JPWO2016203305A1 - Laminated body for decoration - Google Patents

Abstract

The present invention provides a decorative laminate having simultaneously moldability capable of following a complicated shape and excellent physical properties such as sufficient hardness and chemical resistance. More specifically, the present invention is a decorative laminate having at least a base material layer and a surface protective layer, and having a grazing pencil hardness based on JIS K 5600 of F or more, The protective layer is an outermost layer formed of an ultraviolet curable resin, the elongation at break of the surface protective layer at 120 ° C. is 50% or more, the haze of the surface protective layer is 5% or less, and the surface protection A decorative laminate is provided in which the dynamic friction coefficient of the layer is 1.0 or less.

Description

The present invention relates to a decorative laminate. Specifically, the present invention relates to a decorative layer laminate that is excellent in physical properties such as hardness and chemical resistance while having excellent moldability.
This application claims the priority based on Japanese Patent Application No. 2015-120338 for which it applied on June 15, 2015, and uses the content here.

  Conventionally, when protecting the surface of automobile interior / exterior parts, parts for home appliances, parts for building materials, or decorating (decorating), after processing the molded body by injection molding or vacuum molding, The surface has been coated with a paint by spraying or the like, and then dried and heat-cured. However, in addition to the problem that the discharge of volatile organic solvents deteriorates the working environment, such painting requires work processes and production facilities for each molded part, and also requires repeated coating of paint. Therefore, there was a problem that the yield of the paint was poor and the productivity was low.

  In recent years, resin molded bodies have been used as molded bodies (adhered bodies) for the purpose of reducing the weight of automobile interior and exterior parts, home appliance parts, building material parts, and the like. In many cases, spray coating is not suitable for decoration (decoration) of a resin molded body, and various methods have been developed to decorate the surface of the resin molded body (adhered body). Among them, the method of obtaining the decorative molded body by decorating the outermost surface of the molded body (adhered body) with a decorative film is more flexible in design than the method of applying or printing on the surface using a paint or the like. And has the advantage of excellent productivity. Moreover, since the surface of the molded object (adhered body) which has a three-dimensional unevenness | corrugation can also decorate the decorating method using a decorating film, it is used for various uses.

  As a method of decorating the surface of a molded body (adhered body) having three-dimensional unevenness with a decorative film, there is three-dimensional covering molding (TOM molding) (Patent Document 1). TOM molding is a molding method under vacuum conditions or reduced pressure conditions, and is a method of decorating an adherend by pressing a decorative film and the adherend. In TOM molding, it is possible to decorate regardless of the material of the adherend. Moreover, a reverse taper part and a terminal winding part can be coating-molded, without providing a vacuum hole in a to-be-adhered body.

  As the decorative film used for TOM molding, for example, a film having a resin layer such as a substrate and a surface protective layer and an adhesive layer is preferably used. When such a film is used for TOM molding, it is not necessary to melt the resin layer, and the decorative film and the adherend can be bonded using the adhesive force of the adhesive layer.

Japanese Patent No. 3733564

However, the conventional decorative film has a problem that it does not have sufficient moldability and cannot follow an adherend having a complicated shape. Moreover, even if the conventional decorative film has sufficient moldability, there has been a problem that physical properties such as hardness and chemical resistance are insufficient. That is, the conventional decorative film has a problem that sufficient moldability and excellent physical properties cannot be achieved at the same time.
The present invention has been made in view of the above circumstances. The present invention is obtained by laminating a decorative laminate having excellent moldability and physical properties such as hardness and chemical resistance, and the decorative laminate on an adherend. An object is to provide a decorative molded body.

  As a result of intensive studies, the inventors of the present invention formed a surface protective layer with an ultraviolet curable resin, and the fracture elongation at 120 ° C. of the surface protective layer was a predetermined value or more, and the dynamic friction coefficient was a predetermined value or less. Yes, a layer having a contact angle of xylene within a predetermined range is disposed as the outermost layer of the decorative laminate, and / or scratch hardness based on JIS K 5600 of a surface protective layer formed of an ultraviolet curable resin By making the (pencil method) a predetermined value or more and setting the weight average molecular weight of the ultraviolet curable resin within a predetermined range, etc., excellent formability capable of following a complicated shape, and sufficient hardness and chemical resistance, etc. The present invention has been completed by finding that a decorative laminate having both physical properties can be obtained.

The present invention has the following aspects.
[1] A decorative laminate having at least a base material layer and a surface protective layer, and having a scratch hardness (pencil method) based on JIS K 5600 of F or more, wherein the surface protective layer is UV curable. It is an outermost layer formed of a resin, the elongation at break at 120 ° C. of the surface protective layer is 50% or more, the haze of the surface protective layer is 5% or less, and the dynamic friction coefficient of the surface protective layer is 1 A decorative laminate, which is 0.0 or less.
[2] The decorative laminate according to [1], wherein the surface protective layer has a xylene contact angle of 20 ° to 70 °.
[3] The decorative laminate according to [1] or [2], wherein the ultraviolet curable resin has a weight average molecular weight of 20,000 to 3,000,000.
[4] For decoration according to any one of [1] to [3], wherein the laminate further includes an adhesive layer and a separator layer in this order on the surface of the base material layer opposite to the surface protective layer. Laminated body.
[5] The decorative laminate according to any one of [1] to [4], which is used for molding under vacuum conditions or reduced pressure conditions.
[6] The decorative laminate according to any one of [1] to [5], wherein the laminate is used for an automobile member, an electronic device, or a building material.
[7] A decorative structure in which a decorative laminate is bonded to an adherend via an adhesive layer, and the decorative laminate includes at least a base material layer, a surface protective layer, and The scratch hardness (pencil method) based on JIS K 5600 is F or more, the surface protective layer is an outermost layer formed of an ultraviolet curable resin, and the elongation at break at 120 ° C. of the surface protective layer is Is 50% or more, the haze of the surface protective layer is 5% or less, and the dynamic friction coefficient of the surface protective layer is 1.0 or less.

The present invention may have the following aspects.
[1A] A decorative laminate having at least a base material layer and a surface protective layer, and having a scratch hardness (pencil method) based on JIS K 5600 of F or more, wherein the surface protective layer is UV curable A decorative laminate, which is an outermost layer formed of a resin and has a weight average molecular weight of 20,000 to 3,000,000.
[2A] The elongation at break at 120 ° C. of the surface protective layer is 50% or more, the haze of the surface protective layer is 5% or less, and the dynamic friction coefficient of the surface protective layer is 1.0 or less. The decorative laminate according to [1A], which is characterized.
[3A] The decorative laminate according to [1A] or [2A], wherein the surface protective layer has a xylene contact angle of 20 ° to 70 °.
[4A] The decorative body according to any one of [1A] to [3A], wherein the laminate further includes an adhesive layer and a separator layer in this order on the surface of the base material layer opposite to the surface protective layer. Laminated body.
[5A] The decorative laminate according to any one of [1A] to [4A], which is used for molding under vacuum conditions or reduced pressure conditions.
[6A] The decorative laminate according to any one of [1A] to [5A], wherein the laminate is used for an automobile member, an electronic device, or a building material.
[7A] A decorative structure in which a decorative laminate is bonded to an adherend via an adhesive layer, and the decorative laminate includes at least a base material layer, a surface protective layer, The scratch hardness (pencil method) based on JIS K 5600 is F or more, the surface protective layer is an outermost layer formed of an ultraviolet curable resin, and the elongation at break at 120 ° C. of the surface protective layer is Is 50% or more, the haze of the surface protective layer is 5% or less, and the dynamic friction coefficient of the surface protective layer is 1.0 or less.

  The present invention provides a decorative laminate having simultaneously moldability capable of following a complicated shape and excellent physical properties such as sufficient hardness and chemical resistance.

It is the schematic which shows the structure of the laminated body for decorating of this invention.

  Hereinafter, the present invention will be described in detail. The description of the constituent elements described below may be made based on representative embodiments and specific examples, but the present invention is not limited to such embodiments. In the present specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.

(Deposits for decoration)
FIG. 1 is a cross-sectional view showing an example of the configuration of the decorative laminate of the present invention. As shown in FIG. 1, the decorative laminate 1 of the present invention has a surface protective layer 11, a base material layer 10, an adhesive layer 12, and a separator 13 in this order. The surface protective layer 11 is formed on one surface of the base material layer 10. The adhesive layer 12 is formed on the other surface of the base material layer 10. The separator 13 is attached to the adhesive surface of the adhesive layer 12. The decorative laminate of FIG. 1 is obtained, for example, by applying a resin composition as a material for the surface protective layer 11 and the adhesive layer 12 to both sides of the base material layer 10 and drying and / or curing the resin composition. Can do.

(Surface protective layer 11)
The surface protective layer 11 is a layer that constitutes the outermost layer of the decorative laminate, and is therefore a layer that constitutes the outermost surface of the adherend to be decorated. In particular, when a member requiring strength such as an automobile interior / exterior part is an adherend, it is desirable that the surface protective layer 11 has resistance to scratching, strength, and the like. That is, the surface protective layer 11 is preferably a scratch-resistant resin layer or a so-called hard coat layer. The surface protective layer preferably has a pencil hardness of F or higher, more preferably H or higher, and even more preferably 2H or higher.

  The surface protective layer 11 is formed of an ultraviolet curable resin. The surface protective layer 11 is preferably a layer formed by curing an ultraviolet curable resin composition. The ultraviolet curable resin composition for forming the surface protective layer 11 preferably contains, for example, an ultraviolet curable resin, a solvent, a photoinitiator, a leveling agent, and a surfactant. A solvent is not specifically limited, A well-known thing can be used.

  Examples of the ultraviolet curable resin include acrylic resins, silicone resins, urethane resins, olefin resins, ester resins, etc., but acrylic resins and urethane resins are easy to handle and process. And epoxy resins are preferred. In view of durability, an acrylic resin is particularly preferable. The acrylic resin is preferably acrylic acrylate, the urethane resin is urethane acrylate, and the epoxy resin is preferably epoxy acrylate. Acrylic acrylate is a (meth) acrylate polymer having a (meth) acryloyl group in the side chain.

  The weight average molecular weight of the ultraviolet curable resin is preferably 20,000 to 3,000,000, more preferably 30,000 to 1,000,000, and particularly preferably 50,000 to 200,000. By making the weight average molecular weight of the ultraviolet curable resin within the above-mentioned preferable range, it is possible to further improve the followability to the adherend during molding under vacuum or reduced pressure conditions (TOM molding). It becomes possible to decorate the shaped adherend. For the measurement of the weight average molecular weight, it is preferable to use GPC (gel permeation chromatography), measure and calculate the molecular weight in terms of polystyrene using a column of a styrene divinylbenzene base material in a THF developing solvent.

  A well-known thing or a commercial item can be used as a photoinitiator. As a commercial item, photoinitiators, such as Irgacure-184, Irgacure-651 (made by Ciba Specialty Chemicals), Darocur-1173 (made by Merck), etc. can be used, for example. Among these, Irgacure-184 is preferable. The content of the photoinitiator is preferably 1 to 10% by mass when the total mass of the ultraviolet curable resin composition is 100% by mass.

  As the leveling agent, for example, a fluorine leveling agent, a silicone leveling agent, or an acrylic leveling agent can be preferably used. Of these, silicone leveling agents and / or fluorine leveling agents are particularly preferred. The content of the leveling agent is preferably set so that the dynamic friction coefficient of the surface protective layer 11 is a desired value. The content of the leveling agent may be, for example, 0.1 to 10% by mass when the total mass of the ultraviolet curable resin composition is 100% by mass.

  The breaking elongation at 120 ° C. of the surface protective layer 11 is 50% or more. When the breaking elongation is within the above range, the decorative laminate of the present invention can exhibit good followability even to an adherend having a complicated shape. The breaking elongation can be measured by the method described in the examples of the present specification. When the breaking ratio of the laminate is 50% or more, the breaking elongation can be 50% or more. This breaking elongation is preferably 65% or more, more preferably 85% or more, and particularly preferably 100% or more.

  The haze of the surface protective layer 11 is 5% or less. When the haze of the surface protective layer 11 is within the above range, the color and texture of the base material layer can be shown as the appearance of the decorative laminate, and the design of the adherend to be adhered is freely controlled. be able to. The haze as used herein refers to a value measured with an acrylic film (manufactured by Mitsubishi Rayon Co., Ltd., Acryprene HBA001P, pencil hardness 2H, thickness 125 μm) provided with a surface protective layer. Haze can be measured by the method described in the examples of the present specification. The haze of the acrylic film (manufactured by Mitsubishi Rayon Co., Ltd., Acryprene HBA001P, pencil hardness 2H, thickness 125 μm) alone was 0.6%. By reducing the amount of leveling agent and fine particles added, the haze of the surface protective layer 11 can be reduced to 5% or less. The haze of the surface protective layer 11 is preferably 5% or less, more preferably 3% or less, and particularly preferably 1% or less.

  The dynamic friction coefficient of the surface protective layer 11 is 1.0 or less. When the dynamic friction coefficient is within the above range, a sufficient surface protection effect can be exhibited even when used in a severe environment exposed to the outside air and dirt. The dynamic friction coefficient can be measured by the method described in the examples of the present specification. By adding 0.5 part or more of the leveling agent to the surface protective layer, the dynamic friction coefficient of the surface protective layer can be made 1.0 or less. The dynamic friction coefficient of the surface protective layer 11 is preferably 1.0 or less, more preferably 0.8 or less, and particularly preferably 0.5 or less.

  The surface protective layer 11 preferably has a xylene contact angle of 20 ° to 70 °. When the contact angle of xylene is within the above range, the surface protective layer 11 has suitable oil repellency, and exhibits sufficient chemical resistance even in applications exposed to harsh environments such as automobile exterior members. it can. By increasing the leveling agent or selecting an ultraviolet curable resin, the contact angle of xylene on the surface protective layer can be within the above range. The contact angle of xylene can be measured by the method described in the examples of the present specification. The contact angle of xylene of the surface protective layer is preferably 20 ° or more and 70 ° or less, more preferably 25 ° or more and 60 ° or less, and particularly preferably 30 ° or more and 50 ° or less. In the present invention, the contact angle of xylene is a value obtained by the method described in the examples.

  The surface protective layer 11 may contain an ultraviolet absorber. In this case, it is preferable that the surface protective layer 11 has a 380 nm ultraviolet transmittance of 10% or less. Since the surface protective layer 11 absorbs ultraviolet rays, the adhesive layer and the adherend can be prevented from aging due to ultraviolet rays. Therefore, the decorative laminate and the decorative laminate of the present invention are attached. The durability of the adherend is improved. The content of the ultraviolet absorber is preferably 1 to 15% by mass, more preferably 2 to 12% by mass, when the dry weight of the surface protective layer 11 is 100% by mass. Examples of the ultraviolet absorber include benzotriazole, benzophenone, salicylate, cyanoacrylate, nickel, and triazine.

  The thickness of the surface protective layer 11 is preferably 0.5 to 20 μm, more preferably 1.0 to 15 μm, and further preferably 2.0 to 10 μm. When the thickness of the surface protective layer 11 is within the above range, physical properties such as moldability and rigidity are achieved in a balanced manner.

(Base material layer)
The base material layer 10 is a layer that functions as a so-called base material for forming and holding the surface protective layer 11 and the adhesive layer 12. Moreover, the base material layer 10 may have a function as a decoration layer for giving the designability to the external appearance of the laminated body for decoration. The base material layer 10 may be composed of a plurality of layers. For example, the base material layer 10 may have a two-layer structure (not shown) in which a decorative layer having a color and a transparent resin layer are laminated. Good. In this case, the decorative laminate of the present invention preferably has a surface protective layer, a transparent resin layer, a decorative layer, an adhesive layer, and a separator in this order. Furthermore, you may have a surface protective layer, a transparent resin layer, a decoration layer, an adhesion layer or an adhesion layer, a thermoplastic resin, an adhesion layer, and a separator in this order.
Moreover, the resin layer which comprises the base material layer 10 may be metal-deposited for the purpose of providing designability etc.

  The material of the layers (decorative layer and transparent resin layer) constituting the base material layer 10 is preferably plastic, for example. Examples of the plastic include ABS resin (acrylonitrile, butadiene and styrene copolymer), AS resin (acrylonitrile and styrene copolymer), acrylic resin, polyethylene terephthalate, polybutylene terephthalate, nylon, polyacetal, and polyphenylene oxide. , Phenolic resin, urea resin, melamine resin, liquid crystal polymer, polytetrafluoroethylene, polyvinylidene fluoride, polysulfone, polyethersulfone, polyacetal, polyetheretherketone, polyphenylene sulfide, polyetherimide, polyamideimide, polycarbonate, polyethylene, polypropylene, Polystyrene, urethane resin and the like are preferable. Among these, ABS resin or acrylic resin is more preferable. The decorative layer may be a colored layer in which carbon (graphite) or the like is blended with these resins.

  The acrylic resin constituting the layer constituting the base material layer 10 is preferably a resin obtained by polymerizing a resin composition whose main component is a monomer component having a (meth) acryloyl group. The main component of the monomer component is preferably a (meth) acrylic acid ester, and is preferably methyl methacrylate. As a plastic film obtained using such a resin component, for example, commercially available products such as acryloprene HBA001P, HBS010P, and HBA002P can be used. Moreover, the layer which comprises the base material layer 10 may be obtained by extruding a resin component.

  The thickness of the base material layer 10 is, for example, preferably 5 to 500 μm, more preferably 10 to 400 μm, still more preferably 20 to 300 μm, and particularly preferably 30 to 250 μm. When the thickness of the base material layer 10 is within the above preferable range, the balance between the moldability and physical properties such as rigidity is further improved.

  The decorative laminate of the present invention preferably has an adhesive layer and a separator in this order on the surface opposite to the surface protective layer of the base material layer. The preferable form of an adhesion layer and a separator is demonstrated below.

(Adhesive layer)
As an adhesive which comprises the adhesion layer 12, a well-known adhesive can be utilized. Examples of the pressure sensitive adhesive include natural rubber pressure sensitive adhesive, synthetic rubber pressure sensitive adhesive, acrylic pressure sensitive adhesive, urethane pressure sensitive adhesive, and silicone pressure sensitive adhesive. The pressure-sensitive adhesive may be any of a solvent system, a solventless system, an emulsion system, and an aqueous system. Among these, from the viewpoints of transparency, weather resistance, durability, cost, etc., acrylic pressure-sensitive adhesives, particularly solvent-based ones are preferred.
Other auxiliary agents may be added to the adhesive as necessary. Other auxiliary agents include antioxidants, tackifiers, silane coupling agents, UV absorbers, hindered amine compounds and other light stabilizers, thickeners, pH adjusters, binders, crosslinking agents, adhesive particles, Examples include antifoaming agents, antiseptic / antifungal agents, pigments, inorganic fillers, stabilizers, wetting agents, wetting agents and the like.
Examples of tackifiers include aliphatic (C5) petroleum resins, aromatic (C9) petroleum resins, copolymerized (C5 / C9) petroleum resins, dicyclopentadiene (DCPD) petroleum resins, and coumarone indene. Examples thereof include resins, acrylic resins, styrene resins, rosins, rosin ester resins, terpene resins, aromatic modified terpene resins, terpene phenol resins, and hydrogenated resins thereof.
It is preferable that content of the tackifier in an adhesive is 50 mass parts or less with respect to 100 mass parts of adhesives.
The thickness of the adhesive layer 12 is preferably 10 to 100 μm, and more preferably 20 to 80 μm. When the thickness of the adhesive layer 12 is within the above range, both sufficient adhesiveness and economical efficiency can be achieved.

  The adhesive strength of the adhesive layer measured based on JIS Z 0237 is preferably 10 to 100 N / 25 mm, and more preferably 25 to 75 N / 25 mm.

  Moreover, you may contain the following component as needed for adhesive force improvement. For example, a component having a carboxyl group, preferably acrylic acid, methacrylic acid, maleic acid, crotonic acid, crotonic acid, β-carboxyethyl acrylate, and / or a component having a hydroxyl group, preferably 2-hydroxyethyl (meth) acrylate , Humanoxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, chloro-2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydrooctyl Mention may be made of (meth) acrylates and / or copolymerizable unsaturated components, preferably acrylamide, methacrylamide, vinyl acetate, (meth) acrylonitrile and macromers.

(separator)
The separator 13 is a layer that temporarily protects the adhesive layer 12 until the decorative laminate of the present invention is attached to an adherend. It is preferable that the separator 13 is provided with a release layer such as silicone on the surface of a resin film such as polyethylene terephthalate (PET), polyethylene, and polypropylene.

The decorative laminate of the present invention is preferably used for molding under vacuum conditions or reduced pressure conditions.
The decorative laminate of the present invention is laminated on an adherend by pressing one side of the film (the surface on which the adhesive layer is not formed) in a non-contact manner in a decompressed molding chamber. Is preferred. Pressurizing in a non-contact manner means applying pressure by a gas such as air or gas to a decorative laminate or the like without physically contacting a mold or the like. In the present specification, “under reduced pressure” means that the pressure in the molding chamber is 5 kPa or less. In addition, it is more preferable to apply atmospheric pressure or compressed air to one side of the decorative laminate (the surface on which the pressure-sensitive adhesive layer is not formed) with the molding chamber in a substantially vacuum state.

In the present invention, the decorative laminate is preferably laminated on the adherend by a so-called TOM molding method. Unless otherwise specified in the present specification, the TOM molding method is disclosed in Japanese Patent Application Laid-Open No. 2002-079573, “Vacuum Forming Apparatus” (Fuse Vacuum Co., Ltd.), Japanese Patent Application Laid-Open No. 2002-067137, “Vacuum”. "Molding device" (Fusi Vacuum Co., Ltd.), Japanese Patent Application Laid-Open No. 2012-116094, "Vacuum Forming Method" (Fuse Vacuum Co., Ltd.) It is preferable to carry out according to the method described in “Substrate for Vacuum and Vacuum Forming Method” (Fuse Vacuum Co., Ltd.).
The apparatus used for the TOM molding method is preferably an NGF molding machine (manufactured by Fuse Vacuum Co., Ltd.), for example.

  It is preferable that the laminated body for decoration of this invention is used for a motor vehicle member (interior and exterior), an electronic device, or a building material. Among these, the use of an automobile exterior member is preferable because it benefits from both excellent moldability and excellent physical properties.

(Adherent)
In this invention, it is preferable that the shape of a to-be-adhered body, ie, the shape of the object on which the laminated body for decorating 1 is laminated, is non-planar. This shape may be, for example, a substantially spherical shape, or an irregular shape such as a convex shape.

  EXAMPLES Hereinafter, although an Example is shown and this invention is demonstrated more concretely, this invention is not limited to these examples.

<Example 1>
(Laminate 1)
An acrylic film (manufactured by Mitsubishi Rayon Co., Ltd., Acryprene HBA001P, pencil hardness 2H, thickness 125 μm) was used as the substrate. An ultraviolet curable resin composition UV1 described later was applied to one side of the substrate using a bar coater so that the thickness after curing was 5 μm. Next, the coated ultraviolet curable resin composition was dried in a hot air oven at 100 ° C. for 1 minute. Then, the surface protective layer is formed by irradiating the ultraviolet curable resin composition by irradiating the ultraviolet ray so that the illuminance of the ultraviolet ray having a wavelength of 365 nm is 100 mW / cm ² and the integrated light amount is 500 mJ / cm ² with a high pressure mercury lamp. Formed. Thus, the laminated body 1 by which the base material layer and the surface protective layer were laminated | stacked in this order was obtained.
As the ultraviolet curable resin composition UV1, the following was used.
(Ultraviolet curable resin composition UV1)
As UV curable resin composition UV1, acrylic acrylate (weight average molecular weight: 78000), toluene, ethyl acetate, and 1-hydroxycyclohexyl phenyl ketone as a photoinitiator (“Irgacure 184” manufactured by Ciba Specialty Chemicals Co., Ltd.) ) And a silicone-based leveling agent, and a mass ratio thereof is 30: 60: 8.5: 1: 0.5.

<Example 2>
(Laminate 2)
A laminate 2 was obtained in the same manner as in Example 1 except that UV2 described later was used as the ultraviolet curable resin composition.
As the ultraviolet curable resin composition UV2, the following was used.
(Ultraviolet curable resin composition UV2)
As UV curable resin composition UV2, acrylic acrylate (weight average molecular weight: 78000), toluene, ethyl acetate, and 1-hydroxycyclohexyl phenyl ketone (Irgacure 184, manufactured by Ciba Specialty Chemicals Co., Ltd.) as a photoinitiator ) And an acrylic group-containing silicone-based leveling agent, and a mass ratio of these was 30: 60: 8.5: 1: 0.5.

<Example 3>
(Laminate 3)
A laminate 3 was obtained in the same manner as in Example 1 except that UV3 described later was used as the ultraviolet curable resin composition.
As the ultraviolet curable resin composition UV3, the following were used.
(Ultraviolet curable resin composition UV3)
As UV curable resin composition UV3, acrylic acrylate (weight average molecular weight: 78000), toluene, ethyl acetate, and photoinitiator 1-hydroxycyclohexyl phenyl ketone ("Irgacure 184" manufactured by Ciba Specialty Chemicals Co., Ltd.) ) And a fluorine-based leveling agent, and the mass ratio of these was 30: 60: 8.5: 1: 0.5.

<Example 4>
(Laminate 4)
A laminate 4 was obtained in the same manner as in Example 1 except that UV4 described later was used as the ultraviolet curable resin composition.
As the UV curable resin composition UV4, the following was used.
(Ultraviolet curable resin composition UV4)
As UV curable resin composition UV4, acrylic acrylate (weight average molecular weight: 78000), urethane acrylate (weight average molecular weight: 78000), toluene, ethyl acetate, and 1-hydroxycyclohexyl phenyl ketone (1) as a photoinitiator ( Ciba Specialty Chemicals Co., Ltd. “Irgacure 184”) and a silicone leveling agent were used, and the mass ratio thereof was 15: 15: 60: 8.5: 1: 0.5.

<Example 5>
(Laminate 5)
A laminate 5 was obtained in the same manner as in Example 1 except that UV5 described later was used as the ultraviolet curable resin composition.
As the ultraviolet curable resin composition UV5, the following were used.
(Ultraviolet curable resin composition UV5)
As UV curable resin composition UV5, urethane acrylate (weight average molecular weight: 78000), toluene, ethyl acetate, and photoinitiator 1-hydroxycyclohexyl phenyl ketone ("Irgacure 184" manufactured by Ciba Specialty Chemicals Co., Ltd.) ) And a silicone leveling agent, and the mass ratio of these was 30: 56.5: 8.5: 1: 4.

<Example 6>
(Laminated body 6)
A laminate 6 was obtained in the same manner as in Example 1 except that UV6 described later was used as the ultraviolet curable resin composition.
As the UV curable resin composition UV6, the following was used.
(Ultraviolet curable resin composition UV6)
As UV curable resin composition UV6, acrylic acrylate (weight average molecular weight: 78000), toluene, ethyl acetate, and photoinitiator 1-hydroxycyclohexyl phenyl ketone ("Irgacure 184" manufactured by Ciba Specialty Chemicals Co., Ltd.) ) And a silicone-based leveling agent, and the mass ratio of these was 30: 60: 6: 1: 3.

<Example 7>
(Laminate 7)
A laminate 7 was obtained in the same manner as in Example 1 except that UV7 described later was used as the ultraviolet curable resin composition.
As the ultraviolet curable resin composition UV7, the following were used.
(Ultraviolet curable resin composition UV7)
As UV curable resin composition UV7, acrylic acrylate (weight average molecular weight: 78000), toluene, ethyl acetate, and 1-hydroxycyclohexyl phenyl ketone as photoinitiator (“Irgacure 184” manufactured by Ciba Specialty Chemicals Co., Ltd.) ) And an acrylic group-containing silicone-based leveling agent, and a mixture having a mass ratio of 30: 60: 6: 1: 3 was used.

<Example 8>
(Laminated body 8)
A laminate 8 was obtained in the same manner as in Example 1 except that UV8 described later was used as the ultraviolet curable resin composition.
As the UV curable resin composition UV8, the following was used.
(Ultraviolet curable resin composition UV8)
As UV curable resin composition UV8, acrylic acrylate (weight average molecular weight: 78000), toluene, ethyl acetate, and photoinitiator 1-hydroxycyclohexyl phenyl ketone ("Irgacure 184" manufactured by Ciba Specialty Chemicals Co., Ltd.) ) And a fluorine-based leveling agent, and the mass ratio of these was 30: 60: 6: 1: 3.

<Comparative Example 1>
(Laminate 11)
A laminate 11 was obtained in the same manner as in Example 1 except that UV11 described later was used as the ultraviolet curable resin composition.
The following was used as said ultraviolet curable resin composition UV11.
(Ultraviolet curable resin composition UV11)
As UV curable resin composition UV11, acrylic acrylate (weight average molecular weight: 78000), toluene, ethyl acetate, and 1-hydroxycyclohexyl phenyl ketone as a photoinitiator (“Irgacure 184” manufactured by Ciba Specialty Chemicals Co., Ltd.) And a mass ratio of 30: 60: 9: 1 was used.

<Comparative example 2>
(Laminated body 12)
A laminate 12 was obtained in the same manner as in Example 1 except that UV12 described later was used as the ultraviolet curable resin composition.
As the ultraviolet curable resin composition UV12, the following was used.
(Ultraviolet curable resin composition UV12)
As ultraviolet curable resin composition UV12, acrylic acrylate (weight average molecular weight: 15000), methyl isobutyl ketone, and 1-hydroxycyclohexyl phenyl ketone (“Irgacure 184” manufactured by Ciba Specialty Chemicals Co., Ltd.) as a photoinitiator And a silicone leveling agent, and a mass ratio of these was 60: 38.5: 1: 0.5.

<Comparative Example 3>
(Laminated body 13)
A laminate 13 was obtained in the same manner as in Example 1 except that the ultraviolet curable resin composition was changed to UV13 and an electron beam was used for curing the coating film.
The following was used as said electron beam curable resin composition UV13.
(Ultraviolet curable resin composition UV13)
The electron beam curable resin composition UV13 includes acrylic acrylate (weight average molecular weight: 78000), toluene, ethyl acetate, and a silicone leveling agent, and the mass ratio thereof is 30: 60: 9.5: 0. A mixture of .5 was used.

<Comparative Example 4>
(Laminated body 14)
A laminate 14 was obtained in the same manner as in Example 1 except that UV14 described later was used as the ultraviolet curable resin composition.
As the ultraviolet curable resin composition UV14, the following was used.
(Ultraviolet curable resin composition UV14)
As UV curable resin composition UV14, urethane acrylate (weight average molecular weight: 78000), toluene, ethyl acetate, and photoinitiator 1-hydroxycyclohexyl phenyl ketone ("Irgacure 184" manufactured by Ciba Specialty Chemicals Co., Ltd.) ) And a silicone-based leveling agent, and a mass ratio thereof is 30: 60: 8.5: 1: 0.5.

<Comparative Example 5>
(Laminate 15)
A laminate 15 was obtained in the same manner as in Example 1 except that UV15 described later was used as the ultraviolet curable resin composition.
The following were used as said ultraviolet curable resin composition UV15.
(Ultraviolet curable resin composition UV15)
As UV curable resin composition UV15, urethane acrylate (weight average molecular weight: 78000), toluene, ethyl acetate, and photoinitiator 1-hydroxycyclohexyl phenyl ketone ("Irgacure 184" manufactured by Ciba Specialty Chemicals Co., Ltd.) And a mass ratio of 30: 60: 9: 1 was used.

<Comparative Example 6>
(Laminated body 16)
A laminate 16 was obtained in the same manner as in Example 1 except that UV16 described later was used as the ultraviolet curable resin composition.
As the ultraviolet curable resin composition UV16, the following was used.
(Ultraviolet curable resin composition UV16)
As UV curable resin composition UV16, urethane acrylate (weight average molecular weight: 78000), toluene, ethyl acetate, and photoinitiator 1-hydroxycyclohexyl phenyl ketone ("Irgacure 184" manufactured by Ciba Specialty Chemicals Co., Ltd.) ) And a silicone leveling agent, and the mass ratio of these was 30: 56.5: 8.5: 1: 5.

(Formability evaluation test)
About the surface protective layer of the laminated body of the said Example and comparative example, the draw ratio of the laminated body longitudinal direction and the width direction is 50% under 120 degreeC using a TOM molding machine (Fuse Vacuum Co., Ltd. make, NGF molding machine). Molding was performed under the above conditions to obtain a molded body. About the said molded object, the moldability was evaluated according to the following evaluation criteria.
◯: No destruction of the surface protective layer of the laminate was observed at the maximum stretched portion of the laminate (stretching ratio in the longitudinal direction of the laminate and the width direction of 50% or more).
Δ: Some destruction of the surface protective layer of the laminate was observed at the maximum stretched portion of the laminate (stretch ratio of the laminate in the longitudinal direction and the width direction of 50% or more), but there is no practical problem.
X: Destruction of the surface protective layer of the laminate was observed at the maximum stretched portion of the laminate (stretch ratio of the laminate in the longitudinal direction and the width direction was 50% or more).

(Dynamic friction coefficient evaluation test)
In the above Examples and Comparative Examples, the surface protection of the laminate was carried out using a tensile tester “Tensilon RTC-1210A” manufactured by Orientec in accordance with “JIS K 7125: 1999 Plastic-Film and Sheet-Friction Coefficient Test Method”. The dynamic friction coefficient of the layer was measured.

(Contact angle evaluation test)
In each of the laminates of the above Examples and Comparative Examples, a sample was obtained by cutting into a rectangle having a length of 40 mm and a width of 15 mm. The contact angle of the surface protective layer of the laminate was measured using an automatic contact angle meter (DM501, manufactured by Kyowa Interface Science Co., Ltd.) and xylene. Each sample was measured five times, and the average value was obtained. Evaluation was performed using the average value.

(Xylene resistance evaluation test)
Each sample was obtained by cutting out each laminated body of the said Example and the said comparative example into the rectangle of length 40mm x width 15mm. 0.2 mL of xylene was dropped on the surface of these samples and left at 23 ° C. and 50% humidity for 30 minutes. After 30 minutes, the xylene was wiped off with a cloth. The surface feel of these samples was evaluated according to the following evaluation criteria.
○: No change △: Partial change ×: Large change

(Evaluation of scratch resistance)
The work gloves cut out to 4 cm ² were placed on the surface protective layers of the laminates of the above examples and comparative examples, and after reciprocating a distance of 50 mm 50 times under a load of 9.8 N, the following evaluation criteria According to the above, the surface texture of these samples was evaluated.
○: No scratch Δ: There are 1 to 10 scratches ×: There are 10 or more scratches

(Measurement of scratch hardness)
Scratch hardness (pencil method) was measured for the surface protective layer of each laminate of the above Examples and Comparative Examples according to JIS K 5600.

(Measure haze)
Each laminate of the above Examples and Comparative Examples was measured according to JIS K 7136 with a haze meter “NDH-5000” manufactured by Nippon Denshoku Industries Co., Ltd.

(Weight average molecular weight)
For weight average molecular weight measurement, GPC (gel permeation chromatography) was used, a styrene divinylbenzene-based column was used in a THF developing solvent, and a molecular weight obtained in terms of polystyrene was used.

  DESCRIPTION OF SYMBOLS 1 ... Laminated body for decorating, 10 ... Base material layer, 11 ... Surface protective layer, 12 ... Adhesive layer, 13 ... Separator.

Claims (7)

  A decorative laminate having at least a base material layer and a surface protective layer and having a scratched pencil hardness based on JIS K 5600 of F or more, wherein the surface protective layer is formed of an ultraviolet curable resin. It is an outer layer, the elongation at break of the surface protective layer at 120 ° C. is 50% or more, the haze of the surface protective layer is 5% or less, and the dynamic friction coefficient of the surface protective layer is 1.0 or less. A decorative laminate characterized by the following.   2. The decorative laminate according to claim 1, wherein the surface protective layer has a xylene contact angle of 20 ° to 70 °.   The laminate for decoration according to claim 1 or 2, wherein the ultraviolet curable resin has a weight average molecular weight of 20,000 to 3,000,000.   The laminated body for decorating of any one of Claims 1-3 in which the said laminated body has an adhesion layer and a separator layer in this order on the surface opposite to the said surface protective layer of the said base material layer.   The laminated body for decoration of any one of Claims 1-4 used for shaping | molding on vacuum conditions or pressure reduction conditions.   The laminate for decoration according to any one of claims 1 to 5, wherein the laminate is used for an automobile member, an electronic device, or a building material. A decorative structure in which the decorative laminate is bonded to an adherend via an adhesive layer,
The decorative laminate has at least a base material layer and a surface protective layer, a scratch pencil hardness based on JIS K 5600 is F or more, and the surface protective layer is formed of an ultraviolet curable resin. It is the outermost layer, the breaking elongation at 120 ° C. of the surface protective layer is 50% or more, the haze of the surface protective layer is 5% or less, and the dynamic friction coefficient of the surface protective layer is 1.0 or less. A decorative structure characterized by that.

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