WO2013121848A1 - Feuille de protection de surface - Google Patents

Feuille de protection de surface Download PDF

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Publication number
WO2013121848A1
WO2013121848A1 PCT/JP2013/051371 JP2013051371W WO2013121848A1 WO 2013121848 A1 WO2013121848 A1 WO 2013121848A1 JP 2013051371 W JP2013051371 W JP 2013051371W WO 2013121848 A1 WO2013121848 A1 WO 2013121848A1
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WO
WIPO (PCT)
Prior art keywords
layer
adhesive layer
black
weight
white
Prior art date
Application number
PCT/JP2013/051371
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 WO2013121848A1 publication Critical patent/WO2013121848A1/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
    • C09J153/025—Vinyl aromatic monomers and conjugated dienes modified
    • 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
    • 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
    • B32B2307/542—Shear strength
    • 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.
  • 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.
  • the object of the present invention is a surface that is extremely excellent in weather resistance, has a very small difference in adhesive strength due to temperature change, and can effectively prevent adhesive residue from being adhered to an adherend even if it is peeled off at a high temperature after application. It is to provide a protective sheet.
  • 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 shear storage modulus at 1 Hz of the pressure-sensitive adhesive layer is 2.0 MPa or less at 0 ° C., and the rate of change of the shear storage modulus when heated to 60 ° C. is within 1/100.
  • the base material layer includes at least two layers of a white layer and a black layer.
  • the styrenic resin is a hydrogenated product of a block copolymer of styrene and butadiene.
  • the surface is extremely excellent in weather resistance, has a very small difference in adhesive strength due to temperature change, and can effectively prevent adhesive residue from adhering to the adherend even if peeled off at high temperature after application.
  • a protective sheet 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.
  • 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 styrenic resin is preferably a hydrogenated product of a block copolymer of styrene and butadiene.
  • 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.
  • the shear storage elastic modulus at 1 Hz of the pressure-sensitive adhesive layer is 2.0 MPa or less at 0 ° C., preferably 1.5 MPa or less, more preferably 0.5 to 1.0 MPa. If the shear storage modulus at 1 Hz of the pressure-sensitive adhesive layer is within the above range, the weather resistance is very good, and the difference in pressure-sensitive adhesive force due to temperature changes is extremely small. It is possible to provide a surface protective sheet that can effectively prevent adhesive residue from being left behind.
  • the shear storage modulus at 1 Hz of the pressure-sensitive adhesive layer is such that the rate of change of the shear storage modulus when heated from 0 ° C. to 60 ° C. is within 1/100, preferably within 1/50, more preferably Is within 1/30, particularly preferably within 1/10. If the rate of change of the shear storage modulus when heated from 0 ° C. to 60 ° C. is within the above range, the weather resistance is excellent, and the difference in adhesive strength due to temperature change is extremely small. It is possible to provide a surface protective sheet that can effectively prevent adhesive residue from adhering to the adherend even when peeled.
  • 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.
  • 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.
  • 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 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 can be produced by any appropriate method.
  • the surface protective sheet of the present invention is obtained, for example, by forming a film of the base material layer and the adhesive layer by a coextrusion method using the forming material for forming the base material layer and the forming material for forming the adhesive layer. Can do.
  • 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 and white bilayer film thus obtained is subjected to corona treatment, and the treated surface is blended with the polymer 1 obtained in Production Example 1 and various components as shown in Table 2 and dissolved in toluene.
  • the obtained pressure-sensitive adhesive composition (solid content: 33% by weight) 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 Base material white layer forming material in which 20% by weight of white pigment (manufactured by Dainichi Seika Co., Ltd., HCM2035W) is added to polyethylene (manufactured by Nippon Polyethylene Co., Ltd., Novatec LD-LF547), and polyethylene (manufactured by Nippon Polyethylene Co., Ltd., Novatec LD-LF547)
  • 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 were blended as shown in Table 2.
  • white pigment manufactured by Dainichi Seika Co., Ltd., HCM2035W
  • base black layer forming material added with 2% by weight of carbon black (manufactured by Mitsubishi Chemical, carbon black “# 45”) by T-die coextrusion molding (extruder temperature: 200 ° C., die temperature
  • the black and white bilayer film thus obtained is subjected to corona treatment, and the treated surface is blended with the polymer 3 obtained in Production Example 3 and various components as shown in Table 2 and dissolved in toluene.
  • the obtained pressure-sensitive adhesive composition (solid content: 33% by weight) 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: 33% by weight) 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: 33% by weight) 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: 33% by weight) 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 black and white bilayer film thus obtained is subjected to corona treatment, and on the treated surface, the polymer 2 obtained in Production Example 2 and various components are blended as shown in Table 2 and dissolved in toluene.
  • the obtained pressure-sensitive adhesive composition (solid content: 33% by weight) 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 black and white bilayer film thus obtained is subjected to corona treatment, and the treated surface is blended with the polymer 1 obtained in Production Example 1 and various components as shown in Table 2 and dissolved in toluene.
  • the obtained pressure-sensitive adhesive composition (solid content: 33% by weight) 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 black layer side of the obtained black and white bilayer film is subjected to corona treatment, and on the treated surface, the polymer 4 obtained in Production Example 4 and various components are blended as shown in Table 2, and dissolved in toluene.
  • the obtained pressure-sensitive adhesive composition (solid content: 33% by weight) 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 shear storage modulus at 0 ° C. and 60 ° C. of the pressure-sensitive adhesive layer of the surface protective sheet is a temperature change of ⁇ 60 to 150 ° C. while giving a shear strain of 1 Hz frequency using ARES made by Rheometric Scientific. (Temperature increase rate 5 ° C./min) was given and measured. As a measurement sample, an adhesive layer having a thickness of about 3 mm was prepared and measured.
  • the pressure-sensitive adhesive layer was produced by a casting method using an organic solvent or a heat press method.
  • the measurement of the shear storage elastic modulus of the adhesive layer can be measured by a method such as a method of obtaining by the difference between the shear storage elastic modulus of the surface protective sheet and the shear storage elastic modulus of the base material when these methods cannot be performed. .
  • the results are shown in Table 2.
  • 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 2. ⁇ : 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, the difference in adhesive strength due to temperature change is extremely small, and the adhesive remains on the adherend even if it is peeled off at high temperature after sticking. It turns out that it can prevent effectively.
  • 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 et des différences extrêmement petites dans le pouvoir adhérent dues aux changements de température et étant apte à prévenir efficacement des résidus de colle de l'adhésif sur une partie adhérée, même si celle-ci a été détachée à une température élevée après avoir été attachée. Cette feuille de protection de surface a une couche adhésive formée sur une surface d'une couche de base. La couche adhésive contient une résine de styrène et le module de cisaillement en stockage de la couche adhésive à 1 Hz est de 2,0 MPa ou moins à 0°C et le taux de modification du module de cisaillement en stockage lorsque la couche adhésive a été chauffée à 60°C est dans 1/100.
PCT/JP2013/051371 2012-02-15 2013-01-24 Feuille de protection de surface WO2013121848A1 (fr)

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CN2012100361246A CN103254809A (zh) 2012-02-15 2012-02-15 表面保护片

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Cited By (2)

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WO2016143623A1 (fr) * 2015-03-09 2016-09-15 日東電工株式会社 Feuille adhésive, procédé de production d'élément semi-conducteur lumineux adhésif et procédé de production de dispositif semi-conducteur optique
CN110109201A (zh) * 2018-02-01 2019-08-09 日东电工株式会社 表面保护膜

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JP6417863B2 (ja) * 2014-08-26 2018-11-07 王子ホールディングス株式会社 粘着シート

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WO2008065982A1 (fr) * 2006-12-01 2008-06-05 Kuraray Co., Ltd. Adhésif sensible à la pression pour films optiques
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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
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
JP2005089547A (ja) * 2003-09-16 2005-04-07 Nitto Denko Corp 表面保護シート
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

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016143623A1 (fr) * 2015-03-09 2016-09-15 日東電工株式会社 Feuille adhésive, procédé de production d'élément semi-conducteur lumineux adhésif et procédé de production de dispositif semi-conducteur optique
CN110109201A (zh) * 2018-02-01 2019-08-09 日东电工株式会社 表面保护膜

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