WO2013121885A1 - Feuille de protection de surface - Google Patents

Feuille de protection de surface Download PDF

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Publication number
WO2013121885A1
WO2013121885A1 PCT/JP2013/052140 JP2013052140W WO2013121885A1 WO 2013121885 A1 WO2013121885 A1 WO 2013121885A1 JP 2013052140 W JP2013052140 W JP 2013052140W WO 2013121885 A1 WO2013121885 A1 WO 2013121885A1
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WO
WIPO (PCT)
Prior art keywords
layer
white
weight
base material
polyethylene
Prior art date
Application number
PCT/JP2013/052140
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English (en)
Japanese (ja)
Inventor
生島　伸祐
二郎 山戸
公平 武田
Original Assignee
日東電工株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Priority claimed from JP2012030037A external-priority patent/JP2013166833A/ja
Priority claimed from CN2012100362183A external-priority patent/CN103254819A/zh
Application filed by 日東電工株式会社 filed Critical 日東電工株式会社
Publication of WO2013121885A1 publication Critical patent/WO2013121885A1/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
    • C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J153/02—Vinyl aromatic monomers and conjugated dienes
    • 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
    • C09J7/24—Plastics; Metallised plastics based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/241—Polyolefin, e.g.rubber
    • C09J7/243—Ethylene or propylene 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
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
    • 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
    • C09J2423/04—Presence of homo or copolymers of ethene
    • C09J2423/046—Presence of homo or copolymers of ethene in the substrate
    • 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
    • C09J2425/00—Presence of styrenic polymer

Definitions

  • the present invention relates to a surface protection sheet.
  • this invention relates to the surface protection sheet containing a base material layer and an adhesion layer.
  • the surface protective sheet of the present invention includes, for example, a metal plate, a paint plate, an aluminum sash, a resin plate, a decorative steel plate, a vinyl chloride laminated steel plate, a glass plate and other members, a polarizing film, an optical member such as a liquid crystal panel, and an electronic member. When transporting, processing, curing, etc., it is used for applications such as sticking to the surface for protection.
  • the surface protective sheet is generally provided with an adhesive layer on one side of the base material layer.
  • a method for producing a surface protective sheet including such a base material layer and an adhesive layer a method in which the base material layer and the adhesive layer are integrally formed by coextrusion molding has been proposed (for example, see Patent Document 1). .
  • An object of the present invention is to provide a surface protection sheet including a base material layer and an adhesive layer, and the surface protection sheet does not impair the appearance and feel even if foreign matter is present on the outermost surface of the base material layer. There is to do.
  • the surface protective sheet of the present invention is A surface protective sheet comprising a base material layer and an adhesive layer, The base material layer and the adhesive layer are integrally formed by coextrusion molding, The surface roughness Ra of the outermost surface of the base material layer is 0.10 ⁇ m to 0.60 ⁇ m, The 60 degree gloss of the outermost surface of the base material layer is 20.0 to 71.5.
  • the surface roughness Ra is 0.20 ⁇ m to 0.60 ⁇ m, and the 60 degree gloss is 20.0 to 65.0.
  • the base material layer contains a polyolefin-based resin as a main component.
  • the base material layer includes a white layer.
  • the white layer includes a polyethylene resin as a main component.
  • the polyethylene resin contains autoclaved polyethylene as a main component.
  • the white layer further includes a resin different from the polyethylene resin.
  • the resin different from the polyethylene resin is at least one selected from a polypropylene resin and an ethylene / vinyl acetate copolymer.
  • the white layer contains particles.
  • the substrate layer includes a black layer.
  • the black layer contains a polyethylene resin as a main component.
  • the adhesive layer contains a styrene-based thermoplastic elastomer.
  • a surface protective sheet comprising a base material layer and an adhesive layer, the surface protective sheet not impairing the appearance and tactile sensation even if foreign matter is present on the outermost surface of the base material layer. can do.
  • the surface protective sheet of the present invention is a surface protective sheet including a base material layer and an adhesive layer.
  • the surface protective sheet of the present invention may contain any appropriate other layer as long as the effects of the present invention are not impaired.
  • the thickness of the substrate layer is preferably 20 ⁇ m to 300 ⁇ m, more preferably 30 ⁇ m to 250 ⁇ m, still more preferably 40 ⁇ m to 200 ⁇ m, particularly preferably 45 ⁇ m to 150 ⁇ m, and most preferably 50 ⁇ m to 100 ⁇ m. is there. If the thickness of the base material layer falls within the above range, the base material layer is less likely to be torn or torn when it is peeled off after the surface protective sheet of the present invention is applied to the adherend. Since the increase in stiffness can be suppressed, it is difficult for floating and the like to occur after the surface protective sheet of the present invention is applied to the adherend.
  • the thickness of the adhesive layer is preferably 1 ⁇ m to 50 ⁇ m, more preferably 2 ⁇ m to 40 ⁇ m, still more preferably 3 ⁇ m to 30 ⁇ m, particularly preferably 4 ⁇ m to 20 ⁇ m, and most preferably 5 ⁇ m to 10 ⁇ m. .
  • the total thickness of the surface protective sheet of the present invention is preferably 30 ⁇ m to 150 ⁇ m, more preferably 35 ⁇ m to 140 ⁇ m, still more preferably 40 ⁇ m to 130 ⁇ m, particularly preferably 45 ⁇ m to 120 ⁇ m, and most preferably. Is 50 ⁇ m to 110 ⁇ m.
  • the surface protective sheet of the present invention is formed by integrally forming a base material layer and an adhesive layer by coextrusion molding.
  • coextrusion molding any appropriate coextrusion molding generally used for production of films, sheets and the like can be adopted.
  • coextrusion molding for example, an inflation method, a coextrusion T-die method, or the like can be employed. These coextrusion molding is preferable in terms of cost and productivity.
  • the surface roughness Ra of the outermost surface of the base material layer is 0.10 ⁇ m to 0.60 ⁇ m, preferably 0.20 ⁇ m to 0.60 ⁇ m, more preferably 0.25 ⁇ m to The thickness is 0.60 ⁇ m, more preferably 0.30 ⁇ m to 0.60 ⁇ m, particularly preferably 0.35 ⁇ m to 0.60 ⁇ m, and most preferably 0.40 ⁇ m to 0.60 ⁇ m.
  • the surface roughness Ra of the outermost surface of the base material layer falls within the above range, the outermost surface of the base material layer can be effectively roughened. It is possible to provide a surface protective sheet that does not impair the appearance and feel even if it is inherent. In addition, the detail of the measuring method of surface roughness Ra is mentioned later.
  • the 60 degree gloss of the outermost surface of the base material layer is 20.0 to 71.5, preferably 20.0 to 65.0, more preferably 20.0 to 63. 0.0, more preferably 20.0 to 60.0, particularly preferably 20.0 to 55.0, and most preferably 20.0 to 50.0.
  • the outermost surface of the base material layer can be effectively matted, and even if foreign matter is present on the outermost surface of the base material layer. It is possible to provide a surface protective sheet that does not impair the appearance and feel even if it is inherent. The details of the 60-degree gloss measurement method will be described later.
  • both the surface roughness Ra of the outermost surface of the base material layer and the 60 degree gloss of the outermost surface of the base material layer fall within the above range.
  • the outermost surface roughness Ra of the base material layer is 0.10 ⁇ m to 0.60 ⁇ m, and the outermost surface of the base material layer has a 60 degree gloss. More preferably, the surface roughness Ra is 0.20 ⁇ m to 0.60 ⁇ m, and the 60 ° gloss is 20.0 to 65.0.
  • the outermost surface of the base material layer is effectively roughened and matted. It is possible to effectively provide a surface protective sheet that does not impair the appearance and feel even if foreign substances are present on the outermost surface of the base material layer.
  • the base material layer preferably contains a polyolefin resin as a main component.
  • a polyolefin resin as a main component, it can have heat resistance, solvent resistance, and flexibility, and can be easily wound into a roll.
  • the polyolefin resin contained in the base material layer may be only one type or two or more types.
  • the substrate layer may be a single layer or a plurality of layers.
  • the “main component” in the present invention is preferably 50% by weight or more, more preferably 60% by weight or more, still more preferably 70% by weight or more, and particularly preferably 80% by weight or more. Yes, and most preferably 90% by weight or more.
  • polystyrene resin examples include a polyethylene resin, a polypropylene resin, and an ethylene / ⁇ -olefin copolymer.
  • polystyrene resin examples include polyethylene resins such as high density polyethylene (HDPE), medium density polyethylene, low density polyethylene (LDPE), and linear low density polyethylene (LLDPE); homopolypropylene, block Polypropylene resins such as polypropylene and random polypropylene; poly (1-butene); poly (4-methyl-1-pentene); ethylene / propylene copolymer, ethylene / 1-butene copolymer, ethylene / 1-hexene copolymer Polymer, ethylene / 4-methyl-1-pentene copolymer, ethylene / 1-octene copolymer, ethylene / methyl acrylate copolymer, ethylene / methyl methacrylate copolymer, ethylene / vinyl acetate copolymer , Ethylene ethyl acrylate copolymer, ethylene Ethylene ⁇ alpha-olefin copolymer alcohol copolymer; and the like.
  • each adjacent layer should be selected as a resin component that can form a strong bond with each other by melt coextrusion. Is preferred.
  • the base material layer may include a white layer.
  • a surface protective sheet having excellent weather resistance can be obtained.
  • the base material layer may include a black layer.
  • a surface protective sheet having excellent weather resistance can be obtained.
  • the base material layer preferably includes at least two layers of a white layer and a black layer.
  • a surface protective sheet having excellent weather resistance can be obtained.
  • FIG. 1 is a cross-sectional view schematically showing a configuration example in the case where the surface protective sheet 100 of the present invention has a laminated configuration of “white layer 21 / black layer 22 / adhesive layer 10”. The white layer 21 and the black layer 22 become the base material layer 20.
  • the white layer is a layer showing a white color tone.
  • the whiteness defined by JIS-L-1015 is preferably 60% or more, more preferably 70% or more, and still more preferably. It is 80% or more, and particularly preferably 85% or more.
  • the white layer preferably contains a white pigment. Any appropriate white pigment can be adopted as the white pigment. An example of such a white pigment is titanium oxide.
  • the white layer contains a white pigment, the content thereof is preferably 0.1% by weight to 50% by weight, more preferably 1% by weight to 40% with respect to the resin component forming the white layer. % By weight, more preferably 2% by weight to 30% by weight.
  • a surface protective sheet having excellent weather resistance can be obtained, and extrudability and other moldability are also excellent.
  • the white layer preferably contains a polyolefin resin as a main component.
  • the polyolefin resin that can be contained in the white layer include a polyethylene resin, a polypropylene resin, and an ethylene / ⁇ -olefin copolymer.
  • the polyolefin resin that can be contained in the white layer only one kind may be used, or two or more kinds may be used.
  • polystyrene resin examples include polyethylene such as high density polyethylene (HDPE), medium density polyethylene, low density polyethylene (LDPE), and linear low density polyethylene (LLDPE).
  • Polypropylene resins such as homopolypropylene, block polypropylene, and random polypropylene; poly (1-butene); poly (4-methyl-1-pentene); ethylene / propylene copolymer, ethylene / 1-butene copolymer Ethylene / 1-hexene copolymer, ethylene-4-methyl-1-pentene copolymer, ethylene / 1-octene copolymer, ethylene / methyl acrylate copolymer, ethylene / methyl methacrylate copolymer, Ethylene / vinyl acetate copolymer, ethylene / ethyl acrylate copolymer Coalesced, ethylene-alpha-olefin copolymers such as ethylene-vinyrene (ethylene-viny
  • the content of the polyolefin-based resin in the white layer is preferably 50% by weight or more, more preferably 60% by weight or more, still more preferably 70% by weight or more, and particularly preferably 80% by weight or more. Yes, most preferably 90% by weight or more.
  • the white layer preferably contains a polyethylene resin as a main component.
  • the base layer can have heat resistance, solvent resistance, and flexibility, and the surface protective sheet of the present invention can be easily wound into a roll. Is possible.
  • the polyethylene resin preferably contains a low density polyethylene as a main component.
  • the base material layer can have sufficient heat resistance, solvent resistance, and flexibility, and the surface protection sheet of the present invention can be more easily rolled. It becomes possible to wind up.
  • Examples of the polyethylene resin that can be contained in the white layer include autoclaved polyethylene and tubular polyethylene.
  • Autoclave polyethylene has a relatively wide molecular weight distribution and a large amount of high molecular weight components compared to tubular polyethylene. For this reason, when the autoclave method polyethylene is adopted as the main component of the polyethylene resin that can be contained in the white layer, the outermost surface of the white layer can be effectively matted. In addition, autoclaved polyethylene has long chain branching, and an expansion phenomenon accompanying pressure loss called swell occurs during extrusion. For this reason, when the autoclave method polyethylene is adopted as the main component of the polyethylene resin that can be contained in the white layer, the outermost surface of the white layer can be effectively roughened. As the polyethylene resin that can be contained in the white layer, autoclave polyethylene and tubular polyethylene may be used in combination.
  • the density of the polyethylene resin that can be contained in the white layer is preferably 0.880 g / cm 3 to 0.940 g / cm 3 , more preferably 0.880 g / cm 3 to 0.923 g / cm 3 . , more preferably from 0.880g / cm 3 ⁇ 0.915g / cm 3.
  • the density of the polyethylene resin that can be contained in the white layer falls within the above range, the outermost surface of the white layer can be effectively roughened and matted.
  • the MFR of the polyethylene resin that can be contained in the white layer is preferably 0.1 g / 10 min to 10 g / 10 min, more preferably 0.3 g / 10 min to 5 g / 10 min, and still more preferably 0.3 g / min. 10 min to 3 g / 10 min.
  • the outermost surface of the white layer can be effectively roughened and matte.
  • the white layer may further include a resin different from the polyethylene resin (this may be referred to as “different resin”).
  • a resin different from the polyethylene resin this may be referred to as “different resin”.
  • the white layer contains a different resin, combined with the polyethylene resin, the outermost surface of the white layer can be effectively roughened and matted.
  • any appropriate resin can be adopted as long as the effects of the present invention are not impaired.
  • examples of such a different resin include at least one selected from a polypropylene resin and an ethylene / vinyl acetate copolymer.
  • the white layer contains such a different resin, the content of such a different resin in the white layer is preferably 5% to 70% by weight, more preferably 10% to 50% by weight.
  • the content ratio of such a different resin in the white layer falls within the above range, combined with the polyethylene resin, the outermost surface of the white layer is more effectively roughened and matted. can do.
  • the white layer may contain particles.
  • the white layer contains particles, the outermost surface of the white layer can be effectively roughened and matted.
  • any appropriate particles can be adopted as long as the effects of the present invention are not impaired.
  • examples of such particles include organic particles and inorganic particles.
  • examples of the organic particles include acrylic beads prepared from PMMA and the like.
  • Examples of the inorganic particles include silica and zeolite.
  • the content ratio of such particles in the white layer is preferably 0.3 wt% to 10 wt%, more preferably 0.5 wt% to 7 wt%. % By weight, more preferably 0.5% by weight to 5% by weight, and particularly preferably 0.5% by weight to 3% by weight.
  • the content ratio of such particles in the white layer falls within the above range, the outermost surface of the white layer can be more effectively roughened and matted.
  • any appropriate thickness can be adopted as the thickness of the white layer depending on the purpose.
  • Such a thickness is preferably 2 ⁇ m to 100 ⁇ m, more preferably 3 ⁇ m to 80 ⁇ m, still more preferably 4 ⁇ m to 60 ⁇ m, and particularly preferably 5 ⁇ m to 50 ⁇ m.
  • the black layer is a layer showing a black color tone.
  • the black layer preferably contains a black pigment. Any appropriate black pigment can be adopted as the black pigment.
  • An example of such a black pigment is carbon black.
  • the black layer contains a black pigment, the content thereof is preferably 0.01% by weight to 10% by weight, more preferably 0.1% by weight, with respect to the resin component forming the black layer. Is 5% by weight, more preferably 0.5% by weight to 3% by weight.
  • a surface protective sheet having excellent weather resistance can be obtained, and extrudability and other moldability are also excellent.
  • the black layer preferably contains a polyolefin resin as a main component.
  • the polyolefin resin that can be contained in the black layer include a polyethylene resin, a polypropylene resin, and an ethylene / ⁇ -olefin copolymer.
  • the polyolefin resin that can be contained in the black layer only one kind may be used, or two or more kinds may be used.
  • Polypropylene resins such as homopolypropylene, block polypropylene, and random polypropylene; poly (1-butene); poly (4-methyl-1-pentene); ethylene / propylene copolymer, ethylene / 1-butene copolymer Ethylene / 1-hexene copolymer, ethylene-4-methyl-1-pentene copolymer, ethylene / 1-octene copolymer, ethylene / methyl acrylate copolymer, ethylene / methyl methacrylate copolymer, Ethylene / vinyl acetate copolymer, ethylene / ethyl acrylate copolymer Coalesced, ethylene-alpha-olefin copolymers such as ethylene-
  • the content ratio of the polyolefin resin in the black layer is preferably 50% by weight or more, more preferably 60% by weight or more, further preferably 70% by weight or more, and particularly preferably 80% by weight or more. Yes, most preferably 90% by weight or more.
  • the black layer preferably contains a polyethylene resin as a main component.
  • the base layer can have heat resistance, solvent resistance, and flexibility, and the surface protection sheet of the present invention can be easily wound into a roll. Is possible.
  • the black layer contains a polyethylene resin as a main component
  • the polyethylene resin preferably contains at least one selected from low density polyethylene and linear low density polyethylene.
  • the base material layer can have sufficient heat resistance, solvent resistance, and flexibility. It becomes possible to wind the surface protective sheet in a roll shape more easily.
  • the density of the polyethylene resin that can be contained in the black layer is preferably 0.880 g / cm 3 to 0.940 g / cm 3 , more preferably 0.880 g / cm 3 to 0.924 g / cm 3 . , more preferably from 0.880g / cm 3 ⁇ 0.915g / cm 3.
  • the base layer can have sufficient heat resistance, solvent resistance, and flexibility, and the surface protective sheet of the present invention can be obtained. It can be more easily wound up in a roll shape.
  • the MFR of the polyethylene resin that can be contained in the black layer is preferably 1 g / 10 min to 10 g / 10 min, more preferably 1 g / 10 min to 5 g / 10 min, and further preferably 2 g / 10 min to 4 g / 10 min. is there.
  • the base material layer can have sufficient heat resistance, solvent resistance, and flexibility, and the surface protective sheet of the present invention can be obtained. It can be more easily wound up in a roll shape.
  • any appropriate thickness can be adopted as the thickness of the black layer according to the purpose.
  • Such a thickness is preferably 2 ⁇ m to 100 ⁇ m, more preferably 3 ⁇ m to 80 ⁇ m, still more preferably 4 ⁇ m to 60 ⁇ m, and particularly preferably 5 ⁇ m to 50 ⁇ m.
  • the base material layer may contain any appropriate additive.
  • additives include antioxidants, ultraviolet absorbers, anti-aging agents, light stabilizers, antistatic agents, surface lubricants, leveling agents, plasticizers, low molecular weight polymers, corrosion inhibitors, and polymerization prohibitions.
  • the back surface treatment may be given to the outermost layer on the side opposite to the adhesive layer of the base material layer. Any appropriate method can be adopted as the back surface processing method as long as the effects of the present invention are not impaired. Examples of the back treatment method include surface treatment such as embossing and uneven processing, a method of containing a long-chain alkyl back treatment agent and a fatty acid derivative, and the like. Such long-chain alkyl-based back treatment agents and fatty acid derivatives may be used alone or in combination of two or more.
  • the content ratio of the fatty acid derivative in the base material layer is preferably 0.05% by weight to 1.00% by weight with respect to the resin component in the base material layer, More preferred is 0.10 wt% to 0.90 wt%, and further preferred is 0.30 wt% to 0.80 wt%. If the content ratio of the fatty acid derivative in the base material layer is within the above range with respect to the resin component in the base material layer, the roll-shaped surface protection sheet of the present invention can be easily rewound. Thus, the mold release effect can be sufficiently exhibited, and the contamination of the fatty acid derivative by bleeding can be sufficiently suppressed.
  • the fatty acid derivative refers to a compound containing a fatty acid derivative structure in the molecular structure.
  • fatty acid derivatives examples include saturated fatty acid bisamides, unsaturated fatty acid bisamides, aromatic bisamides, substituted ureas, and fatty acid metal salts.
  • Specific examples of fatty acid derivatives include methylene bis stearamide, ethylene bis stearamide, ethylene bis oleate, N, N-dioleyl adipamide, N-stearyl-N′-stearyl urea, etc. N-stearyl-N′-stearylamide, zinc stearate and the like.
  • the fatty acid derivative is preferably a fatty acid amide, and more preferably at least one selected from methylene bis stearic acid amide, ethylene bis stearic acid amide, and N-stearyl-N′-stearyl acid amide.
  • the fatty acid derivative preferably has a melting point of 100 ° C. or higher.
  • a fatty acid derivative having a melting point of less than 100 ° C. has a significant transfer to the surface of the adhesive layer, and there is a risk that a decrease in adhesive strength is likely to occur.
  • the adhesive layer preferably contains a thermoplastic resin as a main component.
  • the thermoplastic resin contained in the adhesive layer may be only one type or two or more types.
  • thermoplastic resin any appropriate thermoplastic resin can be adopted as the thermoplastic resin.
  • thermoplastic resins include olefin resins, aromatic group-containing olefin / diene copolymers, styrene resins, ester resins, and the like.
  • styrene resins are preferable, and styrene thermoplastic elastomers are more preferable.
  • the styrene thermoplastic elastomer is preferably a styrene block copolymer or a hydrogenated product thereof.
  • styrene block copolymers examples include styrene ABA block copolymers (triblock copolymers) such as styrene / butadiene / styrene copolymers (SBS) and styrene / isoprene / styrene copolymers (SIS).
  • triblock copolymers such as styrene / butadiene / styrene copolymers (SBS) and styrene / isoprene / styrene copolymers (SIS).
  • Styrenic ABAB type block copolymer such as styrene / butadiene / styrene / butadiene copolymer (SBSB), styrene / isoprene / styrene / isoprene copolymer (SISI); styrene / butadiene ⁇ Styrene-based ABABA block copolymer (pentablock copolymer) such as styrene / butadiene / styrene copolymer (SBSBS), styrene / isoprene / styrene / isoprene / styrene copolymer (SISIS); Styrene having repeating units Lock copolymers; and the like.
  • hydrogenated styrenic block copolymers examples include styrene / ethylene-butylene copolymer / styrene copolymer (SEBS), styrene / ethylene-propylene copolymer / styrene copolymer (SEPS), and styrene. And ethylene-butylene copolymer, styrene-ethylene-butylene copolymer copolymer (SEBSEB), and the like.
  • thermoplastic elastomer Only one kind of styrene-based thermoplastic elastomer may be used, or two or more kinds may be used.
  • the styrenic thermoplastic elastomer is a styrenic block copolymer or a hydrogenated product thereof
  • the styrene block content in the styrenic thermoplastic elastomer is preferably 5% by weight to 40% by weight, more preferably 7% by weight. % To 30% by weight, more preferably 9% to 20% by weight.
  • the styrene block content is reduced, adhesive residue due to insufficient cohesive force of the adhesive layer may be easily generated.
  • the pressure-sensitive adhesive layer becomes hard, and there is a possibility that good adhesion to a rough surface cannot be obtained.
  • styrene-based thermoplastic elastomer hydrogenation of a styrene-based block copolymer having a repeating structure (ABA type, ABAB type, ABABA type, etc.) more than a triblock copolymer composed of styrene (A) and butadiene (B). Goods (SEBS, SEBSEB, SEBSEBS, etc.) are preferred.
  • a styrenic thermoplastic elastomer By adopting such a styrenic thermoplastic elastomer, the adhesive force in the state of being applied to the adherend can be increased more moderately, while the adhesive force when peeling off after being attached to the adherend is more appropriate. Therefore, it can be peeled off from the adherend more easily with a slight force, and the increase in adhesive strength when exposed to an environmental load for long-term storage at relatively high temperatures is further suppressed. it can.
  • the proportion of the butylene structure in the ethylene-butylene copolymer block is preferably 60% by weight or more, more preferably 70% by weight or more, and further preferably 75%. % By weight or more.
  • the proportion of the butylene structure in the ethylene-butylene copolymer block falls within the above range, the adhesive force in the state of application to the adherend can be increased more moderately.
  • Adhesive strength at the time of peeling is a more appropriate size. Therefore, it can be peeled off from the adherend more easily with a slight force, and further exposed to the environmental load of long-term storage at a relatively high temperature. In this case, the increase in adhesive strength can be further suppressed.
  • the proportion of the butylene structure in the ethylene-butylene copolymer block is preferably 90% by weight or less.
  • the pressure-sensitive adhesive layer may contain other styrenic thermoplastic elastomers within the range that does not impair the object of the present invention for the purpose of adjusting the pressure-sensitive adhesiveness.
  • styrenic thermoplastic elastomers include styrene block copolymers other than those described above; styrene / butadiene copolymers (SB), styrene / isoprene copolymers (SI), styrene / ethylene-butylene copolymers.
  • AB block polymer such as polymer (SEB) and styrene / ethylene-propylene copolymer (SEP); Styrene random copolymer such as styrene / butadiene rubber (SBR); Styrene / ethylene-butylene copolymer ABC type styrene / olefin crystal block polymers such as polymers / olefin crystal copolymers (SEBC); hydrogenated products thereof, and the like.
  • SEB polymer
  • SEP styrene / ethylene-propylene copolymer
  • SBR butadiene rubber
  • SEBC Styrene / ethylene-butylene copolymer ABC type styrene / olefin crystal block polymers
  • SEBC olefin crystal copolymers
  • the adhesive layer for the purpose of controlling adhesive properties, etc., for example, softening agents, tackifiers, polyolefin resins such as those used for the base material layer, silicone polymers, liquid acrylic copolymers are used.
  • Additives such as ring agents, inorganic and organic fillers (for example, calcium oxide, magnesium oxide, silica, zinc oxide, titanium oxide, etc.), metal powder, colorants, pigments, heat stabilizers, etc. may be added as appropriate. it can.
  • corona discharge treatment ultraviolet irradiation treatment, flame treatment, plasma treatment, sputter etching treatment, and other surface treatments for the purpose of adhesion control and pasting workability are performed on the adhesive layer surface as necessary. You can also.
  • Blending of tackifier is effective for improving adhesive strength.
  • the blending amount of the tackifier is appropriately determined according to the adherend to which the surface protective sheet is applied in order to avoid the occurrence of the adhesive residue problem due to the decrease in cohesive force.
  • the compounding amount of the tackifier is preferably 80% by weight or less, more preferably 40% by weight or less, and further preferably 20% by weight or less with respect to the base polymer of the adhesive layer.
  • the adherend to which the surface protective sheet is applied is a metal plate, it is preferable not to add a tackifier when forming the adhesive layer.
  • tackifier examples include petroleum-based resins such as aliphatic copolymers, aromatic copolymers, aliphatic / aromatic copolymer systems and alicyclic copolymers, and coumarone-indene resins.
  • what is marketed as a blend with an olefin resin can also be used for a tackifier.
  • Softener blending is effective in improving adhesive strength.
  • the softening agent include low molecular weight diene polymers, polyisobutylene, hydrogenated polyisoprene, hydrogenated polybutadiene, and derivatives thereof.
  • such derivatives include those having an OH group or a COOH group at one or both ends.
  • examples thereof include polyisoprene monool.
  • hydrogenated products of diene polymers such as hydrogenated polybutadiene and hydrogenated polyisoprene, olefinic softeners, and the like are preferable for the purpose of suppressing the improvement in adhesiveness to the adherend.
  • a softening agent specifically, trade name “Kuraprene LIR-200” manufactured by Kuraray Co., Ltd. is available. These softeners may be used alone or in combination of two or more.
  • the molecular weight of the softening agent can be appropriately set to any appropriate amount, but if the molecular weight is small, there is a risk of causing material transfer or heavy peeling from the adhesive layer to the adherend, while the molecular weight is large. Therefore, the softening agent has a number average molecular weight of preferably from 5,000 to 100,000, more preferably from 10,000 to 50,000.
  • the amount added can be appropriately set to any appropriate amount. However, as the amount added increases, the adhesive residue tends to increase at high temperatures and when exposed outdoors. On the other hand, it is preferably 100% by weight or less, more preferably 60% by weight or less, and still more preferably 40% by weight or less.
  • the adherend to which the surface protective sheet is applied is a metal plate, it is preferable not to add a softener when forming the adhesive layer.
  • the polyolefin resin may be added to the adhesive layer for the purpose of suppressing an increase in adhesive force.
  • Examples of the polyolefin resin can be the same as those used for forming the base material layer.
  • This polyolefin resin may be only one kind or two or more kinds.
  • the blending amount of the polyolefin resin is preferably 50% by weight or less, more preferably 30% by weight or less, and further preferably 20% by weight or less with respect to the base polymer of the adhesive layer.
  • the adhesive layer can be protected by temporarily attaching a separator or the like until it is put to practical use.
  • the method for producing the surface protective sheet of the present invention is preferably produced by integrally forming the base material layer and the adhesive layer by coextrusion molding.
  • prescribed thickness can be manufactured highly efficiently and cheaply.
  • the coextrusion molding any appropriate coextrusion molding generally used for production of films, sheets and the like can be adopted.
  • the coextrusion molding for example, an inflation method, a coextrusion T-die method, or the like can be employed.
  • the outermost surface on the opposite side of the adhesive layer of the base material layer and the adhesive layer are not in contact with each other in the melt-heated state. There is no production of by-products and no transfer of the by-products to the adhesive layer, and excellent unwinding properties are exhibited, and contamination of the adhesive layer surface can be suppressed.
  • the density (g / cm 3 ) of the resin was a value measured according to ISO 1183.
  • the surface protection sheet was affixed to the SUS430BA plate by a reciprocating 2 kg roller.
  • the surface roughness Ra ( ⁇ m) of the attached surface protective sheet on the white layer side was measured according to JIS B0601 (2001) at a stylus tip diameter of 2 ⁇ m, a measurement length of 4 mm, and a cutoff of 0.8 mm.
  • the surface protective sheet was affixed to the SUS430BA plate by a reciprocating 2 kg roller, and observed visually from the white layer side of the adhered surface protective sheet.
  • the case where bubbles or foreign matters were noticeably observed at the time of pasting was rated as x, and the case where bubbles or foreign matters were hardly seen due to roughening or low gloss of the surface was marked as ⁇ .
  • the surface protective sheet (3) (thickness: 3 layer structure (white layer / black layer / adhesive layer)) was carried out in the same manner as in Example 1 except that the white layer-forming material thus obtained was used.
  • White layer / black layer / adhesive layer 20 ⁇ m / 35 ⁇ m / 5 ⁇ m). The results are shown in Table 1.
  • a surface protective sheet having a three-layer structure (white layer / black layer / adhesive layer) was carried out in the same manner as in Example 1 except that the white layer-forming material obtained by blending 18% by weight was used.
  • the surface protective sheet (6) (thickness: 3 layer structure (white layer / black layer / adhesive layer)) was carried out in the same manner as in Example 1 except that the white layer forming material obtained in this manner was used.
  • White layer / black layer / adhesive layer 20 ⁇ m / 35 ⁇ m / 5 ⁇ m). The results are shown in Table 1.
  • a surface protective sheet (7) having a three-layer structure (white layer / black layer / adhesive layer) (thickness: white layer) was carried out in the same manner as in Example 1 except that the obtained white layer forming material was used.
  • / Black type layer / adhesive layer 20 ⁇ m / 35 ⁇ m / 5 ⁇ m). The results are shown in Table 2.
  • a surface protective sheet (8) having a three-layer structure (white layer / black layer / adhesive layer) (thickness: white layer) was carried out in the same manner as in Example 1 except that the obtained white layer forming material was used.
  • / Black type layer / adhesive layer 20 ⁇ m / 35 ⁇ m / 5 ⁇ m). The results are shown in Table 2.
  • a surface protective sheet (9) having a three-layer structure (white layer / black layer / adhesive layer) (thickness: white layer) was carried out in the same manner as in Example 1 except that the obtained white layer forming material was used.
  • Layer / black layer / adhesive layer 20 ⁇ m / 35 ⁇ m / 5 ⁇ m). The results are shown in Table 2.
  • polypropylene Nippon Polypro
  • white layer forming material obtained by blending 20% by weight manufactured by Novatec PP EG8B
  • white pigment titanium oxide, manufactured by DuPont, trade name: Ti-
  • a vinyl copolymer Mitsubishi Chemical, trade name: Everflex EV360RC
  • a surface protective sheet (12) having a three-layer structure (white layer / black layer / adhesive layer) (thickness: white layer / black) was carried out in the same manner as in Example 1 except that the white layer forming material was used.
  • System layer / adhesive layer 20 ⁇ m / 35 ⁇ m / 5 ⁇ m). The results are shown in Table 2.
  • the surface protective sheet of the present invention is a surface protective sheet including a base material layer and an adhesive layer, and the outermost surface of the base material layer is effectively roughened to form a mat. It can be seen that the appearance and tactile sensation are not impaired even if foreign matter is present.
  • the surface protective sheet of the present invention includes, for example, a metal plate, a coating plate, an aluminum sash, a resin plate, a decorative steel plate, a vinyl chloride laminated steel plate, a glass plate, a member such as a polarizing film, an optical member such as a liquid crystal panel, and an electronic member.
  • a metal plate for example, a metal plate, a coating plate, an aluminum sash, a resin plate, a decorative steel plate, a vinyl chloride laminated steel plate, a glass plate, a member such as a polarizing film, an optical member such as a liquid crystal panel, and an electronic member.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Adhesive Tapes (AREA)
  • Laminated Bodies (AREA)

Abstract

La présente invention concerne une feuille de protection de surface qui comprend une couche de matériau de base et une couche adhésive, et qui ne modifie pas l'aspect extérieur ni son toucher même si de la matière étrangère se trouve sur la surface la plus extérieure de la couche de matériau de base. Ladite feuille de protection de surface comprend une couche de matériau de base et une couche adhésive; on l'obtient en formant monobloc la couche de matériau de base et la couche adhésive par moulage par coextrusion. La rugosité de surface (Ra) de la surface la plus extérieure de la couche de matériau de base se situe dans la plage 0,10µm-0,60µm. La brillance à 60 degrés de la surface la plus extérieure de la couche de matériau de base se situe dans la plage 20,0-71,5.
PCT/JP2013/052140 2012-02-15 2013-01-31 Feuille de protection de surface WO2013121885A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2012-030037 2012-02-15
JP2012030037A JP2013166833A (ja) 2012-02-15 2012-02-15 表面保護シート
CN201210036218.3 2012-02-15
CN2012100362183A CN103254819A (zh) 2012-02-15 2012-02-15 表面保护片

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WO2013121885A1 true WO2013121885A1 (fr) 2013-08-22

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WO2014080806A1 (fr) * 2012-11-22 2014-05-30 日東電工株式会社 Feuille de protection de surface

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JP2003096410A (ja) * 2001-09-25 2003-04-03 Lintec Corp 表面保護用粘着シート
JP2004511002A (ja) * 2000-08-07 2004-04-08 スリーエム　イノベイティブ　プロパティズ　カンパニー 情報表示装置プロテクタ
JP2007070401A (ja) * 2005-09-05 2007-03-22 Nitto Denko Corp 粘着テープ類およびその製造方法
JP2007204713A (ja) * 2006-02-06 2007-08-16 Nitto Denko Corp 表面保護用フィルム基材、ならびに、表面保護用粘着フィルムおよびその製造方法
JP2009241338A (ja) * 2008-03-31 2009-10-22 Dainippon Printing Co Ltd プロテクトフィルム
JP2009275209A (ja) * 2008-04-14 2009-11-26 Nitto Denko Corp 粘着剤、粘着シート及びその製造方法
JP2011006624A (ja) * 2009-06-29 2011-01-13 Dainippon Printing Co Ltd 粘着積層体の製造方法
JP2011236358A (ja) * 2010-05-12 2011-11-24 Nitto Denko Corp 表面保護フィルム

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JP2004511002A (ja) * 2000-08-07 2004-04-08 スリーエム　イノベイティブ　プロパティズ　カンパニー 情報表示装置プロテクタ
JP2002226814A (ja) * 2001-02-05 2002-08-14 Nitto Denko Corp 粘着剤組成物及び粘着シート
JP2002226813A (ja) * 2001-02-05 2002-08-14 Nitto Denko Corp 粘着剤及び粘着シート
JP2003096410A (ja) * 2001-09-25 2003-04-03 Lintec Corp 表面保護用粘着シート
JP2007070401A (ja) * 2005-09-05 2007-03-22 Nitto Denko Corp 粘着テープ類およびその製造方法
JP2007204713A (ja) * 2006-02-06 2007-08-16 Nitto Denko Corp 表面保護用フィルム基材、ならびに、表面保護用粘着フィルムおよびその製造方法
JP2009241338A (ja) * 2008-03-31 2009-10-22 Dainippon Printing Co Ltd プロテクトフィルム
JP2009275209A (ja) * 2008-04-14 2009-11-26 Nitto Denko Corp 粘着剤、粘着シート及びその製造方法
JP2011006624A (ja) * 2009-06-29 2011-01-13 Dainippon Printing Co Ltd 粘着積層体の製造方法
JP2011236358A (ja) * 2010-05-12 2011-11-24 Nitto Denko Corp 表面保護フィルム

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014080806A1 (fr) * 2012-11-22 2014-05-30 日東電工株式会社 Feuille de protection de surface

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