WO2013121846A1 - Feuille de protection de surface - Google Patents

Feuille de protection de surface Download PDF

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Publication number
WO2013121846A1
WO2013121846A1 PCT/JP2013/051369 JP2013051369W WO2013121846A1 WO 2013121846 A1 WO2013121846 A1 WO 2013121846A1 JP 2013051369 W JP2013051369 W JP 2013051369W WO 2013121846 A1 WO2013121846 A1 WO 2013121846A1
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WO
WIPO (PCT)
Prior art keywords
layer
weight
base material
adhesive layer
black
Prior art date
Application number
PCT/JP2013/051369
Other languages
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 date
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Publication of WO2013121846A1 publication Critical patent/WO2013121846A1/fr

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Classifications

    • 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
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • 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
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/51—Elastic
    • 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.
  • a natural rubber pressure-sensitive adhesive in which an appropriate amount of a tackifier or the like is blended with natural rubber or modified natural rubber has been used for a pressure-sensitive adhesive layer of a surface protection sheet that is generally used.
  • a surface protective sheet is not particularly problematic for indoor use.
  • the natural rubber-based pressure-sensitive adhesive has an unsaturated double bond in its structure, and therefore, when exposed outdoors, it causes molecular cleavage by ultraviolet rays. For this reason, when peeling off the surface protection sheet in which the natural rubber-based pressure-sensitive adhesive is used, there arises a problem that the pressure-sensitive adhesive remains on the adherend. Therefore, a surface protective sheet with good weather resistance is desired. Moreover, there exists a problem that it is easy to tear when peeling the surface protection sheet affixed on the adherend.
  • an acrylic pressure-sensitive adhesive having a cohesive force increased by three-dimensionally crosslinking the acrylic copolymer with an isocyanate compound or a methylol compound in order to form an adhesive layer
  • Synthetic rubber adhesives such as polyisobutylene have been proposed.
  • these pressure-sensitive adhesives are solvent-based, there are problems in terms of safety and hygiene of the surface protection sheet, in terms of pollution and economy.
  • An object of the present invention is a surface protective sheet in which an adhesive layer is formed on one side of a base material layer, which has good adhesion to various adherends, excellent anti-tear resistance, and extremely high weather resistance.
  • An object of the present invention is to provide a surface protective sheet that is excellent and has little increase in adhesive force even when used outdoors or stored at high temperatures, and has good peelability when peeled from an adherend.
  • 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 base material layer is a polyolefin resin layer having an initial elastic modulus of 5000 kg / cm 2 or more measured according to JIS-K-7127.
  • the base material layer includes at least two layers of a white layer and a black layer,
  • the adhesive layer is a styrene resin layer having an initial elastic modulus of 1 to 50 kg / cm 2 measured according to JIS-K-7127.
  • the surface protective sheet has an Elmendorf tear strength of 50 g or more.
  • the present invention is a surface protective sheet in which an adhesive layer is formed on one side of a base material layer, has good adhesive strength to various adherends, excellent anti-tearability, and extremely weather resistance. Even when used outdoors or stored at high temperatures, it is possible to provide a surface protective sheet with little increase in adhesive strength and good releasability when peeled from an adherend.
  • an adhesive layer is formed on one side of the base material layer.
  • the base material layer is a polyolefin resin layer having an initial elastic modulus of 5,000 kg / cm 2 or more as measured according to JIS-K-7127.
  • the initial elastic modulus of the base layer preferably 6000kg / cm 2 ⁇ 20000kg / cm 2, more preferably at 6500kg / cm 2 ⁇ 15000kg / cm 2.
  • the base material layer 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.
  • 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 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 having an initial elastic modulus of 1 to 50 kg / cm 2 measured according to JIS-K-7127.
  • the initial elastic modulus of the pressure-sensitive adhesive layer is less than 1 kg / cm 2 , sufficient anti-tear property may not be exhibited.
  • the initial elastic modulus of the adhesive layer exceeds 50 kg / cm 2 , the adhesive layer may become too hard.
  • the initial elastic modulus of the adhesive layer is preferably 3 kg / cm 2 to 40 kg / cm 2 , more preferably 4 kg / cm 2 to 30 kg / cm 2 .
  • the initial elastic modulus of the pressure-sensitive adhesive layer is measured by applying and drying a forming material (pressure-sensitive adhesive composition) for forming the pressure-sensitive adhesive layer on a separator to produce a test piece having only the pressure-sensitive adhesive layer.
  • a forming material pressure-sensitive adhesive composition
  • the adhesive layer 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 for the purpose of controlling adhesive properties, etc., for example, softener, olefin resin, silicone polymer, liquid acrylic copolymer, tackifier, anti-aging agent, hindered amine Additives such as system light stabilizers, UV absorbers, polyethyleneimine, fatty acid amides, phosphate esters, fillers and pigments (for example, calcium oxide, magnesium oxide, silica, zinc oxide, titanium oxide, etc.) are added as appropriate be able to.
  • softener olefin resin, silicone polymer, liquid acrylic copolymer, tackifier, anti-aging agent, hindered amine Additives such as system light stabilizers, UV absorbers, polyethyleneimine, fatty acid amides, phosphate esters, fillers and pigments (for example, calcium oxide, magnesium oxide, silica, zinc oxide, titanium oxide, etc.) are added as appropriate be able to.
  • 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 usually preferably 60% by weight or less, more preferably 50% by weight or less, still more preferably 40% by weight or less, and particularly preferably 30% by weight or less based on the styrene resin.
  • 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 5,000 to 100,000, more preferably 10,000 to 50,000.
  • the amount added can be appropriately set to any appropriate amount, but as the amount added increases, the adhesive residue tends to increase when exposed to high temperatures or outdoors.
  • it is preferably 60% by weight or less, more preferably 50% by weight or less, still more preferably 40% by weight or less, and particularly preferably 30% by weight or less.
  • 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 styrene monomer is carried out using sec-butyllithium or the like in an inert hydrocarbon solvent (for example, cyclohexane, etc.), and then a conjugated diene is added to produce 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 surface protective sheet of the present invention has an Elmendorf tear strength of 50 g or more.
  • Elemendorf tear strength is a value measured according to JIS-P-8116.
  • the surface protection sheet has an Elmendorf tear strength of 50 g or more, a surface protection sheet excellent in anti-tear property can be obtained.
  • 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 the material forming the base material layer and the forming material forming 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 film A is subjected to corona treatment, and on the treated surface, 36% by weight of rosin-based hydrogenated glycerin ester (softening point 85 ° C.) is added to polymer 1 shown in Table 1, 3% by weight of calcium carbonate, phenol-based An anti-aging agent 0.6% by weight was added and dissolved in toluene, and the resulting pressure-sensitive adhesive composition (solid content 60% by weight) was applied to prepare a surface protective sheet.
  • the obtained surface protective sheet had a base material layer thickness of 40 ⁇ m and an adhesive layer thickness of 15 ⁇ m.
  • Example 2 A base-molded polymer material prepared by mixing 60 parts by weight of polypropylene (Idemitsu Petrochemical Co., Ltd., F-744NP) and 40 parts by weight of high-density polyethylene (Tosoh Corp., Nipolon Hard 5700) was prepared.
  • polypropylene Idemitsu Petrochemical Co., Ltd., F-744NP
  • high-density polyethylene Tosoh Corp., Nipolon Hard 5700
  • the black layer side of film B is subjected to corona treatment, and on the treated surface, 20% by weight of an aliphatic petroleum resin (softening point 100 ° C.) is added to polymer 2 shown in Table 1, and an aliphatic petroleum resin (softening point 40 ° C.). 30% by weight and 0.5% by weight of a phenolic anti-aging agent were dissolved in toluene, and the resulting pressure-sensitive adhesive composition (solid content 60% by weight) was applied to prepare a surface protective sheet.
  • the obtained surface protective sheet had a base material layer thickness of 40 ⁇ m and an adhesive layer thickness of 10 ⁇ m.
  • Example 3 A base molding polymer material was prepared by mixing 80 parts by weight of high density polyethylene (Tosoh Corp., Nipolon Hard 5700) and 20 parts by weight of low density polyethylene (Tosoh Corp., Petrocene 225). Substrate white layer forming material to which 20% by weight of a pigment (manufactured by Dainichi Seika Co., Ltd., HCM2035W) is added, carbon black (manufactured by Mitsubishi Chemical, carbon black “# 45”) with polypropylene (Idemitsu Petrochemical Co., Ltd., F-744NP) ) The base black layer forming material to which 2% by weight was added and the adhesive layer forming material obtained by kneading the adhesive composition obtained in Example 2 (excluding toluene) with a kneader at 150 ° C.
  • a pigment manufactured by Dainichi Seika Co., Ltd., HCM2035W
  • carbon black manufactured by Mitsubishi Chemical, carbon black “# 45”
  • Example 4 A base molding polymer material was prepared by mixing 80 parts by weight of high density polyethylene (Tosoh Corp., Nipolon Hard 5700) and 20 parts by weight of low density polyethylene (Tosoh Corp., Petrocene 225). Substrate white layer forming material to which 20% by weight of a pigment (manufactured by Dainichi Seika Co., Ltd., HCM2035W) is added, carbon black (manufactured by Mitsubishi Chemical, carbon black “# 45”) with polypropylene (Idemitsu Petrochemical Co., Ltd., F-744NP) And 2% by weight of the base material black layer forming material was formed into a film by T-die co-extrusion molding (extruder temperature: 200 ° C., die temperature: 200 ° C.).
  • a pigment manufactured by Dainichi Seika Co., Ltd., HCM2035W
  • carbon black manufactured by Mitsubishi Chemical, carbon black “# 45”
  • polypropylene Idemitsu Petrochemical Co., Ltd
  • White layer / black layer 20 ⁇ m / 20 ⁇ m).
  • the black layer side of film C was subjected to corona treatment, and on the treated surface, 33% by weight of an aliphatic petroleum resin (softening point 100 ° C.) was added to polymer 3 shown in Table 1 and dissolved in toluene.
  • a pressure-sensitive adhesive composition (solid content 60% by weight) was applied to prepare a surface protective sheet.
  • the obtained surface protective sheet had a base material layer thickness of 40 ⁇ m and an adhesive layer thickness of 15 ⁇ m.
  • Example 5 The composition corresponding to the polymer 2 shown in Table 1 as an adhesive composition and having a ratio of A / B / A triblock to A / B diblock of 80:20 is mixed with an aliphatic petroleum resin (softening point). (100 ° C.) 42% by weight was added, and a surface protective sheet was prepared in the same manner as in Example 1 except that the pressure-sensitive adhesive composition (solid content 60% by weight) obtained by dissolving in toluene was used. .
  • the obtained surface protective sheet had a base material layer thickness of 40 ⁇ m and an adhesive layer thickness of 15 ⁇ m.
  • a polymer was obtained by performing radical polymerization using a monomer component consisting of 100 parts by weight of butyl acrylate, 10 parts by weight of methyl methacrylate and 2 parts by weight of acrylic acid.
  • This polymer was dissolved in toluene to give a pressure-sensitive adhesive composition (solid content 30% by weight).
  • the pressure-sensitive adhesive composition was the same as in Example 1 except that this pressure-sensitive adhesive was used.
  • the obtained surface protective sheet had a base material layer thickness of 40 ⁇ m and an adhesive layer thickness of 15 ⁇ m.
  • a base-molded polymer material was prepared by mixing 40 parts by weight of high-density polyethylene (manufactured by Tosoh Corporation, Nipolon Hard 5700) and 60 parts by weight of ethylene-vinyl acetate copolymer (EVA) (manufactured by Tosoh Corporation, Ultrasen 515).
  • EVA ethylene-vinyl acetate copolymer
  • a base material white layer forming material in which 20% by weight of a white pigment manufactured by Dainichi Seika Co., Ltd., HCM2035W
  • carbon black Mitsubishi Chemical Co., Ltd., made by Idemitsu Petrochemical Co., Ltd., F-744NP
  • the base black layer forming material added with 2% by weight of carbon black “# 45”) was formed into a film by T-die coextrusion molding (extruder temperature: 200 ° C., die temperature: 200 ° C.).
  • the black layer side of the film D was subjected to corona treatment, and the pressure-sensitive adhesive composition obtained in Example 1 was applied to the treated surface to prepare a surface protective sheet.
  • the obtained surface protective sheet had a base material layer thickness of 40 ⁇ m and an adhesive layer thickness of 15 ⁇ m.
  • Example 3 When the film A in Example 1 was prepared, a white base material and carbon black were not added to the base material, but a single base material layer was prepared only from polypropylene (manufactured by Idemitsu Petrochemical Co., Ltd., F-744NP). A surface protective sheet was produced in the same manner as in Example 1. The obtained surface protective sheet had a base material layer thickness of 40 ⁇ m and an adhesive layer thickness of 15 ⁇ 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 3. ⁇ : 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 has good adhesion to various adherends, excellent anti-tearability, excellent weather resistance, and when used outdoors or stored at high temperatures. Even if it exists, the increase in the adhesive force is little and it turns out that the peelability at the time of peeling from an adherend is favorable.
  • 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.

Abstract

L'invention concerne une feuille de protection de surface ayant une couche adhésive formée sur une surface d'une couche de base, ladite feuille de protection de surface ayant un bon pouvoir adhérent par rapport à diverses parties adhérées, d'excellentes propriétés anti-déchirure, une résistance aux intempéries exceptionnelle et une bonne pelabilité quand elle est pelée à partir d'une partie adhérée, avec une petite augmentation du pouvoir adhérent même quand elle est utilisée en extérieur ou stockée à des températures élevées. Cette feuille de protection de surface a une couche adhésive formée sur une surface d'une couche de base. La couche de base est une couche de résine de polyoléfine avec un module d'élasticité initial d'au moins 5000 kg/cm2, tel que mesuré par JIS-K-7127. La couche de base comprend au moins une couche blanchâtre et une couche noirâtre. La couche adhésive est une couche de résine de styrène avec un module d'élasticité initial de 1-50 kg/cm2, tel que mesuré par JIS-K-7127, et la résistance à la déchirure Elmendorf de la feuille de protection de surface est d'au moins 50 g.
PCT/JP2013/051369 2012-02-15 2013-01-24 Feuille de protection de surface WO2013121846A1 (fr)

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JP6534564B2 (ja) * 2015-06-19 2019-06-26 日東電工株式会社 表面保護フィルム
JP6305468B2 (ja) 2016-07-06 2018-04-04 株式会社ニトムズ 粘着クリーナー

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JPH06271821A (ja) * 1993-03-23 1994-09-27 Lintec Corp 再剥離型粘着保護テープ
JPH07126457A (ja) * 1993-10-29 1995-05-16 Nitto Denko Corp ポリオレフィン系基材フィルム、及び粘着フィルムまたはシート
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JP2005089547A (ja) * 2003-09-16 2005-04-07 Nitto Denko Corp 表面保護シート
JP2007177003A (ja) * 2005-12-27 2007-07-12 Nitto Denko Corp 再剥離用水分散型アクリル系粘着剤組成物及び粘着シート
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WO2011096389A1 (fr) * 2010-02-02 2011-08-11 日本ゼオン株式会社 Composition de résine pour sceller un élément de pile solaire, et module de pile solaire
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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
JPH07126457A (ja) * 1993-10-29 1995-05-16 Nitto Denko Corp ポリオレフィン系基材フィルム、及び粘着フィルムまたはシート
JP2000290622A (ja) * 1999-04-07 2000-10-17 Nitto Denko Corp 粘着テープ用フィルム基材
JP2005089547A (ja) * 2003-09-16 2005-04-07 Nitto Denko Corp 表面保護シート
JP2007177003A (ja) * 2005-12-27 2007-07-12 Nitto Denko Corp 再剥離用水分散型アクリル系粘着剤組成物及び粘着シート
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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