WO2013121847A1 - Feuille de protection de surface - Google Patents

Feuille de protection de surface Download PDF

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Publication number
WO2013121847A1
WO2013121847A1 PCT/JP2013/051370 JP2013051370W WO2013121847A1 WO 2013121847 A1 WO2013121847 A1 WO 2013121847A1 JP 2013051370 W JP2013051370 W JP 2013051370W WO 2013121847 A1 WO2013121847 A1 WO 2013121847A1
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WO
WIPO (PCT)
Prior art keywords
layer
adhesive
weight
white
black
Prior art date
Application number
PCT/JP2013/051370
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English (en)
Japanese (ja)
Inventor
公平 武田
生島　伸祐
二郎 山戸
Original Assignee
日東電工株式会社
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Publication of WO2013121847A1 publication Critical patent/WO2013121847A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/302—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (co)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
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/29—Laminated material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2274/00—Thermoplastic elastomer material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/402—Coloured
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/712—Weather resistant
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2405/00—Adhesive articles, e.g. adhesive tapes
    • 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
    • C09J2423/00—Presence of polyolefin
    • C09J2423/006—Presence of polyolefin 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.
  • the present invention is, for example, when a member such as a metal plate, a painted metal plate, an aluminum sash, a resin plate, a decorative steel plate, a vinyl chloride laminated steel plate, or a glass plate is transported, processed, or cured.
  • the present invention relates to a surface protective sheet that can be used for applications such as sticking to a surface for protection.
  • the characteristics required for the surface protective sheet include that the surface protective sheet does not float or peel off after being attached to the adherend, and that the adhesive layer does not remain on the adherend when it is peeled off.
  • the surface protection sheet attached to the adherend is subjected to harsh conditions such as high temperature or outdoor exposure before the surface protection sheet is peeled off, Even more advanced characteristics are required for the required characteristics.
  • acrylic pressure-sensitive adhesives rubber-based pressure-sensitive adhesives mainly composed of natural rubber, polyisobutylene, and the like have been widely used for the pressure-sensitive adhesive layers of commonly used surface protective sheets.
  • ethylene-vinyl acetate copolymer (EVA) adhesive styrene-butadiene-styrene block copolymer (SBS) adhesive, styrene-isobutylene-styrene block copolymer (SIS) adhesive, etc.
  • EVA ethylene-vinyl acetate copolymer
  • SBS styrene-butadiene-styrene block copolymer
  • SIS styrene-isobutylene-styrene block copolymer
  • An acrylic pressure-sensitive adhesive has an extremely large increase in adhesion to an adherend made of a polar plastic material such as polyvinyl chloride, acrylic, or polycarbonate. For this reason, when peeling after sticking to such an adherend, a very large peel force is required, the workability of the peel becomes extremely poor, and the adhesive remains on the adherend after peeling. There is a problem that will occur.
  • a method for solving such a problem a method in which a surfactant is contained in an adhesive is known. However, in such a method, the surfactant remains on the surface of the adherend after peeling. There is a drawback that it will. If the surfactant remains on the surface of the adherend, there arises a problem that repelling occurs when printing on the surface.
  • the adherend when a surfactant is contained in the adhesive, when the adherend is made of a polar plastic material such as polyvinyl chloride, acrylic, polycarbonate, etc., the effect of suppressing the increase in the adhesive force to the adherend is reduced. Problem arises.
  • EVA adhesives have the same problems as acrylic adhesives, and when the surface of the adherend is rough, the initial adhesive force is small, and if peeled off after sticking, natural peeling will occur. There is a problem that it occurs.
  • a method for solving such a problem a method for devising the composition of the pressure-sensitive adhesive and a method for heating at the time of sticking are known. However, such a method does not solve the problem sufficiently.
  • the SBS adhesive and the SIS adhesive contain a diene block polymer, there is a problem that the weather resistance is inferior. If the weather resistance is poor, the pressure-sensitive adhesive deteriorates over time.
  • a method for solving such a problem a method of containing an antiaging agent or an ultraviolet absorber is known. However, such a method does not solve the problem sufficiently.
  • a method for producing a surface protective sheet by co-extrusion forming a pressure-sensitive adhesive layer made of a thermoplastic elastomer and a base material layer made of a polyolefin-based resin has been studied (for example, see Patent Document 1 and Patent Document 2).
  • these surface protective sheets also have a problem that the weather resistance is not sufficient.
  • the object of the present invention is very excellent in weather resistance, can suppress the increase in adhesive strength over time, can reduce the amount of plasticizer transferred from the adherend, and suppress the decrease in cohesive strength of the adhesive over time
  • Another object of the present invention is to provide a surface protective sheet that can prevent adhesive residue on the adherend after being peeled off after sticking.
  • the surface protective sheet of the present invention is A surface protective sheet in which an adhesive layer is formed on one side of the base material layer,
  • the adhesive layer includes a styrene resin,
  • the increase rate of the adhesive strength with respect to the initial adhesive strength when left at 40 ° C. for 3 months is 2 times or less for any of the polyvinyl chloride plate, the matte acrylic plate and the melamine plate.
  • the base material layer includes at least two layers of a white layer and a black layer.
  • the pressure-sensitive adhesive layer comprises a compound A having an aliphatic double bond and having a bromine number of 15 or less according to JIS-K-2435-1 with respect to the styrene resin. Contains weight percent.
  • the present invention has excellent weather resistance, can suppress an increase in adhesive strength over time, can reduce the amount of plasticizer transferred from the adherend, and suppress a decrease in cohesive strength of the adhesive over time
  • the surface protection sheet which can prevent the adhesive residue of the adhesive to the to-be-adhered body after peeling after sticking can be provided.
  • an adhesive layer is formed on one side of the base material layer.
  • the base material layer can contain any appropriate resin.
  • the base material layer preferably contains a polyolefin resin.
  • the content ratio of the polyolefin resin in the base material layer is preferably 60% by weight or more, more preferably 70% by weight or more, further preferably 80% by weight or more, particularly preferably 85% by weight or more, and most preferably 90% by weight. That's it.
  • Such polyolefin resin may use only 1 type, and may use 2 or more types.
  • any appropriate polyolefin resin can be adopted as the polyolefin resin contained in the base material layer, but from the viewpoint of film formation stability, incineration, etc., a propylene polymer such as polypropylene; low density polyethylene (LDPE) Ethylene-based polymers such as linear low density polyethylene (LLDPE) are preferred.
  • a propylene polymer such as polypropylene; low density polyethylene (LDPE)
  • LDPE low density polyethylene
  • LLDPE linear low density polyethylene
  • the density of the ethylene-based polymer that may be contained in the substrate layer is preferably, 0.88 ⁇ 0.93g / cm 3, more preferably 0.895 ⁇ 0.920g / cm 3.
  • the base material layer preferably includes at least two layers of a white layer and a black layer. Thereby, it can be set as the surface protection sheet excellent in the weather resistance.
  • the white layer is a layer showing a white color tone.
  • the whiteness specified by JIS-L-1015 is preferably 60% or more, more preferably 70% or more, still more preferably 80% or more, Particularly preferably, it is 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 is preferably 0.1 to 50% by weight, more preferably 1 to 30% by weight, based on the resin component forming the white layer. More preferably, it is 5 to 20% by weight.
  • the resin component forming the white layer is preferably a polyolefin resin, more preferably at least one selected from a propylene polymer and an ethylene polymer, and more preferably a density of 0.88 to 0.93 g. / Cm 3 ethylene-based polymer.
  • group layer a polypropylene, a low density polyethylene (LDPE), and a linear low density polyethylene (LLDPE) are mentioned preferably.
  • the content 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, particularly preferably 85% by weight or more, and most preferably 90% by weight. That's it.
  • 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 1 to 50 ⁇ m, more preferably 3 to 40 ⁇ m, still more preferably 5 to 30 ⁇ m, and particularly preferably 10 to 30 ⁇ 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 is preferably 0.01 to 10% by weight, more preferably 0.1 to 5% by weight, based on the resin component forming the black layer. More preferably, it is 0.5 to 3% by weight.
  • the resin component forming the black layer is preferably a polyolefin resin, more preferably at least one selected from a propylene polymer and an ethylene polymer, and more preferably a density of 0.88 to 0.93 g. / Cm 3 ethylene-based polymer.
  • a resin component which forms a black type layer a polypropylene, low density polyethylene (LDPE), and linear low density polyethylene (LLDPE) are mentioned preferably.
  • 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, particularly preferably 85% by weight or more, and most preferably 90% by weight. That's it.
  • 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 1 to 100 ⁇ m, more preferably 5 to 70 ⁇ m, still more preferably 10 to 60 ⁇ m, and particularly preferably 20 to 50 ⁇ m.
  • the base material layer may contain any appropriate additive for the purpose of preventing deterioration.
  • additives include antioxidants; UV absorbers; light stabilizers such as hindered amine light stabilizers; antistatic agents; fillers such as calcium oxide, magnesium oxide, silica, zinc oxide, and titanium oxide. Pigments, anti-scratch agents, lubricants, anti-blocking agents, foaming agents, and polyethyleneimine.
  • any appropriate thickness can be adopted as the thickness of the base material layer depending on the purpose.
  • Such a thickness is preferably 20 to 300 ⁇ m, more preferably 30 to 250 ⁇ m, and still more preferably 40 to 200 ⁇ m.
  • the back surface side of the base material layer may be subjected to uneven processing for the purpose of imparting slip resistance and handy cut property. Furthermore, you may form various functional layers, such as a printing layer, in the back side of a base material layer.
  • the adhesive layer is a styrene resin layer and contains a styrene resin.
  • the content of the styrenic resin in the adhesive layer is preferably 50% by weight or more, more preferably 60% by weight or more, still more preferably 70% by weight or more, particularly preferably 80% by weight or more, and most preferably 90% by weight or more. It is. Only one kind of such styrenic resin may be used, or two or more kinds may be used.
  • the styrenic resin is preferably a hydrogenated product of A / B / A or a mixture of A / B / A and A '/ B'.
  • a and A ' are polymer blocks made of styrenic monomers
  • B and B' are polymer blocks made of conjugated dienes.
  • the molecular weight of the polymer block composed of styrene monomer is preferably 1,000 to 1,000,000, more preferably 2,000 to 100,000.
  • the glass transition temperature of the polymer block made of a styrene monomer is preferably 20 ° C. or higher.
  • the molecular weight of the polymer block composed of conjugated diene is preferably 1,000 to 1,000,000, more preferably 10,000 to 300,000.
  • the glass transition temperature of the polymer block made of conjugated diene is preferably ⁇ 20 ° C. or lower.
  • styrene monomer any appropriate monomer having a styrene structure can be adopted.
  • examples of such styrenic monomers include vinyl styrene, vinyl xylene, ethyl styrene, isopropyl styrene, ⁇ -methyl styrene, and the like. Only one type of styrene monomer may be used, or two or more types may be used.
  • conjugated diene any appropriate monomer having a conjugated diene structure can be adopted.
  • conjugated dienes include butadiene and isoprene. Only one conjugated diene may be used, or two or more conjugated dienes may be used.
  • the hydrogenation in the styrene-based resin is preferably in a state where the polymer block made of conjugated diene is selectively hydrogenated.
  • the degree of hydrogenation of the polymer block composed of conjugated diene in the styrene-based resin is preferably 60% by weight or more, more preferably 80% by weight or more based on the entire conjugated diene component.
  • the degree of hydrogenation of the polymer block composed of conjugated diene in the styrene-based resin is less than 60% by weight based on the entire conjugated diene component, there is a possibility that sufficient anti-tearability cannot be expressed.
  • styrene resins can be mixed for the purpose of adjusting adhesiveness and the like within a range not impairing the object of the present invention.
  • the adhesive layer preferably contains a compound A having an aliphatic double bond and a bromine number according to JIS-K-2435-1 of 15 or less.
  • the content ratio of Compound A in the pressure-sensitive adhesive layer is preferably 20 to 400% by weight, more preferably 20 to 300% by weight, still more preferably 20 to 150% by weight, based on the styrene-based resin in the pressure-sensitive adhesive layer. Particularly preferred is 30 to 150% by weight.
  • the content rate of the compound A in an adhesive layer is less than 20 weight% with respect to the styrene resin in an adhesive layer, there exists a possibility that the initial adhesiveness with respect to a to-be-adhered body may worsen.
  • the content ratio of the compound A in the pressure-sensitive adhesive layer exceeds 400% by weight with respect to the styrene resin in the pressure-sensitive adhesive layer, the affinity for the adherend becomes too high and the peeling after long-term storage may be heavy. In addition, heat resistance and weather resistance may be deteriorated.
  • the bromine number of compound A according to JIS-K-2435-1 is 15 or less, preferably 1-10. If the bromine number of Compound A according to JIS-K-2435-1 is greater than 15, the affinity for the adherend may be increased, the adhesive strength over time may increase, or the substance may migrate from the adherend. There is a risk that the amount of the plasticizer to be increased or the cohesive strength of the pressure-sensitive adhesive will decrease with time, and the adhesive residue on the adherend after peeling after sticking may increase .
  • Compound A is preferably a tackifier or softener. Only one type of compound A may be used, or two or more types may be used.
  • 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.
  • softeners include low molecular weight diene polymers, polyisobutylene, hydrogenated polyisoprene, hydrogenated polybutadiene, process oils such as naphthenes and aromas, plasticizers such as dioctyl phthalate and dioctyl adipate, and aromatic water.
  • Additive resins and derivatives thereof. Examples of such derivatives include those having an OH group or a COOH group at one or both ends.
  • hydrogenated polybutadiene diol, hydrogenated polybutadiene monool, hydrogenated polyisoprene diol, water 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 5,000 to 100,000, more preferably 10,000 to 50,000.
  • the adhesive layer for the purpose of controlling adhesive properties, etc., for example, other softeners, olefin resins, silicone polymers, liquid acrylic copolymers, other tackifiers, aging, etc.
  • Additives such as inhibitors, hindered amine light stabilizers, ultraviolet absorbers, polyethyleneimine, fatty acid amides, phosphate esters, fillers and pigments (eg calcium oxide, magnesium oxide, silica, zinc oxide, titanium oxide) It can be added appropriately.
  • 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.
  • the thickness of the adhesive layer may be appropriately set to any appropriate thickness according to the required adhesive strength.
  • the thickness of the adhesive layer is preferably 1 to 50 ⁇ m, more preferably 2 to 40 ⁇ m, and still more preferably 5 to 20 ⁇ m.
  • the styrene resin before hydrogenation can be produced by any appropriate method.
  • a production method for example, living polymerization of a styrenic monomer is carried out using sec-butyllithium or the like in an inert hydrocarbon solvent (for example, cyclohexane, etc.), and then conjugated diene is added to styrene.
  • a diblock structure of a polymer block composed of a monomer and a polymer block composed of a conjugated diene, and if necessary, a styrene monomer is further added to form a triblock structure.
  • Arbitrary appropriate methods can be employ
  • a styrenic resin is dissolved in an inert hydrocarbon solvent (for example, cyclohexane, etc.), cobalt or nickel reduced with a catalyst such as alkylaluminum is added, and 25 to 50 is added.
  • an inert hydrocarbon solvent for example, cyclohexane, etc.
  • cobalt or nickel reduced with a catalyst such as alkylaluminum
  • 25 to 50 is added.
  • Examples thereof include a method of reacting under a pressure for about 10 to 60 minutes using about 5 to 40 kg / cm 3 of hydrogen at a temperature of about ° C.
  • the rate of increase of the adhesive strength with respect to the initial adhesive strength when left at 40 ° C. for 3 months is less than twice that of any of the polyvinyl chloride plate, the matte acrylic plate and the melamine plate. .
  • the rate of increase is preferably 1.8 times or less, more preferably 1.6 times or less, and even more preferably 1.5 times or less.
  • the weather resistance is very excellent, the increase in adhesive strength over time can be suppressed, the amount of plasticizer that migrates from the adherend can be reduced, and the adhesive aggregates over time. It is possible to provide a surface protective sheet that can suppress a decrease in force and can prevent adhesive residue from remaining on an adherend after peeling after sticking.
  • the measuring method of adhesive force is measured based on the below-mentioned method.
  • the rate of increase of the adhesive strength with respect to the initial adhesive strength when left at 50 ° C. for 1 month is preferably twice that of any of the polyvinyl chloride plate, the matte acrylic plate and the melamine plate.
  • it is more preferably 1.8 times or less, still more preferably 1.7 times or less, and particularly preferably 1.6 times or less.
  • the rate of increase is within the above range, the weather resistance is very excellent, the increase in adhesive strength over time can be suppressed, the amount of plasticizer that migrates from the adherend can be reduced, and the adhesive aggregates over time. It becomes even more possible to provide a surface protective sheet that can suppress a decrease in force and can prevent adhesive residue from being left on the adherend after peeling.
  • the polyvinyl chloride plate for example, “Sanplate” manufactured by Sankyo Kasei Co., Ltd. can be used.
  • the matte acrylic plate for example, “Acrylite (registered trademark) Silky Mat” manufactured by Mitsubishi Rayon Co., Ltd. can be used.
  • a product name “Melamine baking coating plate” manufactured by PALTEC Co., Ltd. can be used as the melamine plate.
  • the surface protective sheet of the present invention can be obtained by forming a base material layer and an adhesive layer by coextrusion using a forming material for forming the base material layer and a forming material for forming the adhesive layer. .
  • the base material layer includes at least two layers of a white layer and a black color layer, there are two or more forming materials for forming the base material layer.
  • the base material layer and the pressure-sensitive adhesive layer can be obtained by forming the base material layer and the pressure-sensitive adhesive layer in multiple layers by a co-extrusion method using two or more kinds of forming materials that form the base material layer and a forming material that forms the pressure-sensitive adhesive layer.
  • the structure of the surface protective sheet of the present invention is not particularly limited, and any structure of “white layer / black layer / adhesive layer” and “black layer / white layer / adhesive layer” can be adopted. .
  • a base material layer it can also be set as the layer structure of 3 or more layers which formed layers other than a black-type layer and a white-type layer.
  • a configuration such as “transparent resin layer / white color layer / black color layer / adhesive layer” may be employed.
  • the thickness of the white layer and the black layer may be the same, and the thickness may be different (a white layer is thinner than the black layer, and a white layer is thicker than the black layer). May be.
  • the co-extrusion method it can be carried out according to the inflation method, T-die method and the like generally used for film production.
  • the substrate layer and the pressure-sensitive adhesive layer can be subjected to the surface treatment as necessary.
  • the adhesive layer can be protected by temporarily attaching a separator or the like until it is put to practical use.
  • a mold release treatment by adding fatty acid amide or polyethyleneimine to the base material layer for the purpose of forming a wound body that can be easily rewound.
  • a coat layer made of an appropriate release agent such as silicone, long chain alkyl, or fluorine.
  • the black layer side of the obtained black and white bilayer film was subjected to corona treatment, and the treated surface was blended with the polymer 1 obtained in Production Example 1 and various components (see Table 3) as shown in Table 1 and toluene.
  • a pressure-sensitive adhesive composition (solid content of 30% by weight) obtained by dissolving in was applied and dried at 100 ° C. for 5 minutes to prepare a surface protective sheet.
  • the obtained surface protective sheet had a base material layer thickness of 60 ⁇ m and an adhesive layer thickness of 10 ⁇ m.
  • Example 2 White base layer forming material in which 20% by weight of white pigment (manufactured by Dainichi Seika Co., Ltd., HCM2035W) is added to polyethylene (Nippon Polyethylene, Novatec LD-LF547), and polyethylene (Nippon Polyethylene, Novatec LD-LF547) Table 1 shows the base black layer forming material added with 2% by weight of carbon black (manufactured by Mitsubishi Chemical, carbon black “# 45”), the polymer 2 obtained in Production Example 2 and various components (see Table 3). An adhesive layer-forming material obtained by kneading 150 ° C.
  • the pressure-sensitive adhesive composition (solid content 30% by weight) obtained by dissolution was applied and dried at 100 ° C. for 5 minutes to prepare a surface protective sheet.
  • the obtained surface protective sheet had a base material layer thickness of 60 ⁇ m and an adhesive layer thickness of 10 ⁇ m.
  • the pressure-sensitive adhesive composition (solid content 30% by weight) obtained by dissolution was applied and dried at 100 ° C. for 5 minutes to prepare a surface protective sheet.
  • the obtained surface protective sheet had a base material layer thickness of 60 ⁇ m and an adhesive layer thickness of 10 ⁇ m.
  • the white layer side of the obtained black and white bilayer film was subjected to corona treatment, and the treated surface was blended with the polymer 3 obtained in Production Example 3 and various components (see Table 3) as shown in Table 1 and toluene.
  • a pressure-sensitive adhesive composition (solid content of 30% by weight) obtained by dissolving in was applied and dried at 100 ° C. for 5 minutes to prepare a surface protective sheet.
  • the obtained surface protective sheet had a base material layer thickness of 60 ⁇ m and an adhesive layer thickness of 10 ⁇ m.
  • the white layer side of the obtained black and white bilayer film is subjected to corona treatment, and the treated surface is blended with the polymer 1 obtained in Production Example 1 and various components (see Table 3) as shown in Table 1 and toluene.
  • a pressure-sensitive adhesive composition (solid content of 30% by weight) obtained by dissolving in was applied and dried at 100 ° C. for 5 minutes to prepare a surface protective sheet.
  • the obtained surface protective sheet had a base material layer thickness of 60 ⁇ m and an adhesive layer thickness of 10 ⁇ m.
  • the obtained surface protective sheet had a base material layer thickness of 60 ⁇ m and an adhesive layer thickness of 10 ⁇ m.
  • the surface protection sheets obtained in Examples and Comparative Examples were cut into strips having a width of 20 mm to prepare evaluation samples. This sample was pressed against a SUS430BA plate by reciprocating a 2 kg roller, and then put into a sunshine carbon weather meter (product of Suga Test Instruments Co., Ltd.) for 1000 hours, and then from one end of the sample to a length of 100 mm Was peeled in the 180 ° direction at a tensile speed of 0.3 m / min. The above results were evaluated according to the following criteria. The results are shown in Table 1. ⁇ : The sample was not broken and could be peeled off very well. X: The sample was broken in the middle due to deterioration of the substrate, or the adhesive remained on the adherend and was contaminated.
  • the surface protective sheet of the present invention is very excellent in weather resistance, can suppress an increase in adhesive strength over time, can reduce the amount of plasticizer that migrates from the adherend, and the adhesive over time. It can be seen that a decrease in cohesive force can be suppressed and adhesive residue on the adherend after peeling after sticking can be prevented.
  • the surface protective sheet of the present invention is, for example, a member such as a metal plate, a painted metal plate, an aluminum sash, a resin plate, a decorative steel plate, a vinyl chloride laminated steel plate, a glass plate, etc. It can be used for purposes such as attaching to the surface to protect.

Landscapes

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

Abstract

L'invention concerne une feuille de protection de surface : ayant une exceptionnelle résistance aux intempéries ; étant capable de supprimer une augmentation du pouvoir adhérent au cours du temps ; étant capable de réduire la quantité de plastifiant pour le transfert à partir d'une partie adhérée ; étant capable de supprimer une diminution du pouvoir adhérant d'un adhésif au cours du temps ; et étant apte à prévenir des résidus de colle de l'adhésif sur une partie adhérée après qu'il ait été pelé après avoir été attaché. Cette feuille de protection de surface a une couche adhésive formée sur une surface d'une couche de base. La couche adhésive est une couche de résine de styrène et le taux d'augmentation du pouvoir adhérent par rapport au pouvoir adhérent initial quand celle-ci est laissée telle quelle pendant trois mois à 40°C n'est pas supérieure à deux fois celui d'une feuille de chlorure de vinyle, une feuille acrylique mat et une feuille de mélamine.
PCT/JP2013/051370 2012-02-15 2013-01-24 Feuille de protection de surface WO2013121847A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN2012100361373A CN103254812A (zh) 2012-02-15 2012-02-15 表面保护片
CN201210036137.3 2012-02-15

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WO2013121847A1 true WO2013121847A1 (fr) 2013-08-22

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103834315A (zh) * 2012-11-22 2014-06-04 日东电工株式会社 表面保护片
CN103834314A (zh) * 2012-11-22 2014-06-04 日东电工株式会社 表面保护片
KR102607556B1 (ko) * 2018-04-16 2023-11-29 도레이 필름 카코우 가부시키가이샤 적층 필름

Citations (7)

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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
JP2004137457A (ja) * 2002-08-22 2004-05-13 Lintec Corp ポリカーボネート用表面保護フィルム
WO2008065982A1 (fr) * 2006-12-01 2008-06-05 Kuraray Co., Ltd. Adhésif sensible à la pression pour films optiques
JP2009241338A (ja) * 2008-03-31 2009-10-22 Dainippon Printing Co Ltd プロテクトフィルム

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4785733B2 (ja) * 2004-03-19 2011-10-05 リンテック株式会社 自動車ブレーキディスクアンチラストフィルム
JP5557599B2 (ja) * 2010-05-21 2014-07-23 日東電工株式会社 両面粘着シート及びその使用方法

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
JP2004137457A (ja) * 2002-08-22 2004-05-13 Lintec Corp ポリカーボネート用表面保護フィルム
WO2008065982A1 (fr) * 2006-12-01 2008-06-05 Kuraray Co., Ltd. Adhésif sensible à la pression pour films optiques
JP2009241338A (ja) * 2008-03-31 2009-10-22 Dainippon Printing Co Ltd プロテクトフィルム

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