WO2013121888A1 - Feuille de protection de surface - Google Patents

Feuille de protection de surface Download PDF

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Publication number
WO2013121888A1
WO2013121888A1 PCT/JP2013/052143 JP2013052143W WO2013121888A1 WO 2013121888 A1 WO2013121888 A1 WO 2013121888A1 JP 2013052143 W JP2013052143 W JP 2013052143W WO 2013121888 A1 WO2013121888 A1 WO 2013121888A1
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WO
WIPO (PCT)
Prior art keywords
layer
protective sheet
surface protective
adhesive
base material
Prior art date
Application number
PCT/JP2013/052143
Other languages
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.)
Filing date
Publication date
Priority claimed from CN2012103693402A external-priority patent/CN103254826A/zh
Priority claimed from JP2012213351A external-priority patent/JP2013189006A/ja
Application filed by 日東電工株式会社 filed Critical 日東電工株式会社
Publication of WO2013121888A1 publication Critical patent/WO2013121888A1/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
    • 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
    • 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
    • C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
    • C09J2301/16—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the structure of the carrier layer
    • C09J2301/162—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the structure of the carrier layer the carrier being a laminate constituted by plastic layers only
    • 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
    • C09J2301/41—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the carrier 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
    • 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
    • C09J2453/00—Presence of block copolymer

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). .
  • the conventional surface protection sheet does not have a sufficiently high adhesive force in the state of being applied to the adherend. For this reason, when processing the adherend to which the conventional surface protective sheet is attached, there is a problem that a part of the surface protective sheet is peeled off.
  • the conventional surface protection sheet has a problem that it has an excessively high adhesive force when it is peeled off after being attached to the adherend, and it is difficult to easily peel off the adherend with a slight force.
  • the conventional surface protection sheet has a problem that the adhesive strength is greatly increased when exposed to an environmental load of long-term storage at a relatively high temperature, and the peelability when peeling from the adherend is deteriorated. is there.
  • the conventional surface protection sheet does not have sufficient weather resistance, and when used outdoors or stored at high temperatures, the adhesive force greatly increases with time, and peels off the adherend. There is a problem in that the peelability at the time becomes worse.
  • An object of the present invention is a surface protective sheet including a base material layer and an adhesive layer, which has a reasonably high adhesive force in a state of being applied to an adherend, and on the other hand, is peeled off after being attached to an adherend. Adhesive strength at the time is moderate, so it can be easily peeled off from the adherend with a slight force, and when exposed to the environmental load of long-term storage at relatively high temperatures It is an object of the present invention to provide a surface protective sheet that suppresses the increase in the temperature and has sufficient weather resistance.
  • 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 initial adhesive force P to the SUS430BA plate at 180 ° peel at a tensile speed of 0.3 m / min is 2.0 N / 20 mm or more
  • the largest initial adhesive force Q (N / 20 mm) is the largest among the initial adhesive forces to the SUS430BA plate at 180 ° peel at tensile speeds of 0.3 m / min, 1 m / min, 10 m / min, and 30 m / min.
  • P is 150% or less.
  • the base material layer contains a polyolefin 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 includes low density polyethylene.
  • the substrate layer includes a black layer.
  • the black layer contains a polyethylene resin as a main component.
  • the polyethylene resin includes low density polyethylene and linear low density polyethylene.
  • the base material layer contains a light stabilizer.
  • the light stabilizer is a hindered amine light stabilizer.
  • the content ratio of the light stabilizer is 0.10% by weight or more based on the total weight of the surface protective sheet.
  • the adhesive layer contains a styrene-based thermoplastic elastomer.
  • the surface protective sheet of the present invention is applied to a SUS430BA plate and stored for 2 weeks under conditions of a temperature of 40 ° C. and a humidity of 92% RH, at a tensile rate of 180 ° peel at 10 m / min.
  • the storage adhesive strength is 7.0 N / 20 mm or less.
  • the surface protective sheet of the present invention is applied to a SUS430BA plate and stored for 2 weeks under conditions of a temperature of 50 ° C. and a humidity of 50% RH, at 180 ° peel at a tensile speed of 10 m / min.
  • the storage adhesive strength is 6.0 N / 20 mm or less.
  • the surface protective sheet of the present invention has an adhesive strength at 180 ° peel at a tensile speed of 10 m / min after being applied to a SUS430BA plate and subjected to a 750 hour sunshine weatherometer test. It is 8.0 N / 20 mm or less.
  • the present invention is a surface protective sheet including a base material layer and an adhesive layer, and has an adequately high adhesive force when applied to an adherend, and on the other hand, peels after being applied to an adherend.
  • Adhesive strength at the time is moderate, so it can be easily peeled off from the adherend with a slight force, and when exposed to the environmental load of long-term storage at relatively high temperatures
  • the surface protection sheet with sufficient weather resistance can be provided.
  • 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 protective sheet of the present invention has an initial adhesive force P of 2.0 N / 20 mm or more, preferably 2.0 N / 20 mm to 5 N / 20 mm for a SUS430BA plate at 180 ° peel at a tensile speed of 0.3 m / min. More preferably 2.1 N / 20 mm to 4 N / 20 mm, still more preferably 2.2 N / 20 mm to 3.8 N / 20 mm, and particularly preferably 2.2 N / 20 mm to 3.5 N / 20 mm. And most preferably from 2.2 N / 20 mm to 3.1 N / 20 mm.
  • the initial adhesive force P to the SUS430BA plate at 180 ° peel at a tensile speed of 0.3 m / min is an index of the adhesive force in the state of being attached to the adherend.
  • the surface protective sheet of the present invention has an appropriate adhesive force in the state of being applied to the adherend.
  • the surface protection sheet becomes difficult to peel off when the adherend to which the surface protection sheet is attached is processed.
  • the measuring method of the initial adhesive force P with respect to the SUS430BA board in 180 degree peel at a tensile speed of 0.3 m / min is mentioned later.
  • the surface protective sheet of the present invention has the largest maximum initial adhesion among the initial adhesion forces to a SUS430BA plate at 180 ° peel at tensile speeds of 0.3 m / min, 1 m / min, 10 m / min, and 30 m / min.
  • the force Q (N / 20 mm) is 150% or less of P, more preferably 80% to 150%, still more preferably 90% to 140%, and particularly preferably 95% to 135%. Most preferably, it is 100% to 130%.
  • the magnification with respect to P is an index of the adhesive strength when peeling after being attached to an adherend.
  • Maximum initial adhesive strength Q (N / 20 mm) among initial adhesive strengths for SUS430BA plate at 180 ° peel at each of tensile speeds of 0.3 m / min, 1 m / min, 10 m / min, and 30 m / min By being within the above range, the surface protective sheet of the present invention can be easily peeled off from the adherend with a slight force.
  • the largest maximum initial adhesive force Q (N / 20 mm) among the initial adhesive forces to the SUS430BA plate at 180 ° peel at each of the tensile speeds of 0.3 m / min, 1 m / min, 10 m / min, and 30 m / min. ) Will be described later.
  • the surface protective sheet of the present invention preferably has a storage adhesive strength at 180 ° peel at a tensile rate of 10 m / min after being attached to a SUS430BA plate and stored for 2 weeks under conditions of a temperature of 40 ° C. and a humidity of 92% RH.
  • Is 7.0 N / 20 mm or less more preferably 2.0 N / 20 mm to 6.0 N / 20 mm, still more preferably 2.0 N / 20 mm to 5.5 N / 20 mm, and still more preferably 2.0 N / 20 mm to 5.0 N / 20 mm, more preferably 2.0 N / 20 mm to 4.0 N / 20 mm, still more preferably 2.2 N / 20 mm to 3.8 N / 20 mm, and particularly preferably 2.N / 20 mm to 4.0 N / 20 mm. It is 4 N / 20 mm to 3.6 N / 20 mm, and most preferably 2.6 N / 20 mm to 3.4 N / 20 mm.
  • the adhesive strength for storage at 180 ° peel at a tensile speed of 10 m / min after being pasted on a SUS430BA plate and stored for 2 weeks under conditions of a temperature of 40 ° C. and a humidity of 92% RH is long-term storage at a relatively high temperature. It is an index of adhesive strength when exposed to environmental loads.
  • the storage adhesive strength at 180 ° peel at a tensile speed of 10 m / min is within the above range.
  • the surface protective sheet has good releasability when peeled from the adherend.
  • a method for measuring the storage adhesive strength at 180 ° peel at a tensile speed of 10 m / min after pasting on a SUS430BA plate and storing for 2 weeks under the conditions of a temperature of 40 ° C. and a humidity of 92% RH will be described later.
  • the surface protective sheet of the present invention preferably has a storage adhesive strength at 180 ° peel at a tensile rate of 10 m / min after being attached to a SUS430BA plate and stored for 2 weeks under conditions of a temperature of 50 ° C. and a humidity of 50% RH.
  • the adhesive strength for storage at 180 ° peel at a tensile speed of 10 m / min after being pasted on a SUS430BA plate and stored for 2 weeks under conditions of a temperature of 50 ° C. and a humidity of 50% RH is long-term storage at a relatively high temperature. It is an index of adhesive strength when exposed to environmental loads.
  • the storage adhesive force at 180 ° peel at a tensile speed of 10 m / min is within the above range, thereby allowing the present invention to
  • the surface protective sheet has good releasability when peeled from the adherend.
  • a method for measuring storage adhesive strength at 180 ° peel at a tensile speed of 10 m / min after pasting on a SUS430BA plate and storing for 2 weeks under conditions of a temperature of 50 ° C. and a humidity of 50% RH will be described later.
  • the surface protective sheet of the present invention has an adhesive strength at 180 ° peel at a tensile speed of 10 m / min after being applied to a SUS430BA plate and subjected to a 750 hour sunshine weatherometer test, preferably 8.0 N / min. 20 N or less, more preferably 2.0 N / 20 mm to 7.5 N / 20 mm, still more preferably 2.0 N / 20 mm to 7.0 N / 20 mm, and still more preferably 2.0 N / 20 mm to 6.N. 5N / 20mm, more preferably 2.0N / 20mm to 6.0N / 20mm, more preferably 2.0N / 20mm to 5.5N / 20mm, and even more preferably 2.0N / 20mm to 5N.
  • Adhesive strength at 180 ° peel at a tensile speed of 10 m / min after a 750 hour sunshine weatherometer test after being attached to a SUS430BA plate is an indicator of weather resistance.
  • the surface protective sheet of the present invention is obtained by putting the adhesive strength at 180 ° peel at a tensile speed of 10 m / min within the above range after the 750 hour sunshine weatherometer test after being attached to a SUS430BA board.
  • the base material layer preferably contains a polyolefin resin as a main component.
  • the base material layer contains a polyolefin-based 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 base material 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.
  • polyolefin resins examples include polyethylene resins, propylene or propylene resins composed of a propylene component and an ethylene component, and ethylene vinyl acetate copolymers.
  • polystyrene resin examples include high density polyethylene (HDPE), medium density polyethylene, low density polyethylene (LDPE), linear low density polyethylene (LLDPE), 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, ethylene / vinyl alcohol copolymer, etc. It is done.
  • HDPE high density polyethylene
  • LDPE low density polyethylene
  • LLDPE linear low density polyethylene
  • polypropylene poly-1-butene
  • 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 resin component forming the white layer is preferably a polyolefin resin, more preferably a propylene polymer or an ethylene polymer.
  • Specific examples of the resin component forming the white layer include homopolypropylene, block polypropylene, random polypropylene, high density polyethylene (HDPE), medium density polyethylene, low density polyethylene (LDPE), and linear low density polyethylene ( LLDPE) is preferred.
  • the white layer preferably contains a polyethylene resin as a main component.
  • the density of the polyethylene resin 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 , and still more preferably 0 .880 g / cm 3 to 0.915 g / cm 3 .
  • the white layer 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 white layer includes a polyethylene resin as a main component, the polyethylene resin preferably includes a low density polyethylene.
  • the base material layer can sufficiently have heat resistance, solvent resistance, and flexibility, and the surface protective sheet of the present invention can be more easily wound into a roll. It becomes possible.
  • the content ratio of the polyolefin resin in the white layer is preferably 60% by weight or more, more preferably 70% by weight or more, further preferably 80% by weight or more, and particularly preferably 85% by weight or more. Yes, most preferably 90% by weight or more.
  • Such polyolefin resin may use only 1 type, and may use 2 or more types.
  • 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 resin component forming the black layer is preferably a polyolefin resin, more preferably a propylene polymer or an ethylene polymer.
  • Specific examples of the resin component forming the black layer include homopolypropylene, block polypropylene, random polypropylene, high density polyethylene (HDPE), medium density polyethylene, low density polyethylene (LDPE), and linear low density polyethylene ( LLDPE) is preferred.
  • the black layer preferably contains a polyethylene resin as a main component.
  • the density of the polyethylene resin 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 , and still more preferably 0 .880 g / cm 3 to 0.915 g / cm 3 .
  • the black layer 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 includes a polyethylene resin as a main component, the polyethylene resin preferably includes a low density polyethylene and a linear low density polyethylene.
  • the base material layer can have sufficient heat resistance, solvent resistance, and flexibility, and the surface protective sheet of the present invention is rolled. It becomes possible to wind it up more easily.
  • the content of the polyolefin resin in the black layer is preferably 60% by weight or more, more preferably 70% by weight or more, still more preferably 80% by weight or more, and particularly preferably 85% by weight or more. Yes, most preferably 90% by weight or more.
  • Such polyolefin resin may use only 1 type, and may use 2 or more types.
  • 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 base material layer preferably contains a light stabilizer.
  • a light stabilizer When the base material layer contains a light stabilizer, sufficient weather resistance can be imparted to the surface protective sheet of the present invention.
  • any appropriate light stabilizer can be adopted as long as the effects of the present invention are not impaired.
  • a light stabilizer for example, a hindered amine light stabilizer (HALS) is preferably exemplified.
  • HALS hindered amine light stabilizer
  • the content ratio of the light stabilizer is preferably 0.10% by weight or more, more preferably 0% with respect to the total weight of the surface protective sheet of the present invention. 20 wt% to 0.64 wt%, more preferably 0.30 wt% to 0.60 wt%, and particularly preferably 0.34 wt% to 0.55 wt%.
  • the base material layer includes a light stabilizer, if the content ratio of the light stabilizer is within the above range with respect to the total weight of the surface protective sheet of the present invention, the surface protective sheet of the present invention is more sufficient. Weather resistance can be imparted.
  • 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 processing such as embossing and uneven processing, a method of containing a fatty acid derivative, and the like. Only one kind of such fatty acid derivative may be used, or two or more kinds thereof may be used.
  • 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.
  • styrene thermoplastic elastomer examples include hydrogenated styrene / butadiene rubber (HSBR), a styrene block copolymer or a hydrogenated product thereof.
  • HSBR hydrogenated styrene / butadiene rubber
  • 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 styrene content in the styrenic thermoplastic elastomer is preferably 1 to 40% by weight, more preferably 5 to 40% by weight, Preferably, it is 7 to 30% by weight, more preferably 9 to 20% by weight, particularly preferably 9 to 15% by weight, and most preferably 9 to 13% by weight.
  • styrene content decreases, there is a risk that adhesive residue due to insufficient cohesive force of the adhesive layer is likely to occur.
  • 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 softening point of the tackifier is preferably 100 ° C. or higher, more preferably 105 ° C. or higher, and further preferably 110 ° C. or higher, in that the effect of the present invention can be expressed sufficiently. Most preferably, it is 115 degreeC or more.
  • the upper limit value of the softening point is, for example, preferably 300 ° C. or lower, more preferably 250 ° C. or lower, and further preferably 200 ° C. or lower.
  • 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 initial adhesion force to the SUS430BA plate at 180 ° peel at each of the tensile speeds of 0.3 m / min, 1 m / min, 10 m / min, and 30 m / min was measured as follows. That is, the initial adhesive strength was measured according to JIS-Z-0237 (2000). Specifically, an SUS430BA plate was used as an adherend, the surface of the SUS430BA plate was washed with toluene, a 2 kg roller was reciprocated once, and an evaluation sample was pressure-bonded.
  • an SUS430BA plate was used as an adherend, the surface of the SUS430BA plate was washed with toluene, a 2 kg roller was reciprocated once, and an evaluation sample was pressure-bonded. Using a machine (manufactured by Shimadzu Corporation, Autograph), the tensile speed was set to the above speed, and the storage adhesive strength was measured at 180 ° peel. At this time, the measurement environment was a temperature of 23 ° C./humidity of 50%.
  • the adhesive strength at 180 ° peel at a tensile speed of 10 m / min after a 750 hour sunshine weatherometer test after being attached to a SUS430BA plate was measured as follows.
  • the surface protection sheet was cut into a strip shape having a width of 20 mm to prepare an evaluation sample.
  • UVA ultraviolet absorber
  • HALS hindered amine light stabilizer
  • a tackifier C5 hydrogenated aromatic petroleum resin, manufactured by Idemitsu Kosan, trade name: Imabu P140)
  • white pigment titanium oxide, manufactured by Dupont, trade name: Ti-Pure R103
  • HALS hindered amine light stabilizer
  • a tackifier C5 hydrogenated aromatic petroleum resin, Eastman Chemical, trade name: EASTOTAC C115W 18% by weight %
  • Example 14 A surface protective sheet (14) 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 13 except that the thickness of the black layer was changed to 45 ⁇ m.
  • System layer / adhesive layer 20 ⁇ m / 45 ⁇ m / 5 ⁇ m). The results are shown in Table 3.
  • IEMAB P140 C5 hydrogenated aromatic petroleum resin, manufactured by Idemitsu Kosan Co., Ltd.
  • Example 16 A surface protective sheet (16) 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 15 except that the thickness of the black layer was changed to 45 ⁇ m.
  • System layer / adhesive layer 20 ⁇ m / 45 ⁇ m / 5 ⁇ m). The results are shown in Table 3.
  • Example 1 A white layer forming material was obtained in the same manner as in Example 1 except that the composition of the white layer forming material was changed as shown in Table 2. Next, it carried out similarly to Example 1 and the black type
  • a base film (thickness: white color layer / black color system) having a two-layer structure (white color layer / black color layer) by the inflation method using the white color layer formation material and black color layer formation material obtained above. Layer 35 ⁇ m / 25 ⁇ m).
  • Example 2 The white layer forming material was obtained in the same manner as in Example 1 except that the composition of the white layer forming material was changed as shown in Table 2 and the thickness of each layer was changed as shown in Table 2. Next, it carried out similarly to Example 1 and the black type
  • a base film (thickness: white color layer / black color system) having a two-layer structure (white color layer / black color layer) by the inflation method using the white color layer formation material and black color layer formation material obtained above. Layer 40 ⁇ m / 30 ⁇ m).
  • Example 3 A white layer forming material was obtained in the same manner as in Example 1 except that the composition of the white layer forming material was changed as shown in Table 2. Next, it carried out similarly to Example 1 and the black type
  • a base film (thickness: white color layer / black color system) having a two-layer structure (white color layer / black color layer) by the inflation method using the white color layer formation material and black color layer formation material obtained above. Layer 35 ⁇ m / 35 ⁇ m).
  • the surface protective sheet of the present invention is a surface protective sheet including a base material layer and an adhesive layer, and the adhesive force in the state of being attached to an adherend is reasonably high enough.
  • the adhesive strength at the time of peeling after sticking to the adherend is an appropriate size, and therefore it can be easily peeled off from the adherend with a slight force, and further, at a relatively high temperature. An increase in adhesive strength when exposed to an environmental load of long-term storage is suppressed, and in addition, sufficient weather resistance is provided.
  • 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.

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 présente une augmentation de son pouvoir adhésif lorsqu'elle est exposée aux conditions environnementales de l'entreposage à long terme dans des conditions de températures relativement élevées et qui présente une résistance aux intempéries appropriée, un pouvoir adhésif suffisamment important lorsqu'elle est appliquée sur une partie adhérée et un degré modéré de pouvoir adhésif lorsqu'on la décolle après qu'elle ait été appliquée sur la partie adhérée, et qui peut donc être facilement enlevée de la partie adhérée avec un minimum de force. La 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. Le pouvoir adhésif de départ (P) par rapport à une feuille SUS430BA soumise à un décollement à 180˚ à une vitesse d'arrachement de 0,3m/min est d'au moins 2,0N/20mm. Le pouvoir adhésif de départ maximum le plus élevé (Q) (N/20mm) parmi les pouvoirs adhésifs de départ par rapport à une feuille SUS430BA soumise à un décollement à 180˚ respectivement à une vitesse d'arrachement de 0,3m/min, 1m/min, 10m/min, et 30m/min est au maximum égal à 150% de P.
PCT/JP2013/052143 2012-02-15 2013-01-31 Feuille de protection de surface WO2013121888A1 (fr)

Applications Claiming Priority (8)

Application Number Priority Date Filing Date Title
JP2012-030034 2012-02-15
JP2012030034 2012-02-15
CN201210036165 2012-02-15
CN201210036165.5 2012-02-15
CN2012103693402A CN103254826A (zh) 2012-02-15 2012-09-27 表面保护片
JP2012213351A JP2013189006A (ja) 2012-02-15 2012-09-27 表面保護シート
CN201210369340.2 2012-09-27
JP2012-213351 2012-09-27

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Publication Number Publication Date
WO2013121888A1 true WO2013121888A1 (fr) 2013-08-22

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5469156U (fr) * 1977-10-27 1979-05-16
JPS63106737U (fr) * 1986-12-26 1988-07-09
JPH06271821A (ja) * 1993-03-23 1994-09-27 Lintec Corp 再剥離型粘着保護テープ
JPH09118864A (ja) * 1995-10-24 1997-05-06 Sekisui Chem Co Ltd 表面保護フィルムの製造方法
JP2001348548A (ja) * 2000-06-06 2001-12-18 Nichiban Co Ltd 表面保護粘着シート及びそのためのゴム系粘着剤組成物
JP2009241338A (ja) * 2008-03-31 2009-10-22 Dainippon Printing Co Ltd プロテクトフィルム
JP2011236358A (ja) * 2010-05-12 2011-11-24 Nitto Denko Corp 表面保護フィルム

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5469156U (fr) * 1977-10-27 1979-05-16
JPS63106737U (fr) * 1986-12-26 1988-07-09
JPH06271821A (ja) * 1993-03-23 1994-09-27 Lintec Corp 再剥離型粘着保護テープ
JPH09118864A (ja) * 1995-10-24 1997-05-06 Sekisui Chem Co Ltd 表面保護フィルムの製造方法
JP2001348548A (ja) * 2000-06-06 2001-12-18 Nichiban Co Ltd 表面保護粘着シート及びそのためのゴム系粘着剤組成物
JP2009241338A (ja) * 2008-03-31 2009-10-22 Dainippon Printing Co Ltd プロテクトフィルム
JP2011236358A (ja) * 2010-05-12 2011-11-24 Nitto Denko Corp 表面保護フィルム

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