WO2013042485A1 - Feuille pour protéger un film de revêtement et son procédé de préparation - Google Patents

Feuille pour protéger un film de revêtement et son procédé de préparation Download PDF

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Publication number
WO2013042485A1
WO2013042485A1 PCT/JP2012/070456 JP2012070456W WO2013042485A1 WO 2013042485 A1 WO2013042485 A1 WO 2013042485A1 JP 2012070456 W JP2012070456 W JP 2012070456W WO 2013042485 A1 WO2013042485 A1 WO 2013042485A1
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Prior art keywords
pressure
coating film
adhesive layer
sensitive adhesive
temperature plasma
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PCT/JP2012/070456
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English (en)
Japanese (ja)
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健一 柴田
紘子 池永
與倉　三好
久志 勝又
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日東電工株式会社
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Publication of WO2013042485A1 publication Critical patent/WO2013042485A1/fr

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    • 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
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J123/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
    • C09J123/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
    • C09J123/22—Copolymers of isobutene; Butyl rubber ; Homo- or copolymers of other iso-olefines
    • 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
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J123/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
    • C09J123/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
    • 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
    • C09J7/22—Plastics; Metallised plastics
    • 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]
    • 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
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/306—Applications of adhesives in processes or use of adhesives in the form of films or foils for protecting painted surfaces, e.g. of cars
    • 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
    • C09J2423/00—Presence of polyolefin
    • 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
    • C09J2423/00—Presence of polyolefin
    • C09J2423/006—Presence of polyolefin in the substrate

Definitions

  • the present invention relates to a coating film protective sheet provided with a pressure-sensitive adhesive (hereinafter also referred to as pressure-sensitive adhesive) layer mainly composed of an isobutylene polymer and a method for producing the same.
  • a pressure-sensitive adhesive hereinafter also referred to as pressure-sensitive adhesive
  • This application claims priority based on Japanese Patent Application No. 2011-206185 filed on Sep. 21, 2011, the entire contents of which are incorporated herein by reference.
  • a coating film protective sheet using an isobutylene polymer as an adhesive layer is, for example, a coating film when transporting, storing, curing, and constructing (hereinafter, also referred to as transport) of articles such as painted automobiles and parts thereof. It is widely used for the purpose of preventing surface damage, contamination, glossy blur, and discoloration.
  • the surface of the coating film is exposed to the external environment for a long period (for example, several days to several tens of days) when the automobile and its parts are transferred. May be exposed.
  • the protective sheet may be peeled off due to deterioration of the adhesive force over time, and there is a possibility that the protection of the coating film located at the peeled portion may be insufficient. Therefore, it would be beneficial if a coating film protective sheet having excellent adhesive strength over time is provided.
  • the coating film protection sheet provided by the present invention is a coating film protection sheet provided with an adhesive layer mainly composed of an isobutylene polymer.
  • the element ratio of oxygen atoms on the surface of the pressure-sensitive adhesive layer measured by the ESCA method is 1.0 at% to 8.0 at% of the entire surface.
  • the present inventors have been intensively studying the temporal stability of the adhesive force, and on the surface of the pressure-sensitive adhesive layer, For example, by performing treatment such as low-temperature plasma treatment and introducing oxygen atoms at a predetermined element ratio, it was found that the adhesive force is stable over a long period of time, and the present invention has been completed. That is, according to the coating film protective sheet having such a configuration, oxygen atoms on the surface of the adhesive layer measured by the ESCA method (Electron Spectroscopy for Chemical Analysis: X-ray photoelectron spectroscopy) are 1.0 at% to 8 in the entire surface. As a result of being introduced so as to be in the range of 0.0 at%, it is possible to suppress a change with time in the adhesive force of the pressure-sensitive adhesive layer and to stabilize the adhesive force over a long period of time.
  • ESCA method Electrodectron spectroscopy
  • “good initial adhesive strength” is not particularly limited because it is appropriately set according to the purpose of use, etc., but it is difficult to peel off when protecting the coating film. Because it is easy to peel off (excellent re-peelability), when it is adhered to a coating mainly composed of an acrylic resin, which is a typical difficult adhesion coating formed on a steel plate,
  • the adhesive strength after 48 hours under typical atmospheric pressure conditions is preferably 2.0 N / 25 mm or more, more preferably 3.0 N / 25 mm or more (typically 4.N.
  • the coating film which has acrylic resin as a main component means that the content rate of acrylic resin in a coating film exceeds 50 mass%, Preferably it is 60 mass% or more, More preferably, it is 80 mass%. That's it.
  • the coating film protective sheet disclosed herein is bonded to a coating film mainly composed of an acrylic resin formed on a steel plate and is subjected to room temperature (typically 20 ° C. to 35 ° C.) and atmospheric pressure conditions.
  • room temperature typically 20 ° C. to 35 ° C.
  • the adhesive strength after 30 days below is 50% or more (more preferably 60% or more, typically 70% or more) of the adhesive strength after 48 hours from the adhesion to the coating film.
  • the above-described maintenance of the adhesive force according to the present invention is preferably realized not under room temperature but also under conditions exceeding 35 ° C. (typically under conditions where the temperature is 50 ° C. or higher).
  • Such a coating film protection sheet can be preferably used as a coating film protection sheet for automobiles and parts thereof exposed to the external environment during transportation or the like. Furthermore, from the viewpoint of easy peeling after use, the adhesive strength after 30 days after bonding to a coating film mainly composed of an acrylic resin formed on a steel sheet is 150 of the adhesive strength after 48 hours after bonding to the coating film. % Or less is preferable. For example, as described above, the fact that the adhesive force is stable over time in the present invention is remarkably excellent, unlike the temporal stability of adhesive force exhibited by the prior art.
  • the pressure-sensitive adhesive layer is provided on a polyolefin-based substrate, and the thickness of the substrate is 30 ⁇ m to 50 ⁇ m.
  • the layer thickness is 10 ⁇ m to 20 ⁇ m.
  • Such a coating film protection sheet can be preferably used, for example, as a coating film protection sheet for automobiles and parts thereof.
  • a method for producing such a coating film protective sheet includes forming the pressure-sensitive adhesive layer on a predetermined substrate, and subjecting the surface of the formed pressure-sensitive adhesive layer to low-temperature plasma treatment, and the low-temperature plasma. The treatment is performed so that the element ratio of oxygen atoms measured by the ESCA method on the surface of the pressure-sensitive adhesive layer is 1.0 at% to 8.0 at% of the entire surface.
  • low temperature plasma treatment means a discharge that starts and continues by applying a high voltage of direct current or alternating current between electrodes, for example, corona discharge under atmospheric pressure or glow discharge in vacuum. A treatment performed by exposing a substrate.
  • the low temperature plasma treatment is performed under a condition in which an inert gas is introduced into a predetermined chamber and the pressure is reduced to 0.01 MPa or less.
  • oxygen atoms are introduced into the surface of the pressure-sensitive adhesive layer when the pressure is returned to atmospheric pressure.
  • the low temperature plasma treatment is performed by an internal electrode type low temperature plasma treatment machine, and the strength of the low temperature plasma treatment is 15 W ⁇ min / m 2 to 1000 W. - in the range of min / m 2.
  • the strength of the low temperature plasma treatment is 15 W ⁇ min / m 2 to 1000 W. - in the range of min / m 2.
  • the coating film protective sheet according to the present invention (for example, an automotive coating film protective sheet used for protecting automobiles and parts thereof) has a configuration in which an adhesive layer mainly composed of an isobutylene polymer is provided.
  • the coating film protective sheet 10 has a configuration in which an adhesive layer 2 is provided on one side of a substrate 1, and the adhesive layer 2 is attached to an adherend (an article to be protected).
  • adherend an article to be protected
  • it is used by being attached to an article having a coating film such as an automobile or its parts.
  • the protective sheet 10 before use (that is, before sticking to an adherend) has a release liner (not shown) in which the surface (adhesive surface) of the pressure-sensitive adhesive layer 2 is at least a release surface on the pressure-sensitive adhesive layer side. It can be in a protected form.
  • the other surface (back surface) of the base material 1 is a release surface, and the protective sheet 10 is wound in a roll shape so that the pressure-sensitive adhesive layer 2 comes into contact with the other surface to protect the surface.
  • the form of the protective sheet 10 may be used.
  • the coating film protective sheet 10 has an intermediate layer (between the base material 1 and the pressure-sensitive adhesive layer 2) for the purpose of preventing the phenomenon that the pressure-sensitive adhesive remains on the adherend side at the time of peeling (that is, adhesive residue). (Not shown) may be provided.
  • an intermediate layer for example, the primer layer disclosed in Patent Document 2 described above can be preferably used.
  • the configuration in which the intermediate layer is provided between the base material 1 and the pressure-sensitive adhesive layer 2 is also included in the fact that the pressure-sensitive adhesive layer 2 is provided on the base material 1.
  • the pressure-sensitive adhesive layer (hereinafter, also referred to as polyisobutylene-based pressure-sensitive adhesive layer) having an isobutylene-based polymer as a main component provided in the coating film protective sheet disclosed herein is composed of an isobutylene-based polymer as a base polymer (among polymer components). It can be a pressure-sensitive adhesive layer formed from a pressure-sensitive adhesive composition.
  • the isobutylene-based polymer may be a homopolymer of isobutylene (homoisobutylene) or a copolymer having isobutylene as a main monomer.
  • the copolymer includes, for example, a copolymer of isobutylene and normal butylene, a copolymer of isobutylene and isoprene (regular butyl rubber, chlorinated butyl rubber, brominated butyl rubber, partially crosslinked butyl rubber, etc.), vulcanized products and modified products thereof. (For example, those modified with a functional group such as a hydroxyl group, a carboxyl group, an amino group, and an epoxy group).
  • Examples of the isobutylene polymer preferably used from the viewpoint of the stability of the adhesive strength include homoisobutylene and isobutylene-normal butylene copolymers. Of these, homoisobutylene is preferable.
  • the molecular weight of the isobutylene polymer is not particularly limited, and for example, those having a mass average molecular weight (Mw) of about 10 ⁇ 10 4 to 150 ⁇ 10 4 can be appropriately selected and used.
  • Mw mass average molecular weight
  • Mw is about 20 ⁇ 10 4 or more (preferably about 30 ⁇ 10 4 or more, more preferably about 35 ⁇ 10 4 or more), and about 70 ⁇ 10 4 or less (preferably Is about 60 ⁇ 10 4 or less, more preferably about 50 ⁇ 10 4 or less).
  • the isobutylene-based polymer is an isobutylene-based polymer (preferably, the molecular weight is decreased so as to achieve the above-described preferable mass average molecular weight) by subjecting a higher molecular weight isobutylene-based polymer to a slicking treatment.
  • Shak solution processing body The crushing treatment is preferably performed so as to obtain an isobutylene polymer having a Mw of about 10% to 80% before the crushing treatment. Further, it is preferable to carry out so as to obtain an isobutylene polymer having a number average molecular weight (Mn) of about 10 ⁇ 10 4 to 40 ⁇ 10 4 .
  • Mn number average molecular weight
  • Such shak solution processing can be performed based on, for example, the description of Japanese Patent No. 3878700.
  • the polyisobutylene-based pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer may be one having at least one selected from such isobutylene-based polymers as a base polymer.
  • the “pressure-sensitive adhesive layer mainly composed of an isobutylene-based polymer” means that the content of the isobutylene-based polymer in the pressure-sensitive adhesive layer exceeds 50% by mass.
  • the content of the polymer is preferably 80% by mass or more, more preferably 90% by mass or more. Therefore, in addition to the base polymer, the polyisobutylene-based pressure-sensitive adhesive may contain a polymer other than the polyisobutylene-based polymer as an auxiliary component.
  • polymers examples include poly (meth) acrylic acid esters, polybutadiene, polystyrene, polyisoprene, polyurethane, polyacrylonitrile, polyamide and the like.
  • the content of these polymers other than the polyisobutylene-based polymer is usually preferably 10% by mass or less of the entire polymer component contained in the polyisobutylene-based adhesive.
  • An adhesive that does not substantially contain a polymer other than polyisobutylene may be used.
  • polyisobutylene-based pressure-sensitive adhesive examples include various additives such as tackifiers, softeners, pigments, fillers, antioxidants, light stabilizers (radical scavengers, ultraviolet absorbers, etc.) and other stabilizers. Can be blended as necessary.
  • tackifiers examples include alkylphenol resins, terpene phenol resins, epoxy resins, coumarone indene resins, rosin resins, terpene resins, hydrogenated products thereof, and the like.
  • softener examples include process oil and petroleum softener.
  • Examples of materials that can be preferably used as the pigment or filler include inorganic powders such as titanium oxide, zinc oxide, calcium oxide, magnesium oxide, and silica.
  • examples of antioxidants include those containing alkylphenols, alkylene bisphenols, thiopropionic esters, organic phosphites, amines, hydroquinones, hydroxylamines and the like as active ingredients.
  • Examples of light stabilizers include those containing benzotriazoles, hindered amines, benzoates and the like as active ingredients.
  • Each of these additives can be used alone or in combination of two or more.
  • the compounding quantity of an additive can be made into the same grade as the normal compounding quantity in the field
  • the elemental ratio of oxygen atoms on the surface of the polyisobutylene-based pressure-sensitive adhesive layer is 1.0 at% to 8.0 at% of the entire surface when measured by the ESCA method.
  • the element ratio of the oxygen atom is preferably 1.2 at% or more (more preferably 1.5 at% or more), and is preferably 7.0 at% or less (more preferably 6.0 at% or less).
  • the formed functional groups It is avoided that the adhesive force changes with time by moving from the surface of the pressure-sensitive adhesive layer to the inside, so that the functional group that acts on the adhesive force can exist stably on the surface of the pressure-sensitive adhesive layer. It is presumed that the adhesive force is stable over time.
  • the thickness of the pressure-sensitive adhesive layer is not particularly limited and can be appropriately determined according to the purpose. Usually, it is appropriate that the average thickness is about 2 ⁇ m to 30 ⁇ m, preferably about 3 ⁇ m or more (typically about 10 ⁇ m or more), and preferably about 25 ⁇ m or less (typically about 20 ⁇ m). The following). For example, the above range can be preferably adopted as the thickness of the pressure-sensitive adhesive layer provided in the automobile paint film protective sheet.
  • the technology disclosed herein is a resin sheet mainly composed of a resin component such as polyolefin or polyester (typically a resin film formed by molding a resin composition mainly composed of such a resin component into a film shape). It can apply preferably to the coating-film protection sheet which uses as a base material.
  • a particularly preferable application target is a polyolefin-based substrate (hereinafter, also referred to as a polyolefin-based resin sheet (film)) in which a resin component constituting the substrate is mainly a polyolefin-based resin.
  • a substrate having such a composition is preferable from the viewpoint of recyclability and the like.
  • the resin component constituting the sheet is mainly a polypropylene resin (hereinafter also referred to as PP resin) (in other words, the resin component exceeds 50% by mass and the PP resin).
  • PP resin polypropylene resin
  • a resin sheet in which approximately 60% by mass or more (more preferably approximately 75% by mass or more) of the resin component is PP resin is preferable.
  • a resin sheet in which a continuous structure (continuous phase) of PP resin is formed can be preferably used.
  • the resin component may be a resin sheet substantially composed of one or two or more types of PP resins (that is, containing a PP resin alone as a resin component).
  • the protective sheet using the resin sheet having the continuous structure of the PP resin as a base material causes a situation where the protective sheet floats from the adherend (coating film) due to a thermal history such as a temperature rise during outdoor curing, for example. It is preferable because it is easy to prevent.
  • the substrate may have a single layer structure or a multilayer structure of two or more layers. In the case of a multilayer structure, at least one layer is preferably a layer having a continuous structure of the PP resin.
  • propylene-based polymers containing propylene as components can be used as the PP resin for the base material.
  • the concept of propylene-based polymer here includes, for example, the following polypropylene.
  • Propylene homopolymer homopolypropylene).
  • Random copolymers random polypropylene of propylene and other ⁇ -olefins (typically one or more selected from ethylene and ⁇ -olefins having 4 to 10 carbon atoms).
  • a random polypropylene containing propylene as a main monomer main constituent monomer, that is, a component occupying 50% by mass or more of the whole monomer).
  • random polypropylene obtained by random copolymerization of 96 mol% to 99.9 mol% of propylene and 0.1 mol% to 4 mol% of the other ⁇ -olefin (preferably ethylene and / or butene).
  • a copolymer obtained by block copolymerization of propylene with other ⁇ -olefin typically one or more selected from ethylene and ⁇ -olefin having 4 to 10 carbon atoms
  • Block copolymer (block polypropylene), which further comprises a rubber component, typically containing propylene and at least one of the other ⁇ -olefins as a by-product.
  • a block polypropylene further comprising a rubber component containing at least one of the other ⁇ -olefins as a component.
  • the PP resin for the base material may be substantially composed of one or two or more of such propylene polymers (such as the polypropylene), and a large amount of rubber component is added to the propylene polymer. It may be a reactor blend type obtained by copolymerization or a dry blend type thermoplastic olefin resin (TPO) or thermoplastic elastomer (TPE) obtained by mechanically dispersing the rubber component.
  • TPO thermoplastic olefin resin
  • TPE thermoplastic elastomer
  • a PP resin containing a copolymer of a monomer having another functional group (functional group-containing monomer) and propylene a PP resin obtained by copolymerizing such a functional group-containing monomer with a propylene-based polymer, etc. There may be.
  • the polyolefin resin sheet contains another resin component in addition to the PP resin, as a preferred example of the other resin component, an olefin polymer containing ethylene or an ⁇ -olefin having 4 or more carbon atoms as a main monomer is a main component.
  • a polyolefin-based resin polyethylene-based resin (hereinafter also referred to as PE resin) having an ethylene-based polymer as a main component).
  • PE resin polyethylene-based resin
  • a polyolefin resin sheet containing a PE resin and a PP resin as resin components can be preferably used as the base material of the protective sheet disclosed herein.
  • any of high-density polyethylene and low-density polyethylene (high-density, medium-density and low-density polyethylene as defined in the former JIS K6748: 1995) can be used. Further, it may be a PE resin containing a copolymer of ethylene and another ⁇ -olefin (for example, an ⁇ -olefin having 3 to 10 carbon atoms).
  • ⁇ -olefin for example, an ⁇ -olefin having 3 to 10 carbon atoms.
  • the ⁇ -olefin include 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene and the like.
  • a PE resin containing a copolymer of a monomer having another functional group (functional group-containing monomer) and ethylene a PE resin obtained by copolymerizing such a functional group-containing monomer with an ethylene polymer, etc.
  • ethylene-vinyl acetate copolymer EVA
  • EAA ethylene-acrylic acid copolymer
  • EAA ethylene-methacrylic acid copolymer
  • ethylene-acrylic ethylene-acrylic.
  • EMA Acid methyl copolymer
  • EAA ethylene-ethyl acrylate copolymer
  • EMMA ethylene-methyl methacrylate copolymer
  • EMA Acid methyl copolymer
  • EAA ethylene-ethyl acrylate copolymer
  • EMMA ethylene-methyl methacrylate copolymer
  • EMA Acid methyl copolymer
  • EAA ethylene-ethyl acrylate copolymer
  • EMMA ethylene-methyl methacrylate copolymer
  • EMA ethylene- (meth) acrylic acid (ie, acrylic acid and / or methacrylic acid)
  • the copolymer is crosslinked with a metal ion.
  • low density polyethylene preferably linear low density polyethylene having a density of 0.94 g / cm 3 or less (typically 0.90 g / cm 3 to 0.94 g / cm 3 ), medium density polyethylene, density 0 .86 g / cm 3 to 0.90 g / cm 3 of an ethylene- ⁇ -olefin copolymer or the like is preferably used as a component of the polyolefin resin sheet (preferably a resin sheet containing a PE resin and a PP resin). it can.
  • the resin sheet used as the base material of the protective sheet disclosed herein may contain an appropriate component that is allowed to be contained in the base material as necessary.
  • pigments typically inorganic pigments
  • fillers typically antioxidants
  • light stabilizers such as radical scavengers and ultraviolet absorbers
  • additives such as slip agents and antiblocking agents can be appropriately blended.
  • Examples of materials that can be preferably used as pigments or fillers include inorganic powders such as titanium oxide, zinc oxide, and calcium carbonate.
  • the blending amount of the inorganic pigment and filler may be appropriately set in consideration of the degree of effect obtained by the blending and the moldability of the substrate according to the resin sheet molding method (extrusion molding, cast molding, etc.). it can.
  • the blending amount of inorganic pigment and filler (the total amount when blending plural kinds) is about 2 to 20 parts by mass (more preferably about 5 parts by mass) with respect to 100 parts by mass of the resin component. Part to 15 parts by mass).
  • antioxidants include those containing alkylphenols, alkylenebisphenols, thiopropylene acid esters, organic phosphite esters, amines, hydroquinones, hydroxylamines and the like as active ingredients.
  • light stabilizers include those containing benzotriazoles, hindered amines, benzoates and the like as active ingredients.
  • the compounding amount of the additive can be, for example, about the same as the usual compounding amount in the field of resin sheets used as a base material of a coating film protective sheet (for example, an automobile coating film protective sheet).
  • the resin sheet (preferably polyolefin resin sheet) can be produced by appropriately adopting a conventionally known general film forming method.
  • a molding material containing the above resin component preferably a resin component containing PP resin alone or a resin component containing PP resin as a main component and PE resin as an auxiliary component
  • a method of extrusion molding can be preferably employed.
  • a release treatment for example, a general purpose is performed on the surface (back surface) opposite to the surface on which the pressure-sensitive adhesive layer 2 is provided as necessary.
  • a treatment for applying a release treatment agent such as a silicone-based, long-chain alkyl-based, fluorine-based or the like into a thin film typically having a thickness of about 0.01 ⁇ m to 0.1 ⁇ m may be performed.
  • an intermediate layer such as a primer layer is provided between the substrate 1 and the pressure-sensitive adhesive layer 2
  • acid treatment, corona discharge treatment, ultraviolet irradiation treatment, plasma treatment is performed on the surface on which the intermediate layer is provided.
  • a surface treatment such as the above may be applied.
  • the thickness of the substrate can be appropriately selected according to the purpose.
  • the average thickness is suitably about 20 ⁇ m to 100 ⁇ m, preferably about 30 ⁇ m to 70 ⁇ m (for example, about 30 ⁇ m to 50 ⁇ m).
  • a base material having such a thickness is suitable as a base material for an automobile paint film protective sheet, for example.
  • the formation of the polyisobutylene-based pressure-sensitive adhesive layer can be performed according to a method for forming a pressure-sensitive adhesive layer in a known pressure-sensitive adhesive sheet.
  • a pressure-sensitive adhesive composition is prepared (manufacturing, purchasing, etc.) in which a pressure-sensitive adhesive layer-forming material containing a polymer component mainly composed of an isobutylene polymer and an additive blended as necessary is dissolved or dispersed in a suitable solvent.
  • the composition is directly applied (typically applied) to the surface of the base material or the intermediate layer and dried to form an adhesive layer on the base material or the intermediate layer (direct method). ) Can be preferably employed.
  • the pressure-sensitive adhesive composition is applied to a surface having good releasability such as a release liner or a release-treated substrate back surface and dried to form a pressure-sensitive adhesive layer on the surface, and the pressure-sensitive adhesive layer A method (transfer method) may be employed in which the substrate is transferred to the surface of the substrate or intermediate layer.
  • the pressure-sensitive adhesive layer is typically formed continuously, but may be formed in a regular or random pattern such as a dot or stripe depending on the purpose and application.
  • drying can be promoted by heating as necessary.
  • the drying temperature at this time is not particularly limited, but for example, a drying temperature of about 60 ° C. to 130 ° C. can be preferably employed.
  • the surface of the pressure-sensitive adhesive layer (pressure-sensitive adhesive layer mainly composed of isobutylene polymer) of the coating film protective sheet produced as described above typically has an oxygen atom element ratio of less than 1.0 at% (for example, 0.6 at% or less). Therefore, in carrying out the present invention, the element ratio of oxygen atoms measured by the ESCA method is 1.0 at% to 8.0 at of the entire surface on the surface of the pressure-sensitive adhesive layer provided on the coating film protective sheet. The process which introduce
  • the element ratio of oxygen atoms on the surface of the pressure-sensitive adhesive layer is not particularly limited as a method for adjusting the atomic ratio of the entire surface to 1.0 at% to 8.0 at%, but surface treatment such as corona discharge treatment, ultraviolet irradiation treatment, and plasma treatment may be performed. To apply. Among these, low temperature plasma treatment is preferable because the element ratio of oxygen atoms is easily set within the above range.
  • the low temperature plasma treatment is preferably performed under a condition in which an inert gas is introduced into a predetermined chamber and the pressure is reduced.
  • an inert gas is introduced into a predetermined chamber and the pressure is reduced.
  • the inert gas i.e. a non-oxidizing and non-reducing gas
  • the inert gas is not particularly limited, He, Ne, Ar, N 2 , and these may be used alone or in mixed state. Among these, Ar is preferable from the viewpoint of discharge starting efficiency.
  • the processing pressure pressure inside the chamber is not particularly limited as long as the pressure is reduced (less than 0.1 MPa), but is preferably 0.01 MPa or less (for example, 1 Pa to 0.01 MPa, typically 10 Pa to 1000 Pa). The pressure is reduced within the range.
  • the low temperature plasma treatment is preferably performed by an internal electrode type low temperature plasma treatment machine.
  • a low-temperature plasma processing machine that can be used in the present invention will be described.
  • Such a low-temperature plasma processing machine has a structure as schematically shown in FIG. That is, the low-temperature plasma processing apparatus 101 has a process chamber (chamber) 102 that can be sealed.
  • a processing roller 103 and a part of the periphery of the processing roller 103 typically
  • an electrode 104 is provided that surrounds at least a predetermined interval.
  • a high frequency power source 105 is connected to the electrode 104.
  • the inside of the processing chamber 102 is configured to be depressurized by opening a decompression valve 106 connected to a vacuum pump (not shown), and a supply valve 107 connected to a gas supply source (not shown). By being opened, the processing gas is supplied to the processing (discharge) section. Further, the low-temperature plasma processing machine 101 is also provided with a pressure gauge 108 for measuring the pressure in the processing chamber 102.
  • the low temperature plasma processing by the low temperature plasma processing machine 101 is generally performed as follows. First, the uncoated coating film protection sheet S wound in a roll shape is pulled out from the supply unit 109 and guided into the processing chamber 102. And it passes through the process part between the electrodes 104 so that it may wind around the process roller 103 for one round. Here, low-temperature plasma treatment is performed on the surface of the coating film protective sheet S on which the pressure-sensitive adhesive layer is provided. The treated coating film protective sheet S is pulled out from the processing chamber 102 and is taken up again in the winding unit 111. These series of steps are performed while being guided by a plurality of guide rollers 110 provided inside and outside the processing chamber 102.
  • the processing intensity of the low-temperature plasma treatment is preferably 15 W ⁇ min / m 2 or more, more preferably 20 W ⁇ min / m 2 or more (typically 30 W ⁇ min / m 2 or more).
  • the treatment intensity is 1000 W ⁇ min / m 2 or less, more preferably 500 W ⁇ min / m 2 or less (typically 300 W ⁇ min / m 2 or less).
  • the element ratio of oxygen atoms on the surface of the pressure-sensitive adhesive layer is 1.0 at% to 8.0 at the time of returning to the atmospheric pressure after the completion of the low temperature plasma treatment. %, Oxygen atoms tend to be introduced easily.
  • the coating film protective sheet according to the present invention is, for example, an article to be protected that has been coated with a paint having various compositions such as acrylic, polyester, alkyd, melamine, urethane, or a composite thereof (the above-described coating treatment).
  • automobiles that are highly likely to be stored outdoors for a long period of time or transported to tropical and other climatic areas, and have a high level of demand for the appearance design of coating films (for example, for exterior coatings on automobile bodies). It is suitable as a protective sheet.
  • the polyisobutylene-based pressure-sensitive adhesive has a large difference in solubility parameter (SP value) from a coating film (for example, a coating film for automobiles), so that it is difficult for mass transfer to occur between the two. This is preferable because it hardly causes a mark on the protective sheet.
  • SP value solubility parameter
  • such an adhesive layer has a high elastic modulus and is suitable as a re-peelable adhesive.
  • Example 1 38 parts of propylene homopolymer (product of Nippon Polypro Co., Ltd., trade name “Novatech PP (registered trademark) FY4”), 37 parts of ethylene / propylene block copolymer (product of the same company, trade name “Novatech PP (registered trademark) BC3F”), 15 parts of linear low density polyethylene (LLDPE) (product of Nippon Polyethylene Co., Ltd., trade name “Kernel (registered trademark) KF380”), rutile type titanium dioxide (product of Ishihara Sangyo Co., Ltd., trade name “TIPAQUE” (registered trademark) ) CR-95 ”)” and 10 parts of light stabilizer (Ciba Specialty Chemicals product, trade name "Chimasorb (registered trademark) 944”) And a base material having an average thickness of 40 ⁇ m extruded from the T die of the molding machine. Polyolefin resin film) was molded.
  • Example 2 A processing gas containing 80 vol% or more of Ar is introduced into the chamber on the surface of the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet according to Example 1 using the low-temperature plasma processing machine having the structure shown in FIG. A low-temperature plasma treatment was performed at a treatment intensity of 46 W ⁇ min / m 2 under the reduced pressure condition until the inside. Thus, the coating-film protection sheet which concerns on Example 2 was produced.
  • Example 3 The processing intensity of the low temperature plasma processing machine was changed to 115 W ⁇ min / m 2 . About the other point, it carried out similarly to Example 2, and produced the coating-film protection sheet which concerns on Example 3.
  • Example 4 The processing intensity of the low temperature plasma processing machine was changed to 1500 W ⁇ min / m 2 . About the other point, it carried out similarly to Example 2, and produced the coating-film protection sheet which concerns on Example 4.
  • FIG. 4 The processing intensity of the low temperature plasma processing machine was changed to 1500 W ⁇ min / m 2 . About the other point, it carried out similarly to Example 2, and produced the coating-film protection sheet which concerns on Example 4.
  • Example 5 The processing intensity of the low temperature plasma processing machine was changed to 2000 W ⁇ min / m 2 . About the other point, it carried out similarly to Example 2, and produced the coating-film protection sheet which concerns on Example 5.
  • FIG. 5 The processing intensity of the low temperature plasma processing machine was changed to 2000 W ⁇ min / m 2 . About the other point, it carried out similarly to Example 2, and produced the coating-film protection sheet which concerns on Example 5.
  • the coating film protective sheets prepared in Examples 1 to 5 were subjected to the following evaluation tests.
  • Adhesive strength The coating film protective sheet according to each example was cut into a strip having a width of 25 mm and a length of 150 mm to prepare a test piece. Electrodeposition coating, intermediate coating, and metallic coating are applied on the steel plate in order, and then an acid rain resistant clear coating (acrylic / styrene-based, non-melamine cross-linking type, containing silicone surface conditioner) is thickened. It formed so that it might become 50 micrometers.
  • a test piece was attached to the coating film in a standard environment adjusted to a temperature of 23 ⁇ 2 ° C. and a humidity of 50 ⁇ 15% RH.
  • the affixing was performed by reciprocating a 2 kg rubber roller specified in JIS Z 0237: 2000 once at a speed of 0.3 m / min. After pasting, a peel test was performed under the following conditions for those stored for 48 hours (initial), one month, and three months under atmospheric pressure conditions adjusted to a temperature of 23 ⁇ 2 ° C. and a humidity of 50 ⁇ 15% RH. Peel test: Using an Autograph AG-10G type tensile tester manufactured by Shimadzu Corporation, peel strength [N / 25 mm under conditions of peel speed (crosshead speed) 300 mm / min, peel angle 180 °, peel length 100 mm ] was measured. The measurement was performed three times, and the average of these was recorded in Table 1 as a measured value.
  • the initial adhesive force is 4.3 N / 25 mm. As described above, good initial adhesive strength was exhibited. In addition, no decrease in adhesive strength was observed after 3 months. Thus, the coating film protective sheet according to Examples 2 and 3 had a good initial adhesive force and was excellent in the temporal stability of the adhesive force.
  • Example 1 using the pressure-sensitive adhesive layer having a surface oxygen atom ratio of less than 1.0 at%, the initial adhesive strength was lower than that in Examples 2 and 3, and the adhesive strength further decreased after one month.
  • Examples 4 and 5 using a pressure-sensitive adhesive layer having a surface oxygen atom ratio exceeding 8.0 at% also have a lower initial adhesive strength than Examples 2 and 3, and particularly the adhesive strength after one month is significantly reduced. The tendency to do was recognized.
  • the functional groups having oxygen atoms that affect the adhesion to the coating film were not sufficiently formed or excessively formed, so that the initial adhesion was inferior to those in Examples 2 and 3, and the surface oxygen
  • the pressure-sensitive adhesive layer having an atomic ratio of more than 8.0 at% was used, the formed functional group having oxygen atoms could not be stably present on the surface of the pressure-sensitive adhesive layer. Presumed to have fallen.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

L'invention concerne une feuille pour la protection d'un film de revêtement, qui présente une bonne force d'adhésion initiale, la stabilité à long terme de la force d'adhésion étant hautement supérieure. La feuille pour protéger un film de revêtement proposée par la présente invention comprend une couche d'agent adhésif contenant un polymère d'isobutylène en tant que composant principal. Dans la feuille pour protéger un film de revêtement, le taux élémentaire d'un atome d'oxygène tel que mesuré par un procédé ESCA sur la surface de la couche d'agent adhésif est de 1,0 à 8,0 % at. de celui sur la surface entière de la feuille.
PCT/JP2012/070456 2011-09-21 2012-08-10 Feuille pour protéger un film de revêtement et son procédé de préparation WO2013042485A1 (fr)

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JP2011-206185 2011-09-21

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CN111149191A (zh) * 2017-12-07 2020-05-12 琳得科株式会社 工件加工用片及已加工工件的制造方法

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JPS52114632A (en) * 1976-03-22 1977-09-26 Sekisui Chem Co Ltd Pressure sensitive adhesive tape or sheet
JPH07173441A (ja) * 1993-12-17 1995-07-11 Fujimori Kogyo Kk 粘着剤層の粘着力改良方法
JP2000073029A (ja) * 1998-08-26 2000-03-07 Nitto Denko Corp 粘着部材及びその製造方法
JP2000256625A (ja) * 1999-03-08 2000-09-19 Nitto Denko Corp 粘着部材
JP2001240820A (ja) * 2000-02-29 2001-09-04 Nitto Denko Corp 塗膜保護シート、その製造方法及び施工方法
JP2001354917A (ja) * 2000-06-14 2001-12-25 Nitto Denko Corp 粘着部材及びその製造方法

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Publication number Priority date Publication date Assignee Title
JPS52114632A (en) * 1976-03-22 1977-09-26 Sekisui Chem Co Ltd Pressure sensitive adhesive tape or sheet
JPH07173441A (ja) * 1993-12-17 1995-07-11 Fujimori Kogyo Kk 粘着剤層の粘着力改良方法
JP2000073029A (ja) * 1998-08-26 2000-03-07 Nitto Denko Corp 粘着部材及びその製造方法
JP2000256625A (ja) * 1999-03-08 2000-09-19 Nitto Denko Corp 粘着部材
JP2001240820A (ja) * 2000-02-29 2001-09-04 Nitto Denko Corp 塗膜保護シート、その製造方法及び施工方法
JP2001354917A (ja) * 2000-06-14 2001-12-25 Nitto Denko Corp 粘着部材及びその製造方法

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MASAYOSHI KAWABE ET AL.: "Diffusion Behavior of Poly(isobutylene) on Poly(isobutylene)/Paint Interfaces", JOURNAL OF THE ADHESION SOCIETY OF JAPAN, vol. 36, no. 5, 1 May 2000 (2000-05-01), pages 185 - 190 *
MASAYOSHI KAWABE: "Nenchaku Tape no Hyomen Kaishitsu to Nenchaku Tokusei", NITTO TECHNICAL REPORT, vol. 38, no. 2, November 2000 (2000-11-01), pages 18 - 23 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111149191A (zh) * 2017-12-07 2020-05-12 琳得科株式会社 工件加工用片及已加工工件的制造方法
CN111149191B (zh) * 2017-12-07 2023-08-29 琳得科株式会社 工件加工用片及已加工工件的制造方法

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