include a leveling agent, a light stabilizer, an antioxidant, a plasticizer, a surfactant, a colorant, a brightening agent, and a filler.

  The thickness of the surface layer 1 is not particularly limited and is selected according to the application. The thickness of the surface layer 1 is, for example, not less than 1 μm and not more than 300 μm. From the viewpoints of workability and followability for attaching to an adherend, protection of the metal layer 3, wear resistance, etc., the thickness of the surface layer 1 is preferably 2 μm or more and 200 μm or less, and 30 μm or more and 150 μm or less. More preferably, it is 40 μm or more and 100 μm or less.

[Primer layer 2]
The primer layer 2 of this embodiment is provided between the surface layer 1 and the metal layer 3.

  The primer layer 2 contains a urethane resin (I) and an isocyanate crosslinking agent (II), and the urethane resin (I) contains a urethane resin having a silyl group.

  By containing a urethane resin having a silyl group in the urethane resin (I), a coupling reaction occurs between the primer layer 2 and the metal layer 3, so that the adhesion between the primer layer 2 and the metal layer 3 can be improved. Moreover, since a crosslinking reaction occurs between silyl groups or between a silyl group and a hydroxyl group, the water resistance and chemical resistance of the laminate 10 can be improved. Further, the urethane resin having a silyl group contained in the urethane resin (I) is preferably composed of an ester urethane resin or an ether urethane resin, and particularly preferably an ether urethane resin from the viewpoint of moldability. .

  The glass transition temperature (Tg) of the urethane resin (I) is preferably 110 ° C. or lower. By setting the glass transition temperature of the urethane resin (I) to 110 ° C. or less, the adhesion between the primer layer 2 and the metal layer 3 is further increased. In order to improve the adhesion between the primer layer 2 and the metal layer 3, or to adjust the viscosity of the composition, the urethane resin (I) may be used alone as long as it is a urethane resin having a silyl group. Two or more types may be used in combination. Moreover, you may use together the urethane resin which does not contain a silyl group. From the viewpoint of moldability, it is preferable to use an ether urethane resin and an ester urethane resin or a carbonate urethane resin in combination. From the viewpoint of water resistance and chemical resistance, use a urethane resin having a silyl group in combination. Is preferred.

  Further, by adding the isocyanate crosslinking agent (II) to the primer layer 2, the fuel resistance and water resistance of the primer layer 2 can be improved.

  There is no restriction | limiting in particular as said isocyanate crosslinking agent (II), Choose one or more from the isocyanate crosslinking agent which has an aliphatic hydrocarbon chain, the isocyanate crosslinking agent which has an alicyclic ring, and the isocyanate crosslinking agent which has an aromatic ring. Can do.

  The amount of the isocyanate crosslinking agent (II) added to the urethane resin composition is preferably 1 part by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the solid content of the urethane resin (I). More preferably, it is at least 15 parts by mass. By making the addition amount of the isocyanate crosslinking agent (II) 1 part by mass or more, the water resistance and fuel resistance of the primer layer 2 can be further improved. Moreover, it can suppress that a pot life becomes short because the addition amount of isocyanate crosslinking agent (II) shall be 20 mass parts or less.

  The thickness of the primer layer 2 is not particularly limited, but can be, for example, 0.1 μm or more and 10 μm or less, and preferably 0.5 μm or more and 2 μm or less.

[Metal layer 3]
The metal layer 3 is formed, for example, by depositing or sputtering a metal or metal oxide on the primer layer 2. When the laminate 10 includes such a metal layer 3, the laminate 10 is given a metallic appearance, and the laminate 10 is a metal-like laminate. Examples of the metal used for the metal layer 3 include aluminum, tin, and indium. Among these, indium and tin are particularly preferable from the viewpoint of moldability, and indium is more preferable. By using indium or tin for the metal layer 3, whitening of the metal layer 3 can be suppressed when the laminated body 10 is formed as compared with the case where another metal is used.

  The thickness of the metal layer 3 is not particularly limited. For example, the thickness of the metal layer 3 can be set so that the total light transmittance is about 2% or more and 10% or less. By evaporating the metal so that the total light transmittance of the metal layer 3 is 2% or more, a texture peculiar to the metal can be imparted to the laminate 10. Moreover, metal gloss can be provided to the laminated body 10 by vapor-depositing a metal so that the total light transmittance of the metal layer 3 is 10% or less.

[Back layer 4]
The back surface layer 4 is a layer provided on the surface opposite to the surface layer 1 side of the metal layer 3 for the purpose of protecting the metal layer 3, decorating the laminate 10, or improving formability.

  Although the material and thickness of the back layer 4 are not particularly limited, for example, 0.1 μm or more and 500 μm or less are preferable.

  For example, from the viewpoint of protecting the metal layer 3, the thickness of the back surface layer 4 is preferably 0.1 μm or more. By setting it as 0.1 micrometer or more, it is prevented that the metal layer 3 gets damaged at the time of conveyance to another process, and the water resistance and chemical-resistance of the metal layer 3 can improve. Moreover, by making the back surface layer 4 20 μm or less, other layers can be laminated for the purpose of decorating and improving formability without impairing followability to the adherend during integral molding. From the viewpoint of protecting the metal layer 3, it is more preferable to use the same material as the primer layer 2. That is, it is preferable that the back surface layer 4 contains a urethane resin (i) and an isocyanate crosslinking agent (ii).

  From the viewpoint of decoration, the thickness of the back surface layer 4 is preferably 5 μm or more, for example. When the back layer 4 is a colored layer, the color tone before molding can be maintained even when the back layer 4 is stretched by molding by setting the thickness to 5 μm or more.

  From the viewpoint of improving the formability of the laminate 10, the thickness of the back surface layer 4 is preferably 150 μm or more and 500 μm or less, for example. By setting it as 150 micrometers or more, even if it is a shaping | molding method which needs to hold | maintain a shape with the laminated body 10 single-piece | units, such as insert molding, the laminated body 10 can shape | mold without using a shaping | molding auxiliary layer. Further, by setting the thickness to 500 μm or less, the laminated body 10 can be made to follow the fine shape of the adherend at the time of integral forming such as vacuum forming, pressure forming, or vacuum / pressure forming.

  As described above, the laminate 10 of the present embodiment includes the primer layer 2 having good adhesion to the metal layer 3, and the primer layer 2 can be composed of a single layer. Therefore, the laminate 10 of the present embodiment includes the primer layer 2 that can improve the adhesion with the metal layer 3 with a simple layer configuration. Moreover, the laminated body 10 of this embodiment has the various performances suitable for decorations, such as a badge, an emblem, a nameplate, a ribbon, etc. as mentioned above.

(Second Embodiment)
Next, a second embodiment of the present invention will be described in detail with reference to FIG. In addition, about the component which is the same as that of 1st Embodiment, or equivalent, except the case where it demonstrates especially, the same referential mark is attached | subjected and the overlapping description is abbreviate | omitted.

  FIG. 2 is a diagram schematically showing a cross-section of the metallic laminate 20 according to the second embodiment of the present invention. As shown in FIG. 2, the metallic tone laminate 20 of the present embodiment is filled with a laminate 15 including a surface layer 1, a primer layer 2, and a metal layer 3, and a recess 16 formed in the laminate 15. The adhesive layer 5 which covers the agent 17 and the filler 17 from the opposite side to the laminated body 15 is provided.

  The laminate 15 of the present embodiment is formed so as to have at least one recess 16, and the recess 16 is filled with a filler 17. As the filler 17, for example, a urethane resin can be used, and the urethane resin is preferably a two-component curable urethane resin.

  The adhesive layer 5 is a layer provided for attaching the metallic tone laminate 20 to the adherend. The adhesive layer 5 is provided to seal the filler 17 in the concave portion 16 formed in the laminate 15. Therefore, the adhesive layer 5 is provided so as to cover the recess 16 and is in close contact with the laminate 15 outside the recess 16. The adhesive which comprises such an adhesive layer 5 will not be specifically limited if it can adhere | attach on the adherend of the laminated body 15, the filler 17, and the metallic tone laminated body 20. FIG.

  Thus, by forming the laminate 15 and filling the recess 16 with the filler 17 made of urethane resin, the metal tone laminate 20 is given a desired three-dimensional shape, and the design of the metal tone laminate 20 is achieved. Can be improved.

  As mentioned above, although the said embodiment was demonstrated to the example about this invention, this invention is not limited to these. For example, layers other than the primer layer 2 and the metal layer 3 among the layers constituting the laminate 10 and the metal-like laminate 20 are not essential, and other layers may be omitted, and are illustrated as necessary. No layers may be provided.

  For example, in the laminated body 10 of 1st Embodiment, the adhesive bond layer, adhesive layer, etc. similar to the adhesive bond layer 5 of the metal tone laminated body 20 of 2nd Embodiment may be provided as needed.

  Moreover, the laminated body 10 and the metal-tone laminated body 20 may be provided with a printing layer or a colored layer from the viewpoint of improving design properties. The print layer is formed, for example, by printing an ink containing a resin, a colorant, a solvent, and the like by a method such as screen printing, and performing steps such as drying and curing as necessary.

  Hereinafter, the content of the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

  First, the preparation method of the surface layer used for the metallic tone laminated body which concerns on the Example and comparative example which are demonstrated later is demonstrated below. Table 1 shows the blending ratios of the four surface layers from Production Example 1 to Production Example 4 in parts by mass. In Table 1, the ratio of the solid content of each composition constituting the surface layer is given in parentheses.

(Production Example 1)
100 parts by mass of resamine NE-8836 (manufactured by Dainichi Seika Kogyo Co., Ltd., solid content: 25 wt%) as a urethane resin and Plaxel 305 (manufactured by Daicel Industries, Ltd., solid content: 100 wt%, weight average molecular weight) as a polycaprolactone polyol : 550, hydroxyl value: 300-310 mg KOH / g), 37.5 parts by mass, 10 parts by mass of tert-butyl alcohol and 25 parts by mass of dimethylformamide (DMF) as a solvent, and H ₆ XDI as a crosslinking agent Originated isocyanate crosslinker Takenate D-120N (Mitsui Chemicals, Inc., ethyl acetate solution of a crosslinker containing trimethylolpropane (TMP) adduct derived from H ₆ XDI, solid content: 75 wt%, NCO%: 11%) Was added to prepare a resin solution for the surface layer. Thereafter, the resin solution was coated on a polyethylene terephthalate (PET) film P756050 (manufactured by Lintec Corporation, thickness 75 μm) so that the layer thickness after drying was 50 μm, and dried at 150 ° C. for 5 minutes. Thereafter, the film was cured at 60 ° C. for 2 days to obtain a transparent film in which a surface layer having a thickness of 50 μm was formed on the PET film.

(Production Example 2)
As a crosslinking agent, 38.7 parts by mass of an isocyanate crosslinking agent D-120N derived from H ₆ XDI and an isocyanate crosslinking agent coronate HX derived from HDI (manufactured by Nippon Polyurethane Industry Co., Ltd., a crosslinking agent containing an isocyanurate body derived from HDI, NCO %: 20%, solid content: 100 wt%) was added in the same manner as in Production Example 1 except that 21.3 parts by mass of the resin solution for the surface layer was prepared. Thereafter, a transparent film was obtained in the same manner as in Production Example 1.

(Production Example 3)
A surface layer resin solution was prepared in the same manner as in Production Example 2 except that the amount of Takenate D-120N added was 23.2 parts by mass and the amount of Coronate HX added was 29.8 parts by mass as a crosslinking agent. Thereafter, a transparent film was obtained in the same manner as in Production Example 2.

(Production Example 4)
As polycaprolactone polyol, 37.5 parts by mass of Plaxel 303 (manufactured by Daicel Kogyo Co., Ltd., solid content: 100 wt%, weight average molecular weight: 300, hydroxyl value: 530 to 550 mg KOH / g) is blended in place of Plaxel 305, and crosslinked. A resin solution for the surface layer was prepared in the same manner as in Production Example 1 except that the amount of Takenate D-120N added was changed to 128.8 parts by mass. Thereafter, a transparent film was obtained in the same manner as in Production Example 1.

  Next, the coating liquid used for the primer layer or back surface layer of the metal tone laminated body which concerns on the Example and comparative example which are demonstrated later was prepared. Table 2 shows the composition of seven coating liquids from Production Example 5 to Production Example 11. In addition, the numerical value shown in Table 2 means a mass part, and the ratio of the solid content of each composition is attached in parentheses.

(Production Example 5)
33.3 parts by mass of Takerac W-605 (manufactured by Mitsui Chemicals, solid content: 30 wt%) which is an ester-based aqueous urethane resin, and Takelac WS-6021 (Mitsui Chemicals, Inc.) which is a silanol group-containing ether-based urethane resin Manufactured, solid content: 30 wt%) 66.7 parts by mass and Takenate WD-725 (Mitsui Chemicals, solid content: 100 wt%), which is a water-dispersed isocyanate crosslinking agent, is mixed with 2.8 parts by mass. A coating solution was prepared.

(Production Example 6)
57.1 parts by mass of Takelac WS-6021, 42.9 parts by mass of Takelac WS-5100 (Mitsui Chemicals, solid content: 30 wt%), which is a silanol group-containing carbonate-based aqueous urethane resin, and Takenate WD-725 Was mixed with 2.8 parts by mass to prepare a coating solution.

(Production Example 7)
50 parts by mass of Takelac WS-6021, 50 parts by mass of Takelac WS-5100, and 2.5 parts by mass of Takenate WD-725 were mixed to prepare a coating solution.

(Production Example 8)
A coating solution was prepared by mixing 66.7 parts by mass of Takelac WS-6021, 33.3 parts by mass of Takelac WS-5100, and 5.6 parts by mass of Takenate WD-725.

(Production Example 9)
A coating solution was prepared in the same manner as in Production Example 8 except that Takenate WD-725 was not blended.

(Production Example 10)
100 parts by mass of Takelac W-605 and 2.5 parts by mass of Takenate WD-725 were mixed to prepare a coating solution.

(Production Example 11)
66.7 parts by mass of DESMOSEALXP2458 (manufactured by Bayer Holding Co., Ltd., solid content: 90 wt%), which is a silane-terminated ether-based urethane resin, and resamine UD-8345 (manufactured by Dainichi Seika Kogyo Co., Ltd., solid), which is a polycarbonate-based urethane resin 33.3 parts by mass of (min: 50 wt%) and 15 parts by mass of an isocyanate crosslinking agent (manufactured by Asahi Kasei Corporation, trade name: Duranate D-201, solid content 100 wt%) were mixed to prepare a coating solution. .

<Preparation of metallic laminate>
The configuration of each layer was as shown in Tables 3 to 5, and metal-like laminates according to Examples and Comparative Examples were produced.

Example 1
The coating liquid obtained in Production Example 5 is coated on the surface layer of the transparent film obtained in Production Example 1 so that the film thickness after drying is 1 μm, and the coating liquid is dried to form a primer layer. did. Thereafter, indium (In) was deposited on the primer layer so that the total light transmittance was 5%, thereby forming a metal layer. Thereafter, the coating liquid of Production Example 6 was coated on the metal layer so that the film thickness after drying was 1 μm, and the coating liquid was dried to form a back layer. Finally, the PET film was peeled off to produce a metallic laminate having the surface layer obtained in Production Example 1.

(Example 2)
A metallic laminate was produced in the same manner as in Example 1 except that the coating liquid of Production Example 6 was used for the primer layer.

(Example 3)
A metallic laminate was produced in the same manner as in Example 2 except that the transparent film of Production Example 2 was used for the surface layer.

Example 4
A metallic laminate was produced in the same manner as in Example 2 except that the transparent film of Production Example 3 was used for the surface layer.

(Example 5)
A metallic laminate was produced in the same manner as in Example 2 except that the transparent film of Production Example 4 was used for the surface layer.

(Example 6)
A metallic laminate was produced in the same manner as in Example 2 except that a vinyl chloride film Hi-S Paint N-15FU06B (Nippon Carbide Industries, Ltd., thickness 50 μm) was used as the surface layer.

(Example 7)
A metallic laminate was produced in the same manner as in Example 2 except that A-PETPT-700M N-N0 (manufactured by Polytech Co., Ltd., thickness 200 μm) was used as the surface layer.

(Example 8)
A metallic laminate was produced in the same manner as in Example 2 except that the coating liquid of Production Example 7 was used for the primer layer.

Example 9
A metallic laminate was produced in the same manner as in Example 2 except that the coating liquid of Production Example 8 was used for the primer layer.

(Example 10)
A metallic laminate was produced in the same manner as in Example 2 except that aluminum (Al) was deposited as a metal layer.

(Example 11)
A metal laminate was produced in the same manner as in Example 2 except that the back layer was not formed.

(Example 12)
A-PETPT-700M N—N0 was laminated as a molding auxiliary layer on the surface layer side of the metal-like laminate obtained in Example 11, pressure 85 bar (8.5 MPa), upper and lower heater temperature 340 ° C., heating time 5 seconds, heating The metal layered product was pressed from the opposite side of the surface layer under a pressure time of 4 seconds, and a recess in the shape of each character of “NCI” with a character height of 2.3 mm, a height of 30 mm, and a line width of 10 mm was thermoformed. Two-part curable urethane obtained by mixing 100 parts by mass of the main agent perurethane MU-662A (manufactured by Pernox Corporation) and 20.5 parts by mass of the curing agent perurethane MU-210B (manufactured by Pernox Corporation) in the concave portion. Resin (filler) was filled so that air could not enter between the metallic laminate. Thereafter, the concave portion was covered with double-sided tape (manufactured by 3M Co., Ltd., 468MP) so that air could not enter between the filler and allowed to stand at 23 ° C. for 24 hours to cure the filler. The molded product thus obtained was punched out, the molding auxiliary layer was removed, and a metal-like laminate having “NCI” three-dimensional letters was produced.

(Example 13)
A metallic laminate was produced in the same manner as in Example 2 except that the coating liquid of Production Example 11 was used for the primer layer.

(Comparative Example 1)
A metallic laminate was produced in the same manner as in Example 2 except that the coating liquid of Production Example 9 was used for the primer layer.

(Comparative Example 2)
A metallic laminate was produced in the same manner as in Example 2 except that the water-based urethane resin Takelac W-605 was used for the primer layer.

(Comparative Example 3)
A metallic laminate was produced in the same manner as in Example 2 except that silanol group-containing water-based urethane resin Takelac WS-6021 was used for the primer layer.

(Comparative Example 4)
A metallic laminate was produced in the same manner as in Example 2 except that silanol group-containing water-based urethane resin Takelac WS-5100 was used for the primer layer.

(Comparative Example 5)
A metallic laminate was produced in the same manner as in Example 2 except that an ether-based water-based urethane resin (manufactured by ADEKA, trade name: Adekabon titer HUX-550, solid content: 28 wt%) was used for the primer layer.

(Comparative Example 6)
A metallic laminate was produced in the same manner as in Example 2 except that the coating liquid of Production Example 10 was used for the primer layer.

<Evaluation method>
By the method demonstrated below, the metal tone laminated body which concerns on the said Example and comparative example was evaluated.

(productivity)
It was visually confirmed whether each layer constituting the metallic laminate was formed without any problem. The results are evaluated according to the following criteria, and the evaluation results are shown in Tables 3 to 5.
○: Each layer was formed without any problem.
Δ: The metal layer could be formed without any problem.
X: A metal layer could not be formed.

(Thermoformability)
A-PET (manufactured by Polytech Co., Ltd., trade name: PT-700M N-N0, thickness 200 μm) is stacked on the surface layer side of the metallic laminate as a forming auxiliary layer, pressure 85 bar (8.5 MPa), upper and lower heater temperature The shape of the character “NCI” is 2.3 mm in height, 30 mm in length, and 50 mm in width when the metal-like laminate is pressed from the back layer side under the conditions of 340 ° C., heating time 5 seconds, and pressurization time 4 seconds. The recess was thermoformed. In addition, about the metal-tone laminated body of Example 11, a film layer (Oike Industry Co., Ltd. make, Ecomold FI-PM (D) -75 (H) -W) is laminated | stacked on a metal layer as a temporary back surface layer. Then, the thermoforming was performed, and the film layer was removed after thermoforming. Moreover, the metal tone laminated body of Example 12 was obtained by performing thermoforming as described above, and this evaluation was performed at the time of thermoforming in the manufacturing process. The appearance of the metal-like laminate after thermoforming is evaluated according to the following criteria, and the evaluation results are shown in Tables 3 to 5.
○: Molding was possible without problems.
Δ: Slight whitening was observed after molding.
X: A big difference was seen in the metallic appearance before and after forming.

(Heat-resistant)
After pasting a white paint plate on the surface opposite to the surface layer of the metal-like laminate using a double-coated tape (468MP) manufactured by 3M Co., Ltd., it was allowed to stand at 80 ° C. for 168 hours, and the appearance change was visually confirmed. did. The results are evaluated according to the following criteria, and the evaluation results are shown in Tables 1 to 3.
○: No change.
Δ: Slight whitening was observed.
×: Clear whitening, cracks and wrinkles were clearly seen on the entire surface.

(water resistant)
After pasting the white paint plate on the surface opposite to the surface layer of the metallic laminate using a double-sided tape (468MP) manufactured by 3M Co., Ltd., it was immersed in warm water at 40 ° C. for 168 hours, and the appearance change was visually observed. confirmed. The results are evaluated according to the following criteria, and the evaluation results are shown in Tables 1 to 3.
○: No change.
Δ: Slight whitening was observed.
×: Clear whitening, cracks and wrinkles were clearly seen on the entire surface.

(Alkali resistance)
After pasting a white paint plate on the surface opposite to the surface layer of the metal-like laminate using a double-sided tape (468MP) manufactured by 3M Co., Ltd., it was immersed in an aqueous 0.1N sodium hydroxide solution for 8 hours to change the appearance. Was confirmed visually. The results are evaluated according to the following criteria, and the evaluation results are shown in Tables 1 to 3.
○: No change.
Δ: Slight whitening was observed.
×: Clear whitening, cracks and wrinkles were clearly seen on the entire surface.

(Fuel resistance)
After pasting a white paint plate on the surface opposite to the surface layer of the metallic laminate using a double-sided tape (468MP) manufactured by 3M Corporation, Fuel-C (mixed in equal amounts of toluene and isooctane (ASTMD 471)) ) For 1 hour, and the appearance change was visually confirmed. The results are evaluated according to the following criteria, and the evaluation results are shown in Tables 1 to 3.
○: No change.
Δ: Slight whitening was observed.
×: Clear whitening, cracks and wrinkles were clearly seen on the entire surface.

(Gasohol resistance)
A white painted plate is attached to the surface opposite to the surface layer of the metallic laminate using a double-sided tape (468MP) manufactured by 3M Co., Ltd., then immersed in gasohol containing 20 wt% ethanol in high-octane gasoline. Then, it was taken out and dipped again 20 seconds later, and the appearance change was visually confirmed. The results are evaluated according to the following criteria, and the evaluation results are shown in Tables 1 to 3.
○: No change.
Δ: Slight whitening was observed.
×: Clear whitening, cracks and wrinkles were clearly seen on the entire surface.

  As shown in Table 3 to Table 5, the metal-tone laminates according to the examples are comprehensively superior to the metal-tone laminates according to the comparative examples in the evaluation items. Metallic laminates according to such examples include, for example, flexible emblems, emblems, emblems, stickers, stickers, stickers, labels, labels for attaching to the exterior of vehicles such as automobiles and the surfaces of objects installed outdoors. It is particularly suitable as a nameplate, ribbon, etc.

  As described above, according to the present invention, there is provided a metallic laminate having excellent performance suitable for decoration such as flexible emblems, emblems, emblems, stickers, seals, labels, nameplates, ribbons and the like. It is expected to be used in the field of vehicle decoration such as automobiles.

DESCRIPTION OF SYMBOLS 1 ... Surface layer 2 ... Primer layer 3 ... Metal layer 4 ... Back surface layer 5 ... Adhesive layer 10 ... Laminated body 20 ... Metal-like laminated body

Claims (5)

A primer layer containing a urethane resin (I) and an isocyanate crosslinking agent (II); and a metal layer formed on the primer layer and containing a metal,
The urethane resin (I) contains a urethane resin containing a silyl group,
The urethane resin (I) contains an ether urethane resin and an ester urethane resin or a polycarbonate urethane resin. A surface layer is laminated on the surface of the primer layer opposite to the metal layer,
The metal surface laminate according to claim 1, wherein the surface layer contains a thermoplastic resin (A), a polycaprolactone polyol (B), and an isocyanate crosslinking agent (C). The metal layered product according to claim 1, wherein the metal layer contains indium. A back layer is laminated on the surface of the metal layer opposite to the primer layer,
The said back surface layer contains urethane resin (i) and isocyanate crosslinking agent (ii), The metal tone laminated body of any one of Claim 1 to 3 characterized by the above-mentioned. 5. The laminate according to claim 1, wherein a laminate including the primer layer and the metal layer is formed so as to have at least one recess, and the recess is filled with a urethane resin. Metallic laminate.

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