WO2016203305A1 - 加飾用積層体 - Google Patents

加飾用積層体 Download PDF

Info

Publication number
WO2016203305A1
WO2016203305A1 PCT/IB2016/000803 IB2016000803W WO2016203305A1 WO 2016203305 A1 WO2016203305 A1 WO 2016203305A1 IB 2016000803 W IB2016000803 W IB 2016000803W WO 2016203305 A1 WO2016203305 A1 WO 2016203305A1
Authority
WO
WIPO (PCT)
Prior art keywords
surface protective
protective layer
layer
curable resin
decorative laminate
Prior art date
Application number
PCT/IB2016/000803
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
喜寛 太田
新二 竹林
錦織　義治
Original Assignee
王子ホールディングス株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=57546643&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO2016203305(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by 王子ホールディングス株式会社 filed Critical 王子ホールディングス株式会社
Priority to JP2017524134A priority Critical patent/JP6693519B2/ja
Publication of WO2016203305A1 publication Critical patent/WO2016203305A1/ja

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • C09D201/02—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers

Definitions

  • 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.
  • resin molded bodies have been increasingly used as molded bodies (adhered bodies) for the purpose of reducing the weight of automobile interior and exterior parts, household appliance parts, building material parts, and the like.
  • spray coating is not suitable for decoration (decoration) of a resin molded body
  • various methods have been developed to decorate the surface of the resin molded body (adhered body).
  • 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.
  • corrugation can also decorate the decorating method using a decorating film, it is used for various uses.
  • TOM molding As a method of decorating the surface of a molded body (adhered body) having three-dimensional unevenness with a decorative film, there is a 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 pressure-bonding 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.
  • a film having a resin layer such as a substrate and a surface protective layer and an adhesive layer is preferably used.
  • a film having a resin layer such as a substrate and a surface protective layer and an adhesive layer is preferably used.
  • 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.
  • 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.
  • 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
  • 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.
  • 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.
  • 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
  • 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
  • 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.
  • 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 automobile members, electronic devices, or building materials.
  • 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
  • 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
  • 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.
  • a numerical range represented by using “ ⁇ ” means a range including numerical values described before and after “ ⁇ ” as a lower limit value and an upper limit value.
  • FIG. 1 is a cross-sectional view showing an example of the configuration of the decorative laminate of the present invention.
  • 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.
  • 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.
  • 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.
  • the ultraviolet curable resin examples 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.
  • 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.
  • photoinitiator a known product or a commercially available product can be used.
  • photoinitiators such as Irgacure-184, Irgacure-651 (made by Ciba Specialty Chemicals), Darocur-1173 (made by Merck), etc. can be used, for example.
  • 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.
  • a fluorine 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 fracture elongation at 120 ° C. of the surface protective layer 11 is 50% or more.
  • 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.
  • 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.
  • 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 ⁇ m) 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 ⁇ m) alone was 0.6%.
  • 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.
  • 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 °.
  • 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.
  • 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.
  • 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 ⁇ m, more preferably 1.0 to 15 ⁇ m, and still more preferably 2.0 to 10 ⁇ m. 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • a plastic film obtained using such a resin component for example, commercially available products such as acryloprene HBA001P, HBS010P, and HBA002P can be used.
  • 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 ⁇ m, more preferably 10 to 400 ⁇ m, still more preferably 20 to 300 ⁇ m, and particularly preferably 30 to 250 ⁇ m.
  • 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.
  • 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.
  • 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.
  • tackifiers include aliphatic (C5) petroleum resins, aromatic (C9) petroleum resins, copolymerized (C5 / C9) petroleum resins, dicyclopentadiene (DCPD) petroleum resins, and coumarone indene.
  • the thickness of the adhesive layer 12 is preferably 10 to 100 ⁇ m, and more preferably 20 to 80 ⁇ m. 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.
  • a component having a carboxyl group preferably acrylic acid, methacrylic acid, maleic acid, crotonic acid, crotonic acid, ⁇ -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.
  • 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.
  • 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.
  • 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.
  • under reduced pressure means that the pressure in the molding chamber is 5 kPa or less.
  • the decorative laminate is preferably laminated on the adherend by a so-called TOM molding method.
  • 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.
  • the apparatus used for the TOM molding method is preferably, for example, an NGF molding machine (manufactured by Fuse Vacuum Co., Ltd.).
  • the decorative laminate of the present invention is preferably used for automobile members (interior and exterior), electronic devices or building materials.
  • automobile members internal and exterior
  • electronic devices or building materials include electronic devices, electronic devices or building materials.
  • an automobile exterior member is preferable because it benefits from both excellent moldability and excellent physical properties.
  • 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.
  • Example 1> (Laminate 1) An acrylic film (manufactured by Mitsubishi Rayon Co., Ltd., Acryprene HBA001P, pencil hardness 2H, thickness 125 ⁇ m) 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 ⁇ m. Next, the coated ultraviolet curable resin composition was dried in a hot air oven at 100 ° C. for 1 minute.
  • 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.
  • stacked in this order was obtained.
  • the ultraviolet curable resin composition UV1 the following was used.
  • UV1 (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.
  • acrylic acrylate weight average molecular weight: 78000
  • toluene ethyl acetate
  • 1-hydroxycyclohexyl phenyl ketone as a photoinitiator
  • silicone-based leveling agent and a mass ratio thereof is 30: 60: 8.5: 1: 0.5.
  • Example 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.
  • the ultraviolet curable resin composition UV2 the following was used.
  • 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 )
  • an acrylic group-containing silicone-based leveling agent and a mass ratio of these was 30: 60: 8.5: 1: 0.5.
  • Example 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.
  • the ultraviolet curable resin composition UV3 the following were used.
  • 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.)
  • a fluorine-based leveling agent and the mass ratio of these was 30: 60: 8.5: 1: 0.5.
  • Example 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.
  • the UV curable resin composition UV4 the following was used.
  • 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 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.
  • the ultraviolet curable resin composition UV5 the following were used.
  • UV 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.
  • the UV curable resin composition UV6 the following was used.
  • 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.)
  • a silicone-based leveling agent and the mass ratio of these was 30: 60: 6: 1: 3.
  • Example 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.
  • the ultraviolet curable resin composition UV7 the following were used.
  • 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.)
  • 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.
  • the UV curable resin composition UV8 the following was used.
  • 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.)
  • a fluorine-based leveling agent and the mass ratio of these was 30: 60: 6: 1: 3.
  • 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.
  • UV12 As the ultraviolet curable resin composition UV12, the following was used.
  • 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.
  • Example 3 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.
  • 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.
  • UV14 As the ultraviolet curable resin composition UV14, the following was used.
  • UV 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.)
  • Irgacure 184" manufactured by Ciba Specialty Chemicals Co., Ltd.
  • 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.
  • UV16 As the ultraviolet curable resin composition UV16, the following was used.
  • UV 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.)
  • Irgacure 184" manufactured by Ciba Specialty Chemicals Co., Ltd.
  • ⁇ 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 (stretching ratio in the longitudinal direction of the laminate and the width direction of 50% or more).
  • Scratch hardness was measured for the surface protective layer of each laminate of the above Examples and Comparative Examples according to JIS K 5600.
  • 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.
  • SYMBOLS 1 Laminated body for decorating, 10 ... Base material layer, 11 ... Surface protective layer, 12 . Adhesive layer, 13 ... Separator.
PCT/IB2016/000803 2015-06-15 2016-06-13 加飾用積層体 WO2016203305A1 (ja)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2017524134A JP6693519B2 (ja) 2015-06-15 2016-06-13 加飾用積層体

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2015120338 2015-06-15
JP2015-120338 2015-06-15

Publications (1)

Publication Number Publication Date
WO2016203305A1 true WO2016203305A1 (ja) 2016-12-22

Family

ID=57546643

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/IB2016/000803 WO2016203305A1 (ja) 2015-06-15 2016-06-13 加飾用積層体

Country Status (3)

Country Link
JP (1) JP6693519B2 (zh)
TW (1) TWI679120B (zh)
WO (1) WO2016203305A1 (zh)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017095617A (ja) * 2015-11-25 2017-06-01 株式会社クラレ 活性エネルギー線硬化性樹脂組成物、積層体および成形体、並びにそれらの製造方法
JP2020142484A (ja) * 2019-03-08 2020-09-10 日本カーバイド工業株式会社 加飾シート
US11345125B2 (en) * 2018-02-23 2022-05-31 Toppan Printing Co., Ltd. Decorative sheet, decorative material, and method for producing decorative material

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR3106006B1 (fr) * 2020-01-02 2023-10-27 Saint Gobain Système optique, vitrage isolant comportant un tel système optique, procédé de fabrication de ce vitrage isolant et procédé de protection d’un système optique

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010284910A (ja) * 2009-06-12 2010-12-24 Tomoegawa Paper Co Ltd 加飾用ハードコートフィルム、加飾フィルムおよび加飾成形品
JP2014097662A (ja) * 2014-01-29 2014-05-29 Dainippon Printing Co Ltd 三次元成形加飾フィルム及びその製造方法並びにそれを用いた加飾成形品及びその製造方法
JP2014237790A (ja) * 2013-06-10 2014-12-18 株式会社カネカ 活性エネルギー線硬化性コーティング用樹脂組成物
JP2015066796A (ja) * 2013-09-28 2015-04-13 日本製紙株式会社 成型用ハードコートフィルム及びその製造方法

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013087136A (ja) * 2011-10-13 2013-05-13 Kaneka Corp 熱成形用フィルム向け硬化性樹脂組成物とこの樹脂組成物を積層した熱成形用フィルム
JP2013151133A (ja) * 2012-01-26 2013-08-08 Kaneka Corp 熱成形用ハードコートフィルム
TWM444937U (zh) * 2012-06-08 2013-01-11 Jinhong Technology Co Ltd 具有圖案的機殼保護貼

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010284910A (ja) * 2009-06-12 2010-12-24 Tomoegawa Paper Co Ltd 加飾用ハードコートフィルム、加飾フィルムおよび加飾成形品
JP2014237790A (ja) * 2013-06-10 2014-12-18 株式会社カネカ 活性エネルギー線硬化性コーティング用樹脂組成物
JP2015066796A (ja) * 2013-09-28 2015-04-13 日本製紙株式会社 成型用ハードコートフィルム及びその製造方法
JP2014097662A (ja) * 2014-01-29 2014-05-29 Dainippon Printing Co Ltd 三次元成形加飾フィルム及びその製造方法並びにそれを用いた加飾成形品及びその製造方法

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017095617A (ja) * 2015-11-25 2017-06-01 株式会社クラレ 活性エネルギー線硬化性樹脂組成物、積層体および成形体、並びにそれらの製造方法
US11345125B2 (en) * 2018-02-23 2022-05-31 Toppan Printing Co., Ltd. Decorative sheet, decorative material, and method for producing decorative material
CN114683652A (zh) * 2018-02-23 2022-07-01 凸版印刷株式会社 装饰片
JP2020142484A (ja) * 2019-03-08 2020-09-10 日本カーバイド工業株式会社 加飾シート

Also Published As

Publication number Publication date
TW201704010A (zh) 2017-02-01
JPWO2016203305A1 (ja) 2018-04-05
TWI679120B (zh) 2019-12-11
JP6693519B2 (ja) 2020-05-13

Similar Documents

Publication Publication Date Title
CN107001871B (zh) 粘合片
WO2016203305A1 (ja) 加飾用積層体
WO2011111576A1 (ja) 光学用粘着シート
JP2005537951A (ja) 消去可能な物品の製造方法およびその物品
EP2181845A1 (en) Decoration sheet and method of manufacturing the same
JP7224641B2 (ja) ハードコートフィルムおよびこれを用いたフレキシブルディスプレイ
JP6569587B2 (ja) 両面粘着シート及び積層体
JP6717650B2 (ja) 装飾部材の凹凸面に適用するための追従性粘着フィルム及びその製造方法
TW202138512A (zh) 附剝離薄膜的黏著片
WO2011065341A1 (ja) 光学用両面感圧性接着シート
JP6627576B2 (ja) 加飾用積層体、加飾成形体及び加飾成形体の製造方法
JP6601494B2 (ja) 粘着フィルム、積層体、及び加飾成形体
KR20160113865A (ko) 양면 코팅 테이프, 이를 포함하는 전자 장치 및 양면 코팅 테이프의 제조 방법
TW202113016A (zh) 光交聯性黏著劑及其利用
KR102542711B1 (ko) 가식 성형용 점착 시트
TW202144174A (zh) 積層體
KR20210047958A (ko) 플렉서블 화상 표시 장치 및 이에 이용하는 광학 적층체
JP6493113B2 (ja) 印刷用シート、剥離層付き印刷用シート、および加飾シート
JP7298191B2 (ja) 加飾成形用両面粘着シート、加飾成形用積層粘着シート及び加飾成形積層体
JP7467962B2 (ja) 加飾フィルム及び加飾成形体
JP6544262B2 (ja) 加飾成形用積層体、加飾成形体及び加飾成形体の製造方法
WO2021039808A1 (ja) 加飾フィルム及び加飾成型品
JP7258497B2 (ja) 透明粘着フィルム
WO2022030198A1 (ja) 接合体の分離方法
JP2021160164A (ja) 加飾フィルム及び加飾成形体

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 16811090

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2017524134

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 16811090

Country of ref document: EP

Kind code of ref document: A1