WO2024089528A1 - Film adhésif - Google Patents

Film adhésif Download PDF

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Publication number
WO2024089528A1
WO2024089528A1 PCT/IB2023/060421 IB2023060421W WO2024089528A1 WO 2024089528 A1 WO2024089528 A1 WO 2024089528A1 IB 2023060421 W IB2023060421 W IB 2023060421W WO 2024089528 A1 WO2024089528 A1 WO 2024089528A1
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WO
WIPO (PCT)
Prior art keywords
acrylic
approximately
adhesive
mass
meth
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PCT/IB2023/060421
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English (en)
Inventor
Hidetoshi Abe
Original Assignee
3M Innovative Properties Company
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Publication of WO2024089528A1 publication Critical patent/WO2024089528A1/fr

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Classifications

    • 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
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/385—Acrylic polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/08—Ingredients agglomerated by treatment with a binding agent
    • 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
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer
    • 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
    • C09J2433/00—Presence of (meth)acrylic polymer

Definitions

  • the present disclosure relates to an adhesive film.
  • Adhesive films with metallic appearance have been widely used in, for example, markings on vehicles, ships, and aircraft, interior and exterior of buildings, and illuminated signs.
  • Such an adhesive film is typically a laminate including a film layer and a pressuresensitive adhesive layer, and has a structure in which the film layer, the pressure-sensitive adhesive layer, or another optional intermediate layer contains a metallic pigment, or a metal layer such as metal plating, a metal-deposited film, or a metal foil is arranged on top of the surface of the film layer or in between the layers constituting the adhesive film.
  • Patent Document 1 JP 2006-088593 A describes "a metallic adhesive sheet for decoration obtained by laminating an acrylic resin layer (A) containing a UV absorbing agent and having a total light transmittance of visible light of 85% or greater, a metallic adhesive layer (B) obtained by blending an aluminum metal powder and a pearl pigment in an acrylic adhesive agent, a soft vinyl chloride resin layer (C) that is colored, and an acrylic adhesive layer (D), in this order.
  • a surface to which an adhesive film is adhered such as an interior wall or exterior wall of a building, is a rough surface.
  • the adhesive film may be adhered to a flat surface but it may also be adhered in such a manner that the adhesive film covers a curved surface or a corner portion.
  • the present disclosure provides an adhesive film that can be adhered to various three- dimensional surfaces, such as rough surfaces, curved surfaces, and corner portions, and that can provide an excellent metallic appearance.
  • An ordinary metallic pigment used to impart a metallic appearance such as an aluminum pigment, has low compatibility with a pressure-sensitive adhesive.
  • the inventors of the present disclosure found that the metallic pigment having a resin coating has excellent compatibility with a pressure-sensitive adhesive and can maintain adhesiveness and elongation properties while metallic appearance is imparted to a pressure-sensitive adhesive layer.
  • an adhesive film having a metallic appearance including a clear film layer and an acrylic pressure-sensitive adhesive layer, the acrylic pressure-sensitive adhesive layer including an acrylic adhesive polymer and a resin- coated metal pigment, the acrylic adhesive polymer having a glass transition temperature of - 25°C or less, and the acrylic pressure-sensitive adhesive layer containing from 5 parts by mass to 100 parts by mass of the resin-coated metal pigment relative to 100 parts by mass of the acrylic adhesive polymer is provided.
  • an adhesive film that can be adhered to various three-dimensional surfaces, such as rough surfaces, curved surfaces, and corner portions, and that can provide an excellent metallic appearance is provided.
  • FIG. 1 is a schematic cross-sectional view of an adhesive film according to an embodiment of the present disclosure.
  • (meth)acrylic refers to acrylic or methacrylic
  • (meth)acrylate refers to acrylate or methacrylate
  • the term “film” encompasses articles referred to as "sheets”.
  • pressure-sensitive adhesive(ness) refers to the characteristic of a material or composition that the material or composition adheres to various surfaces with just light pressure for a short time in the temperature range of usage, such as from 0°C to 50°C, and does not exhibit a phase change (from liquid to solid).
  • adheresive(ness) is used interchangeably with "pressure-sensitive adhesive(ness)”.
  • An adhesive film of an embodiment has a clear film layer and an acrylic pressuresensitive adhesive layer and has a metallic appearance.
  • the acrylic pressure-sensitive adhesive layer includes an acrylic adhesive polymer and a resin-coated metal pigment.
  • the resin-coated metal pigment imparts a metallic appearance, which is visible through the clear film layer of the adhesive film, to the acrylic pressure-sensitive adhesive layer.
  • the clear film layer and the acrylic pressure-sensitive adhesive layer may be in a direct contact, or another layer, such as a colored layer, a printed layer, or a bulk layer, may be interposed between these layers.
  • another layer such as a colored layer, a printed layer, a bulk layer, or a surface-protecting layer, may be laminated.
  • the adhesive film may further include another functional layer such as a primer layer that enhances adhesive properties of the clear film layer and the acrylic pressure-sensitive adhesive layer.
  • a surface that is in contact with the acrylic pressure-sensitive adhesive layer of the clear film layer may be subjected to a surface treatment, such as corona treatment and plasma treatment.
  • the adhesive film may include a liner on the surface of the acrylic pressure-sensitive adhesive layer, the surface being on an opposite side of the clear film layer.
  • the liner which is an optional component, include plastic materials such as polyethylenes, polypropylenes, polyesters, and cellulose acetates, papers, and laminated papers coated with such plastic materials. These liners may have a surface that has been subjected to releaseliner treatment with silicone or the like. The thickness of the liner can be typically approximately 10 pm or greater, or approximately 25 pm or greater, and approximately 500 pm or less, or approximately 200 pm or less.
  • FIG. 1 illustrates a schematic cross-sectional view of an adhesive film of an embodiment.
  • the adhesive film 10 has a clear film layer 12, an acrylic pressure-sensitive adhesive layer 14 and, optionally, a liner 16.
  • the acrylic pressure-sensitive adhesive layer 14 includes an acrylic adhesive polymer 142 and resin-coated metal pigments 144 dispersed in the acrylic adhesive polymer 142.
  • plastic films such as polyethylene films, polypropylene films, polyester films, acrylic resin films, polycarbonate films, polyvinyl chloride films, polyvinylidene chloride films, polyurethane films, polystyrene films, and polyamide films, can be used.
  • the thickness can be approximately 5 pm or greater, approximately 10 pm or greater, or approximately 20 pm or greater, and approximately 500 pm or less, approximately 300 pm or less, or approximately 200 pm or less.
  • the visible light transmittance of the clear film layer is approximately 70% or greater, approximately 80% or greater, or approximately 90% or greater.
  • visible light transmittance refers to an average visible light transmittance in the wavelength of 380 nm to 780 nm measured in accordance with JIS A 5759:2008.
  • the acrylic pressure-sensitive adhesive layer includes an acrylic adhesive polymer and resin-coated metal pigments.
  • the acrylic adhesive polymer can be obtained by polymerizing or copolymerizing a polymerizable composition containing a (meth)acrylic monomer and, as necessary, a monomer having another monoethylenic unsaturated group.
  • a (meth)acrylic monomer and a monomer having another monoethylenic unsaturated group are collectively referred to as polymerizable components.
  • the (meth)acrylic monomer and the monomer having another monoethylenic unsaturated group may be used in a combination of one type alone, or in combination of two or more types.
  • the (meth)acrylic monomer typically includes an alkyl (meth)acrylate.
  • the number of carbon atoms of the alkyl group of the alkyl (meth)acrylate may be from 1 to 12.
  • alkyl (meth)acrylate include straight-chain or branched alkyl (meth)acrylate, such as methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, 2-methylbutyl (meth)acrylate, isoamyl (meth)acrylate, n-hexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-nonyl (meth)acrylate, isononyl (meth)acrylate, n-decyl (meth)acrylate, isodecyl (meth)acrylate, and n-dodecyl (
  • the alkyl (meth)acrylate preferably includes methyl acrylate, n-butyl acrylate, 2-methylbutyl acrylate, 2-ethylhexyl acrylate, isooctyl acrylate, or a combination of these.
  • the alkyl (meth)acrylate forms a main component of the acrylic adhesive polymer.
  • the acrylic adhesive polymer is obtained by copolymerizing a polymerizable composition containing the alkyl (meth)acrylate in an amount of approximately 50 mass% or greater, approximately 70 mass% or greater, or approximately 80 mass% or greater, and approximately 99.5 mass% or less, approximately 99 mass% or less, or approximately 98 mass% or less, with respect to the mass of the polymerizable components, and includes structural units derived from the alkyl (meth)acrylate in the mass ratio described above.
  • the (meth)acrylic monomer may include aromatic (meth)acrylate such as phenyl (meth)acrylate and p-tolyl (meth)acrylate; phenoxy alkyl (meth)acrylate such as phenoxy ethyl (meth)acrylate; alkoxy alkyl (meth)acrylate such as methoxypropyl (meth)acrylate and 2-methoxybutyl (meth)acrylate; or cyclic ether-containing (meth)acrylate such as glycidyl (meth)acrylate or tetrahydro furfuryl (meth)acrylate.
  • aromatic (meth)acrylate such as phenyl (meth)acrylate and p-tolyl (meth)acrylate
  • phenoxy alkyl (meth)acrylate such as phenoxy ethyl (meth)acrylate
  • alkoxy alkyl (meth)acrylate such as methoxypropyl (meth)acrylate and 2-
  • the (meth)acrylic monomer or the monomer having another monoethylenic unsaturated group may include a polar monomer that is copolymerizable with the alkyl (meth)acrylate.
  • the polar monomer include carboxy group-containing monomers such as (meth)acrylic acid, phthalic acid monohydroxyethyl (meth)acrylate, [3-carboxyethyl (meth)acrylate, 2-(meth)acryloyloxyethyl succinic acid, 2-(meth)acryloyloxyethyl hexahydrophthalic acid, crotonic acid, itaconic acid, fumaric acid, citraconic acid, and maleic acid; amino group-containing monomers, including aminoalkyl (meth)acrylate such as aminoethyl (meth)acrylate, monoalkylaminoalkyl (meth)acrylate such as butylaminoethyl (meth)acrylate, dialkylamin
  • Examples of the monomer having another monoethylenic unsaturated group include aromatic vinyl monomers such as styrene, a-methyl styrene, and vinyl toluene; and vinyl esters such as vinyl acetate.
  • the acrylic adhesive polymer is preferably a carboxy group-containing (meth)acrylic polymer.
  • the carboxy group-containing (meth)acrylic polymer can be obtained by copolymerizing a polymerizable composition containing a carboxy group-containing monomer as a polymerizable component.
  • the carboxy group-containing (meth)acrylic polymer can enhance adhesive strength by enhancing cohesive force by the presence of the carboxy group.
  • the carboxy group-containing (meth)acrylic polymer may enhance adhesive properties between the clear film layer and the acrylic pressure-sensitive adhesive layer.
  • As the carboxy group-containing monomer (meth)acrylic acid is preferred.
  • the carboxy group-containing (meth)acrylic polymer is obtained by copolymerizing a polymerizable composition containing the carboxy group-containing monomer in an amount of approximately 0.5 mass% or greater, approximately 1 mass% or greater, or approximately 2 mass% or greater, and approximately 15 mass% or less, approximately 10 mass% or less, or approximately 8 mass% or less, relative to the mass of the polymerizable components, and includes structural units derived from the carboxy group- containing monomer in the mass ratio described above.
  • the polymerization or copolymerization of the acrylic adhesive polymer can be performed by radical polymerization.
  • radical polymerization a known polymerization method can be utilized, such as solution polymerization, suspension polymerization, emulsion polymerization, and bulk polymerization. It is advantageous to use solution polymerization that can easily synthesize a polymer with a high molecular weight.
  • an organic peroxide such as benzoyl peroxide, lauroyl peroxide, or bis(4-tert-butylcyclohexyl)peroxydicarbonate
  • an azo-based polymerization initiator such as 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), dimethyl-2,2-azobis(2- methylpropionate), 4,4'-azobis(4-cyanovalerianic acid), dimethyl 2,2'-azobis(2- methylpropionate), or azobis(2,4-dimethylvaleronitrile) (AVN)
  • the used amount of the polymerization initiator is typically approximately 0.01 parts by mass or greater, or approximately 0.05 parts by mass or greater, and approximately 5 parts by mass or less, or approximately 3 parts by mass or less, relative to 100 parts by mass of the polymerizable components.
  • the glass transition temperature (Tg) of the acrylic adhesive polymer is approximately -25°C or lower. By setting the glass transition temperature of the acrylic adhesive polymer to approximately -25°C or lower, pressure-sensitive adhesiveness can be imparted to the acrylic pressure-sensitive adhesive layer at an operating temperature (e.g., from 5°C to 35°C) even when a combination with the resin-coated metal pigments in an amount that is adequate to exhibit a metallic appearance is employed.
  • the glass transition temperature of the acrylic adhesive polymer is approximately -30°C or lower, or approximately -35°C or lower.
  • the glass transition temperature of the acrylic adhesive polymer is approximately -70°C or higher, approximately -65 °C or higher, or approximately -60°C or higher. By setting the glass transition temperature of the acrylic adhesive polymer to approximately -70°C or higher, adhesive strength and retention strength can be imparted to the pressure-sensitive adhesive layer.
  • the glass transition temperature (Tg) of the acrylic adhesive polymer can be determined as a calculated glass transition temperature by using the following Fox equation (Fox, T. G., Bull. Am. Phys. Soc., 1 (1956), p. 123) when the polymer is formed by copolymerization of n types of monomers:
  • Tgi represents the glass transition temperature (°C) of a homopolymer of a component i
  • Xi represents the mass fraction of the monomer of the component i added during polymerization
  • i is a natural number of 1 to n
  • the weight average molecular weight (Mw) of the acrylic adhesive polymer is approximately 150000 or greater, approximately 200000 or greater, or approximately 250000 or greater, and approximately 2000000 or less, approximately 1500000 or less, or approximately 1000000 or less.
  • weight average molecular weight is a molecular weight in terms of polystyrene standard by the gel permeation chromatography (GPC) method.
  • the resin-coated metal pigment is a pigment in which at least a part of a surface of a metallic pigment is covered by a resin, and exhibits excellent compatibility with the acrylic adhesive polymer.
  • the resin-coated metal pigment may be used alone, or a combination of two or more types of the resin-coated metal pigments may be used.
  • the metal contained in the resin-coated metal pigment is not particularly limited, and examples thereof include aluminum, zinc, iron, magnesium, copper, nickel, and alloys thereof. Because metallic luster can be effectively provided with a smaller used amount and because of the low price, the resin-coated metal pigment preferably contains aluminum.
  • the raw material constituting the resin coating of the resin-coated metal pigment is not particularly limited, and examples thereof include acrylic resins, polyolefin, polybutadiene, polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate, fluororesins, polyvinyl ether, polystyrene, and copolymers and blends of these. Because of excellent compatibility with the acrylic adhesive polymer, the resin-coated metal pigment preferably contains the acrylic resin coating.
  • the resin-coated metal pigment is not particularly limited in terms of its shapes, and is available in the form of, for example, scales, spheres, needles, and lumps. Since the metallic luster can be effectively provided with a smaller used amount, the resin-coated metal pigment is preferably scaly.
  • the average particle diameter of the resin-coated metal pigments is approximately 5 pm or greater, approximately 7 pm or greater, or approximately 10 pm or greater, and approximately 70 pm or less, approximately 50 pm or less, or approximately 40 pm or less.
  • the average particle diameter of the resin- coated metal pigments is a volume cumulative particle diameter D50 that can be determined by laser diffraction/scattering particle size distribution measurement.
  • the acrylic pressure-sensitive adhesive layer contains approximately 5 parts by mass or greater and approximately 100 parts by mass or less of the resin-coated metal pigments relative to 100 parts by mass of the acrylic adhesive polymer.
  • the content of the resin-coated metal pigments By setting the content of the resin-coated metal pigments to approximately 5 parts by mass or greater, a metallic appearance can be imparted to the entire acrylic pressure-sensitive adhesive layer.
  • the acrylic pressure-sensitive adhesive layer contains approximately 6 parts by mass or greater, or approximately 8 parts by mass or greater, and approximately 50 parts by mass or less, or approximately 30 parts by mass or less, of the resin-coated metal pigments relative to 100 parts by mass of the acrylic adhesive polymer.
  • the content of the pigments other than the resin-coated metal pigments of the acrylic pressure-sensitive adhesive layer is less than approximately 5 parts by mass, less than approximately 3 parts by mass, or less than approximately 1 part by mass, relative to 100 parts by mass of the acrylic adhesive polymer.
  • the acrylic pressure-sensitive adhesive layer may further include a dispersant that enhances dispersibility of the resin-coated metal pigments in the acrylic adhesive polymer.
  • a dispersant that enhances dispersibility of the resin-coated metal pigments in the acrylic adhesive polymer.
  • examples of the dispersant include low molecular weight dispersants including anionic compounds, cationic compounds, and nonionic compounds, and high molecular weight dispersants having an anionic, cationic, or nonionic polar group.
  • the dispersant may be used alone, or a combination of two or more types of dispersants may be used.
  • the dispersant preferably has a basic group.
  • the dispersant having a basic group can effectively disperse the resin-coated metal pigments in the acrylic adhesive polymer.
  • the acrylic adhesive polymer includes a carboxy group -containing (meth)acrylic polymer
  • the dispersant having a basic group can enhance cohesive force of the acrylic pressure-sensitive adhesive layer by the interaction with the carboxy group-containing (meth)acrylic polymer and, by this, adhesive strength and retention strength of the acrylic pressure-sensitive adhesive layer can be enhanced.
  • the low molecular weight dispersant includes at least one type selected from the group consisting of piperidyl compounds and benzotriazole compounds.
  • the piperidyl compound and the benzotriazole compound can further enhance dispersibility of the resin-coated metal pigments.
  • the acrylic adhesive polymer includes a carboxy group-containing (meth)acrylic polymer
  • a triazole ring or piperidine ring of the piperidyl compound and the benzotriazole compound can enhance cohesive force of the acrylic pressure-sensitive adhesive layer by the interaction with a carbonyl group of the carboxy group-containing (meth)acrylic polymer and, by this, adhesive strength and retention strength of the acrylic pressure-sensitive adhesive layer can be enhanced.
  • the piperidyl compound is preferably a piperidyl compound which has at least two piperidyl groups and in which these piperidyl groups are bonded through a divalent linking group having 4 or more, 6 or more, or 8 or more carbon atoms.
  • the piperidyl compound in which piperidyl groups are bonded through a divalent linking group having 4 or more, 6 or more, or 8 or more carbon atoms has excellent miscibility with the acrylic adhesive polymer.
  • the piperidyl compound may be a piperidyl compound that can be used as a hindered amine light stabilizer (HALS). By using the hindered amine light stabilizer as the piperidyl compound, UV resistance can be imparted to the acrylic pressure-sensitive adhesive layer.
  • HALS hindered amine light stabilizer
  • piperidyl compound examples include bis(l,2,2,6,6-pentamethyl-4- piperidyl)sebacate, bis(2,2,6,6-tetramethyl-l-(octyloxy)-4-piperidyl)sebacate, bis(2, 2,6,6- tetramethyl-4-piperidyl)sebacate, bis(l,2,2,6,6-pentamethyl-4-piperidyl)-[[3,5-bis(l,l- dimethylethyl)-4-hydroxyphenyl]methyl]butylmalonate, polyester having a terminal capped with dimethyl of butanedioic acid and 4-hydroxy-2,2,6,6-tetramethyl-l-piperidineethanol, tetrakis( 1 ,2,2,6,6-pentamethyl-4-piperidyl)butane- 1 ,2,3 ,4-tetracarboxylate, and tetrakis(2,2,6,6-tetramethyl)
  • the benzotriazole compound is preferably a 2H-benzotriazole compound and, more preferably, a substituted or unsubstituted hydroxyphenyl group is arranged at 2-position.
  • the benzotriazole compound may be a benzotriazole compound that can be used as a UV absorbing agent (UVA).
  • UVA UV absorbing agent
  • Examples of the benzotriazole compound include 2-(2H-benzotriazol-2-yl)-p-cresol, 2-(2H-benzotriazol-2-yl)-4-methylphenol, 2-(2H-benzotriazol-2-yl)-4-methyl-6-(straight- chain or branched)dodecylphenol, 2-(2H-benzotriazol-2-yl)-4,6-bis( I -methyl- 1- phenylethyl)phenol, 2-(5-chloro-2H-benzotriazol-2-yl)-6-(l,l-dimethylethyl)-4- methylphenol, 2-(2H-benzotriazol-2-yl)-4-(l,l,3,3-tetramethylbutyl)phenol, 2,2'-methylene- bis[6-(2H-benzotriazol-2-yl)-4-(l,l,3,3-tetramethylbutyl)phenol], and C7-9
  • the high molecular weight dispersant includes an amino group- containing (meth)acrylic polymer.
  • the amino group-containing (meth)acrylic polymer exhibits excellent miscibility with a (meth)acrylic polymer having an acidic group such as a carboxy group, in addition to enhancing dispersibility of the resin-coated metal pigments.
  • the amino group-containing (meth)acrylic polymer can be obtained by copolymerizing a polymerizable composition containing an amino group-containing monomer as a polymerizable component, among polymerizable composition described for the acrylic adhesive polymer.
  • dialkylamino alkyl(meth)acrylate such as N,N-dimethylaminoethyl acrylate (DMAEA) or N,N- dimethylaminoethyl methacrylate (DMAEMA) is preferred.
  • DAEA N,N-dimethylaminoethyl acrylate
  • DMAEMA N,N- dimethylaminoethyl methacrylate
  • the amino group-containing (meth)acrylic polymer is obtained by copolymerizing a polymerizable composition containing the amino group-containing monomer in an amount of approximately 0.5 mass% or greater, approximately 1 mass% or greater, or approximately 3 mass% or greater, and approximately 20 mass% or less, approximately 15 mass% or less, or approximately 10 mass% or less, relative to the mass of the polymerizable components, and includes structural units derived from the amino group- containing monomer in the mass ratio described above.
  • the glass transition temperature (Tg) of the amino group- containing (meth)acrylic polymer is approximately 0°C or higher, approximately 20°C or higher, or approximately 40°C or higher, and approximately 150°C or lower, approximately 135°C or lower, or approximately 120°C or lower.
  • the glass transition temperature of the amino group-containing (meth)acrylic polymer can be determined by using the Fox equation similarly to the acrylic adhesive polymer.
  • the weight average molecular weight of the amino group-containing (meth)acrylic polymer is not particularly limited and, for example, can be approximately 1000 or greater, approximately 5000 or greater, or approximately 10000 or greater, and approximately 200000 or less, approximately 100000 or less, or approximately 80000 or less.
  • the content of the dispersant in the acrylic pressure-sensitive adhesive layer can be approximately 10 parts by mass or greater, approximately 20 parts by mass or greater, or approximately 40 parts by mass or greater, and approximately 500 parts by mass or less, approximately 300 parts by mass or less, or approximately 250 parts by mass or less, relative to 100 parts by mass of the resin-coated metal pigments.
  • the acrylic pressure-sensitive adhesive layer can be formed on the clear film layer, on another layer constituting the laminate having the clear film layer, or on a liner by using the pressure-sensitive adhesive composition containing the acrylic adhesive polymer and the resin-coated metal pigments and, optionally, a dispersant, a crosslinking agent, a solvent, and/or other additives.
  • the crosslinking agent is not particularly limited as long as the crosslinking agent can form a crosslink between polymer chains of the acrylic adhesive polymer.
  • the crosslinking agent By using the crosslinking agent, cohesive force of the acrylic pressure-sensitive adhesive layer can be enhanced and, by this, adhesive strength and retention strength of the acrylic pressuresensitive adhesive layer can be enhanced.
  • the acrylic adhesive polymer is a carboxy group-containing (meth)acrylic polymer
  • an epoxy crosslinking agent, a bisamide crosslinking agent, an aziridine crosslinking agent, a carbodiimide crosslinking agent, or an isocyanate crosslinking agent can be used as the crosslinking agent.
  • the crosslinking agent may be used alone, or a combination of two or more types of crosslinking agents may be used.
  • Examples of the epoxy crosslinking agent include N,N,N',N'-tetraglycidyl-l,3- benzenedi(methanamine) (product name: TETRAD-X (Mitsubishi Gas Chemical Company Inc., Chiyoda-ku, Tokyo, Japan), E-AX and E-5XM (both from Soken Chemical & Engineering Co., Ltd., Toshima-ku, Tokyo, Japan)); and N,N'-(cyclohexane-l,3- diylbismethylene)bis(diglycidylamine) (product name: TETRAD-C (Mitsubishi Gas Chemical Company Inc., Chiyoda-ku, Tokyo, Japan), and E-5C (Soken Chemical & Engineering Co., Ltd., Toshima-ku, Tokyo, Japan)).
  • TETRAD-X Mitsubishi Gas Chemical Company Inc., Chiyoda-ku, Tokyo, Japan
  • E-5XM both from Soken Chemical & Engineering Co., Ltd., Toshima-ku,
  • Examples of the bisamide crosslinking agent include 1,T-(1,3- phenylenedicarbonyl)bis(2-methylaziridine), l,4-bis(ethyleneiminocarbonylamino)benzene, 4,4'-bis(ethyleneiminocarbonylamino)diphenylmethane, and 1,8- bis(ethyleneiminocarbonylamino)octane.
  • aziridine crosslinking agent examples include 2,2-bishydroxymethylbutanol- tris[3-(l-aziridinyl)propionate (trade name: CHEMITITE (registered trademark) PZ-33 (Nippon Shokubai Co., Ltd., Osaka-shi, Osaka, Japan), and Crosslinker CX-100 (DSM Coating Resins B.V., Zwolle, Netherlands)).
  • Examples of the carbodiimide crosslinking agent include Carbodilite V-03, V-05, and V-07 (all from Nisshinbo Chemical Inc., Chuo-ku, Tokyo, Japan).
  • Examples of the isocyanate crosslinking agent include Coronate L and Coronate HK (both from Tosoh Corporation, Minato-ku, Tokyo, Japan).
  • the crosslinking agent can be used in an amount of approximately 0.01 parts by mass or greater, approximately 0.02 parts by mass or greater, or approximately 0.05 parts by mass or greater, and approximately 0.5 parts by mass or less, approximately 0.4 parts by mass or less, or approximately 0.3 parts by mass or less, relative to 100 parts by mass of the acrylic adhesive polymer.
  • Examples of the solvent include methanol, ethanol, hexane, heptane, toluene, acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, and mixed solvents thereof.
  • Examples of other additives include UV absorbing agents, antioxidants, thermal stabilizers, fillers, and tackifiers.
  • the thickness of the acrylic pressure-sensitive adhesive layer is not particularly limited and, for example, can be approximately 5 pm or greater, approximately 10 pm or greater, or approximately 20 pm or greater, and approximately 200 pm or less, approximately 100 pm or less, or approximately 80 pm or less.
  • the adhesive film can be produced by a known method.
  • an acrylic pressure-sensitive adhesive layer is formed by coating a pressure-sensitive adhesive composition on a liner by using a knife coater or a bar coater and drying.
  • the acrylic pressure-sensitive adhesive layer may be heated by using hot air or an oven during the drying.
  • a clear film layer or a laminate having a clear film layer can be layered by a method such as dry lamination, and thus an adhesive film can be produced.
  • the adhesive film can be also produced by directly coating the pressure-sensitive adhesive composition on a clear film layer or another layer constituting a laminate having a clear film layer and drying.
  • the acrylic pressure-sensitive adhesive layer may be solid or may be a porous or foam body.
  • the adhesive surface of the acrylic pressure-sensitive adhesive layer may be flat or may have recesses and protrusions.
  • the adhesive surface with recesses and protrusions include an adhesive surface of the acrylic pressure-sensitive adhesive layer, in which the protrusions containing a solid content or reaction product of the pressure-sensitive adhesive composition and the recesses surrounding the protrusions are formed, and when the adhesive surface is attached to an adherend, a communicating passage is formed between the adherend surface and the adhesive surface, the communicating passage being defined by the recesses and being in communication with the external space.
  • a liner with a release surface including a predetermined recess-and-protrusion structure is prepared.
  • the pressure-sensitive adhesive composition is coated to the release surface of the liner, and as necessary, heated to form an acrylic pressure-sensitive adhesive layer.
  • the recess-and-protrusion structure (negative structure) of the liner is transferred to the surface of the acrylic pressure-sensitive adhesive layer, the surface being in contact with the liner (to serve as the adhesive surface in the adhesive film), and thus an adhesive surface with recesses and protrusions including the predetermined structure (positive structure) at the adhesive surface is formed.
  • the recesses and protrusions of the adhesive surface are designed in advance to include a groove that allows formation of the communicating passage when the protrusions adhere to the adherent body.
  • the groove having a consistent shape may be arranged at the adhesive surface in accordance with a regular pattern to form a regularly-patterned groove, or the groove having an indeterminate shape may be arranged to form an irregularly-patterned groove.
  • the interval at which the grooves are disposed is preferably approximately 10 pm or greater and approximately 2000 pm or less.
  • the depth of the grooves is typically approximately 10 pm or greater, and approximately 100 pm or less.
  • the shape of the groove is also not particularly limited, as long as the effect of the present invention is not impaired.
  • the shape of the groove may be substantially rectangular (including trapezoidal), substantially semicircular, or substantially semi-elliptical at a cross-section of the groove in a direction perpendicular to the adhesive surface.
  • the adhesive strength of the adhesive film of an embodiment is approximately 2.5 N/25 mm or greater, approximately 3 N/25 mm or greater, or approximately 4 N/25 mm or greater, when measurement is performed by using an SUS304 plate as an adherend in accordance with JIS Z 0237:2009.
  • the adhesive strength of the adhesive film is typically approximately 50 N/25 mm or less, approximately 45 N/25 mm or less, or approximately 40 N/25 mm or less.
  • the measurement process and condition of the adhesive strength of the adhesive film refer to "2-3. Adhesive Strength C" described in Examples.
  • the adhesive film of the present disclosure can be used for marking on vehicles, ships, and aircraft, interior and exterior of buildings, and illuminated signs, and especially can be suitably used for applications that imparts metallic appearance to a three-dimensional surface such as a rough surface, a curved surface, or a corner portion.
  • BA n-butyl acrylate
  • 2EHA 2-ethylhexyl acrylate
  • AN acrylonitrile
  • AA acrylic acid
  • 2MB A 2 -methylbutyl acrylate
  • IOA isooctyl acrylate
  • MA methyl acrylate
  • MMA methyl methacrylate
  • BMA butyl methacrylate
  • DMAEMA dimethylaminoethyl methacrylate
  • the pressure-sensitive adhesive composition containing the adhesive polymer 1 (ADH1), dispersant 1 (DPT1), aluminum paste 1 (API), and crosslinking agent 1 (CL1) was prepared.
  • the mass ratio of ADH1:DPT1:AP1:CL1 was 100: 10:5:0.10 based on non-volatile content.
  • the pressure-sensitive adhesive composition was coated on a release liner 1 (LI) by a knife coater. The coated layer was dried at 95°C for 5 minutes. After the drying, the acrylic pressure-sensitive adhesive layer having a thickness of 30 pm was obtained. By adhering the acrylic pressure-sensitive adhesive layer and the film 1 (FL1), the acrylic pressure-sensitive adhesive layer was transferred to the FL 1, and thus an adhesive film of Example 1 was obtained.
  • Adhesive films of Example 2 to Example 27 were obtained by the same procedure as in Example 1 except for changing the compositions of the pressure-sensitive adhesive compositions, the thicknesses of the acrylic pressure-sensitive adhesive layers, and the films to those shown in Table 2.
  • Acrylic pressure-sensitive adhesive layers of Comparative Example 1 and Comparative Example 2 were formed by the same procedure as in Example 1 except for changing the compositions of the pressure-sensitive adhesive compositions to those shown in Table 2.
  • Comparative Example 1 and Comparative Example 2 the appearance of the acrylic pressure-sensitive adhesive layers was unsatisfactory, and thus adhesive films were not produced.
  • Adhesive films of Comparative Example 3 and Comparative Example 4 were obtained by the same procedure as in Example 1 except for changing the compositions of the pressuresensitive adhesive compositions and the thicknesses of the acrylic pressure-sensitive adhesive layers to those shown in Table 2.
  • the acrylic pressure-sensitive adhesive layer of the adhesive film of Comparative Example 4 did not contain any aluminum paste.
  • test piece was produced by cutting an adhesive film into a rectangular shape with a length of 150 mm and a width of 25 mm. The test piece was adhered on a melamine-coated plate (Paltek Corporation, Hiratsuka-shi, Kanagawa, Japan) at 20°C. The adhering method was in accordance with JIS Z 0237:2009. The test piece was left at 20°C for 48 hours.
  • test piece was produced by cutting an adhesive film into a rectangular shape with a length of 150 mm and a width of 25 mm. The test piece was adhered on a melamine-coated plate (Paltek Corporation, Hiratsuka-shi, Kanagawa, Japan) at 20°C. The adhering method was in accordance with JIS Z 0237:2009. The test piece was subjected to heat cycle condition of from 80°C to -30°C for 7 times.
  • test piece was produced by cutting an adhesive film into a rectangular shape with a length of 150 mm and a width of 25 mm.
  • the test piece was adhered on an SUS304BA panel (Paltek Corporation, Hiratsuka-shi, Kanagawa, Japan) at 20°C.
  • the adhering method was in accordance with JIS Z 0237:2009.
  • the test piece was left at 20°C for 1 minute.
  • a test piece was produced by cutting an adhesive film into a square with 50 mm side.
  • the test piece was adhered on a stucco-coated plate (Test Materials Co., Ltd., Chiyoda-ku, Tokyo, Japan) in an environment at 23 °C.
  • the maximum surface roughness of the stucco- coated plate was approximately 1.5 mm.
  • the test piece was pressurized without being heated by using PFA-1 Rivet Brush (3M Japan Ltd., Shinagawa-ku, Tokyo, Japan). By this, the test piece was partially elongated.
  • the appearance of the adhesive film was then visually observed. The case where no change occurred in the appearance of the test piece was evaluated as A.
  • the case where change occurred in the appearance of the test piece was evaluated as B. Evaluation of A was a pass. [0089] 5. Surface Glossiness
  • a test piece was produced by cutting an adhesive film into a square with 50 mm side. The test piece was adhered on an aluminum panel in an environment at 23°C. By using a portable glossmeter GMX-202 (Murakami Color Research Laboratory Co., Ltd., Chuo-ku, Tokyo, Japan), 60 degree gloss on a test piece surface was measured. [0090] 6. Weather Resistance
  • a test piece was produced by cutting an adhesive film into a rectangular shape with a length of 50 mm and a width of 30 mm. The test piece was adhered to an aluminum panel having a thickness of 1 mm at room temperature by using a squeegee. By using a xenon weatherometer Ci5000 Weather-Ometer (Toyo Seiki Seisaku-sho, Ltd., Kita-ku, Tokyo, Japan), the test piece was exposed to xenon light. The test conditions were in accordance with JIS K 5600-7-7:2008. The case where no change occurred in the appearance of the test piece was evaluated as A. The case where the test piece turned yellow was evaluated as B. The case where peeling off from the aluminum panel occurred was evaluated as C. Evaluation of A was a pass.
  • a test piece was produced by cutting an adhesive film into a rectangular shape with a length of 150 mm and a width of 25 mm. The test piece was adhered to an aluminum panel at 20°C. The test piece was subjected to heat cycle condition of from 80°C to -30°C for 7 times. Using a tensile tester (Tensilon (trade name) universal testing machine, model: RTC-1210A, A&D Company, Limited, Toshima-ku, Tokyo, Japan), 180 degree peeling was performed at a peeling rate of 300 mm/min at a temperature of 20°C. The case where no residue of the acrylic pressure-sensitive adhesive layer was observed on the aluminum panel was evaluated as A. The case where separation was observed between the acrylic pressure-sensitive adhesive layer and the film was evaluated as B. The case where a residue of the acrylic pressuresensitive adhesive layer was observed on the aluminum panel was evaluated as C.
  • a test piece was produced by cutting an adhesive film into a rectangular shape with a length of 50 mm and a width of 30 mm.
  • the test piece was adhered to an aluminum panel having a thickness of 1 mm at room temperature by using a squeegee.
  • a xenon weatherometer Ci5000 Weather-Ometer Toyo Seiki Seisaku-sho, Ltd., Kita-ku, Tokyo, Japan
  • the test piece was exposed to xenon light.
  • the test conditions were in accordance with JIS K 5600-7-7:2008.
  • the adhesive film surface was exposed to xenon light for 500 hours.
  • the case where no corrosion was observed in the test piece was evaluated as A.
  • the case where corrosion was observed in the test piece was evaluated as B. Evaluation of A was a pass.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

Film adhésif qui peut être collé à diverses surfaces tridimensionnelles, telles que des surfaces rugueuses, des surfaces incurvées et des parties de coin, et qui peut fournir un excellent aspect métallique. Le film adhésif comprend une couche de film transparent et une couche acrylique adhésive sensible à la pression et a un aspect métallique. La couche acrylique adhésive sensible à la pression comprend un polymère acrylique adhésif et un pigment métallique revêtu de résine, une température de transition vitreuse du polymère acrylique adhésif est inférieure ou égale à -25 °C, et la couche acrylique adhésive sensible à la pression contient de 5 parties en masse à 100 parties en masse du pigment métallique revêtu de résine par rapport à 100 parties en masse du polymère acrylique adhésif.
PCT/IB2023/060421 2022-10-27 2023-10-16 Film adhésif WO2024089528A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2022-172135 2022-10-27
JP2022172135A JP2024063934A (ja) 2022-10-27 2022-10-27 接着フィルム

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WO2024089528A1 true WO2024089528A1 (fr) 2024-05-02

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4248762A (en) * 1977-07-18 1981-02-03 Stauffer Chemical Company Pressure sensitive products with decorative appearance
JPH06172729A (ja) * 1992-12-09 1994-06-21 Nitto Denko Corp 感圧接着剤とその接着シ―ト類
US20060205835A1 (en) * 2002-12-19 2006-09-14 Tesa Ag Transparent acrylate adhesive mass comprising a filler
US20130034694A1 (en) * 2010-03-01 2013-02-07 Kim Michael H Translucent film for protecting rough surfaces
KR20160063372A (ko) * 2013-09-27 2016-06-03 테사 소시에타스 유로파에아 낮은 에너지 또는 굴곡 표면용 감압 접착제 물질

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4248762A (en) * 1977-07-18 1981-02-03 Stauffer Chemical Company Pressure sensitive products with decorative appearance
JPH06172729A (ja) * 1992-12-09 1994-06-21 Nitto Denko Corp 感圧接着剤とその接着シ―ト類
US20060205835A1 (en) * 2002-12-19 2006-09-14 Tesa Ag Transparent acrylate adhesive mass comprising a filler
US20130034694A1 (en) * 2010-03-01 2013-02-07 Kim Michael H Translucent film for protecting rough surfaces
KR20160063372A (ko) * 2013-09-27 2016-06-03 테사 소시에타스 유로파에아 낮은 에너지 또는 굴곡 표면용 감압 접착제 물질

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