WO2022138113A1 - Surface protective film - Google Patents

Surface protective film Download PDF

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Publication number
WO2022138113A1
WO2022138113A1 PCT/JP2021/044740 JP2021044740W WO2022138113A1 WO 2022138113 A1 WO2022138113 A1 WO 2022138113A1 JP 2021044740 W JP2021044740 W JP 2021044740W WO 2022138113 A1 WO2022138113 A1 WO 2022138113A1
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WO
WIPO (PCT)
Prior art keywords
weight
manufactured
polyol
parts
sensitive adhesive
Prior art date
Application number
PCT/JP2021/044740
Other languages
French (fr)
Japanese (ja)
Inventor
翔悟 佐々木
祐輔 山本
Original Assignee
日東電工株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Publication date
Application filed by 日東電工株式会社 filed Critical 日東電工株式会社
Priority to CN202180086861.4A priority Critical patent/CN116685468A/en
Priority to KR1020237024504A priority patent/KR20230122636A/en
Publication of WO2022138113A1 publication Critical patent/WO2022138113A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/08—Polyurethanes from polyethers
    • 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
    • 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
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/02—Halogenated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
    • C08L81/04—Polysulfides
    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • 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
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • 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
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
    • 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
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/50—Additional features of adhesives in the form of films or foils characterized by process specific features
    • C09J2301/504—Additional features of adhesives in the form of films or foils characterized by process specific features process of pretreatment for improving adhesion of rubber on metallic surfaces

Definitions

  • the present invention relates to a surface protective film.
  • a surface protective film is attached to the optical member and electronic member to prevent surface scratches during processing, assembly, inspection, transportation, etc.
  • Such a surface protective film is peeled off from an optical member or an electronic member when the need for surface protection is eliminated (Patent Document 1).
  • a pressure-sensitive adhesive layer composed of various pressure-sensitive adhesives is known.
  • a urethane-based pressure-sensitive adhesive layer composed of a urethane-based pressure-sensitive adhesive is preferable as the pressure-sensitive adhesive layer provided on the surface protective film attached to the optical member or the electronic member in terms of excellent reworkability, wettability, and transparency. It has been adopted.
  • a one-shot method for producing a urethane pressure-sensitive adhesive by directly reacting a polyol with a polyfunctional isocyanate without using a urethane prepolymer, and a reaction between the urethane prepolymer and the polyfunctional isocyanate are performed.
  • the prepolymer method for manufacturing urethane pressure-sensitive adhesives There are two types of manufacturing methods, the prepolymer method for manufacturing urethane pressure-sensitive adhesives.
  • the one-shot method since a polyol having a number average molecular weight of around 10,000 is used, the crosslink density is increased by direct curing by reaction with polyfunctional isocyanate, and light peelability can be ensured. On the other hand, the one-shot method is not suitable for thickening the film because the viscosity of the pressure-sensitive adhesive solution is low (Patent Document 2).
  • the prepolymer method has a high viscosity of the adhesive solution, so it is suitable for thickening the film.
  • it is difficult to secure light peelability because the crosslink density of the pressure-sensitive adhesive obtained by curing by reaction with polyfunctional isocyanate is low. Therefore, a technique for ensuring light exfoliation by using a polyol having a number average molecular weight of 300 or less in combination has been reported (Patent Document 3).
  • the surface protective film according to the embodiment of the present invention is A surface protective film containing a urethane-based adhesive layer
  • the urethane-based pressure-sensitive adhesive layer is composed of a urethane-based pressure-sensitive adhesive formed from a urethane-based pressure-sensitive adhesive composition.
  • the urethane-based pressure-sensitive adhesive composition contains a urethane prepolymer P, a polyol A, and a polyfunctional isocyanate compound B.
  • the polyol A contains a first polyol A1 having a number average molecular weight Mn of 5000 to 20000 and a second polyol A2 having a number average molecular weight Mn of 300 to 4999.
  • the weight ratio of the first polyol A1 to the second polyol A2 is 1.0 ⁇ (A1 / A2) ⁇ 3.5.
  • the urethane-based pressure-sensitive adhesive composition contains an ionic compound, and the content ratio of the ionic compound to the total amount of the urethane prepolymer P and the polyol A is 0.05% by weight or more. be.
  • the urethane-based pressure-sensitive adhesive composition comprises at least one selected from the group consisting of a fluorine-based additive and a silicone-based additive, and the urethane prepolymer P and the polyol A are added to the total amount.
  • the content ratio of the total amount of the fluorine-based additive and the silicone-based additive is 0.01% by weight or more.
  • the weight ratio of the first polyol A1 to the second polyol A2 is 1.0 ⁇ (A1 / A2) ⁇ 2.0.
  • the peeling force when the urethane-based pressure-sensitive adhesive layer is bonded to a glass plate and peeled from the glass plate at 23 ° C. for 30 minutes at a peeling angle of 180 degrees and a peeling speed of 300 mm / min is determined. It is 0.5 gf / 25 mm to 2.0 gf / 25 mm.
  • the urethane adhesive layer is attached to a glass plate and peeled from the glass plate at 23 ° C. for 24 hours at a peeling angle of 180 degrees and a peeling speed of 0.3 m / min, and then the glass is peeled off.
  • the residual adhesion rate to the plate is 80% or more.
  • the optical member according to the embodiment of the present invention is the one to which the surface protective film according to the embodiment of the present invention is attached.
  • the electronic member according to the embodiment of the present invention has a surface protective film according to the embodiment of the present invention attached.
  • a surface protective film capable of thickening the pressure-sensitive adhesive layer, exhibiting light peelability, and realizing low haze. Further, it is possible to provide an optical member and an electronic member to which such a surface protective film is attached.
  • FIG. 3 is a schematic cross-sectional view of a surface protective film according to a preferred embodiment of the present invention.
  • the surface protective film according to the embodiment of the present invention includes a urethane-based pressure-sensitive adhesive layer.
  • An arbitrary appropriate release liner having releasability may be attached to the adhesive surface side of the urethane-based pressure-sensitive adhesive layer as long as the effects of the present invention are not impaired.
  • the surface protective film according to the embodiment of the present invention preferably has a base material layer and a urethane-based pressure-sensitive adhesive layer.
  • the base material layer may be only one layer or two or more layers.
  • the urethane-based pressure-sensitive adhesive layer may be only one layer or may be two or more layers.
  • the surface protective film of the present invention may have any suitable other layer in addition to the base material layer and the urethane-based pressure-sensitive adhesive layer as long as the effects of the present invention are not impaired.
  • FIG. 1 is a schematic cross-sectional view of a surface protective film according to a preferred embodiment of the present invention.
  • the surface protective film 10 includes a base material layer 1 and an adhesive layer 2.
  • the surface protective film of the present invention may further have any suitable other layer, for example, a release liner, if necessary (not shown).
  • a fatty acid amide, polyethyleneimine, or a long-chain alkyl system is applied to the base material layer. It is possible to add an additive or the like to perform a mold release treatment, or to provide a coat layer made of any suitable release agent such as silicone-based, long-chain alkyl-based, and fluorine-based.
  • Examples of the release liner that can be provided on the adhesive surface side of the urethane adhesive layer include a release liner in which the surface of a substrate (liner substrate) such as paper or plastic film is treated with silicone, or a substrate such as paper or plastic film. Examples thereof include a release liner in which the surface of the (liner base material) is laminated with a polyolefin resin.
  • plastic film as the base material of the release liner examples include polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate film, and polybutylene.
  • plastic film examples include polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate film, and polybutylene.
  • examples thereof include a terephthalate film, a polyurethane film, and an ethylene-vinyl acetate copolymer film.
  • the thickness of the release liner is preferably 1 ⁇ m to 500 ⁇ m, more preferably 3 ⁇ m to 450 ⁇ m, further preferably 5 ⁇ m to 400 ⁇ m, and particularly preferably 10 ⁇ m to 300 ⁇ m.
  • the thickness of the surface protective film according to the embodiment of the present invention can be set to an arbitrary appropriate thickness depending on the intended use. Typically, it is preferably 10 ⁇ m to 300 ⁇ m, more preferably 15 ⁇ m to 250 ⁇ m, still more preferably 20 ⁇ m to 200 ⁇ m, and particularly preferably 25 ⁇ m to 150 ⁇ m.
  • the urethane-based pressure-sensitive adhesive layer can be thickened. Therefore, the thickness of the urethane-based pressure-sensitive adhesive layer contained in the surface protective film of the present invention is preferably 1 ⁇ m to 150 ⁇ m, more preferably 5 ⁇ m to 150 ⁇ m, still more preferably 10 ⁇ m to 150 ⁇ m, still more preferably 20 ⁇ m. It is ⁇ 150 ⁇ m, more preferably 30 ⁇ m to 150 ⁇ m, still more preferably 40 ⁇ m to 150 ⁇ m, still more preferably 50 ⁇ m to 150 ⁇ m, particularly preferably 60 ⁇ m to 150 ⁇ m, and most preferably 65 ⁇ m to 150 ⁇ m. If the urethane-based pressure-sensitive adhesive layer can be thickened in this way, the surface protective film according to the embodiment of the present invention is good for the step when protecting a display having a large step such as an organic EL display. Can follow.
  • the surface protective film according to the embodiment of the present invention can exhibit light peelability.
  • the surface protective film of the present invention is peeled off when the urethane adhesive layer contained therein is bonded to a glass plate and peeled off from the glass plate at a peeling angle of 180 degrees and a peeling speed of 300 mm / min after 30 minutes at 23 ° C.
  • the force is preferably 0.5 gf / 25 mm to 5.0 gf / 25 mm, more preferably 0.5 gf / 25 mm to 4.0 gf / 25 mm, and even more preferably 0.5 gf / 25 mm to 3.0 gf / 25 mm.
  • the surface protective film according to the embodiment of the present invention can exhibit excellent light peeling property.
  • the surface protective film according to the embodiment of the present invention can realize low haze.
  • the surface protective film of the present invention has a haze of the urethane-based pressure-sensitive adhesive layer contained therein, preferably 4.5% or less, more preferably 4.0% or less, still more preferably 3.5% or less. Yes, particularly preferably 3.0% or less, and most preferably 2.5% or less.
  • the surface protective film according to the embodiment of the present invention can realize excellent low haze, and can exhibit excellent inspectability, for example.
  • the surface protective film according to the embodiment of the present invention is peeled from the glass plate at a peeling angle of 180 degrees and a peeling speed of 0.3 m / min 24 hours after the urethane adhesive layer contained therein is attached to the glass plate at 23 ° C.
  • the residual adhesion ratio to the glass plate is preferably 60% or more, more preferably 70% or more, further preferably 80% or more, particularly preferably 85% or more, and most preferably. Is 90% or more. When the residual adhesive ratio is within the above range, the surface protective film according to the embodiment of the present invention can reduce the adhesive residue property.
  • the surface protective film according to the embodiment of the present invention is obtained when the urethane adhesive layer contained therein is attached to a glass plate and peeled from the glass plate at 23 ° C. for 24 hours at a peeling angle of 150 degrees and a peeling speed of 30 m / min.
  • the peeling band voltage is preferably 15 kV or less, more preferably 10 kV or less, further preferably 5 kV or less, particularly preferably 2 kV or less, and most preferably 1 kV or less.
  • the surface protective film according to the embodiment of the present invention can effectively prevent charging at the time of peeling.
  • Urethane adhesive layer ⁇ The urethane-based pressure-sensitive adhesive layer is composed of a urethane-based pressure-sensitive adhesive.
  • the urethane-based pressure-sensitive adhesive is formed from a urethane-based pressure-sensitive adhesive composition. That is, the urethane-based pressure-sensitive adhesive formed from the urethane-based pressure-sensitive adhesive composition forms a layer shape to form a pressure-sensitive adhesive layer.
  • the urethane-based pressure-sensitive adhesive can be defined as being formed from a urethane-based pressure-sensitive adhesive composition. This is because the urethane-based pressure-sensitive adhesive becomes a urethane-based pressure-sensitive adhesive when the urethane-based pressure-sensitive adhesive composition causes a cross-linking reaction or the like by heating or irradiation with ultraviolet rays, so that the urethane-based pressure-sensitive adhesive is directly specified by its structure. Since there are circumstances in which it is impossible and almost impractical (“impossible / impractical circumstances”), urethane is stipulated as “formed from a urethane-based pressure-sensitive adhesive composition”. The system adhesive is properly specified as a "thing”.
  • the thickness of the urethane-based pressure-sensitive adhesive layer is preferably 1 ⁇ m to 150 ⁇ m, more preferably, because the surface protective film of the present invention can be made thicker. It is 5 ⁇ m to 150 ⁇ m, more preferably 10 ⁇ m to 150 ⁇ m, still more preferably 20 ⁇ m to 150 ⁇ m, still more preferably 30 ⁇ m to 150 ⁇ m, still more preferably 40 ⁇ m to 150 ⁇ m, still more preferably 50 ⁇ m to 150 ⁇ m. Particularly preferably, it is 60 ⁇ m to 150 ⁇ m, and most preferably 65 ⁇ m to 150 ⁇ m. If the urethane-based pressure-sensitive adhesive layer can be thickened in this way, the surface protective film according to the embodiment of the present invention is good for the step when protecting a display having a large step such as an organic EL display. Can follow.
  • the urethane-based pressure-sensitive adhesive is formed from a urethane-based pressure-sensitive adhesive composition.
  • a forming method any appropriate forming method can be adopted as long as the effect of the present invention is not impaired.
  • the urethane-based pressure-sensitive adhesive composition is directly applied to an arbitrary suitable base film (for example, the base layer in the surface protection film according to the embodiment of the present invention) and dried or cured.
  • a urethane-based pressure-sensitive adhesive composition formed on the surface (peeling surface) of a release liner by applying the urethane-based pressure-sensitive adhesive composition to the surface (peeling surface) and drying or curing the urethane-based pressure-sensitive adhesive layer is formed on a base film (for example, a book).
  • a method (transfer method) of transferring the urethane-based pressure-sensitive adhesive layer by adhering it to a base material layer in the surface protective film according to the embodiment of the present invention can be mentioned. From the viewpoint of anchoring property of the pressure-sensitive adhesive layer, the direct method can be preferably adopted as a representative.
  • Examples of the method for applying (typically applying) the urethane adhesive layer include a roll coat method, a gravure coat method, a reverse coat method, a kiss coat method, a dip roll coat method, a bar coat method, and a roll brush.
  • Various conventionally known methods such as a method, a spray coating method, a knife coating method, an air knife coating method, a spray coating method, a comma coating method, a direct coating method, and a coating method using a die coater can be appropriately adopted.
  • the urethane-based pressure-sensitive adhesive composition can be dried under heating (for example, by heating to about 60 ° C to 150 ° C), if necessary.
  • a means for curing the urethane-based pressure-sensitive adhesive composition for example, ultraviolet rays, laser rays, ⁇ -rays, ⁇ -rays, ⁇ -rays, X-rays, and electron beams can be appropriately adopted.
  • the urethane-based pressure-sensitive adhesive composition contains a urethane prepolymer P, a polyol A, and a polyfunctional isocyanate compound B.
  • the weight ratio of the total amount of the urethane prepolymer P, the polyol A and the polyfunctional isocyanate compound B in the urethane pressure-sensitive adhesive composition is preferably 50% by weight to 100% by weight, more preferably 70% by weight to 100% by weight. It is by weight%, more preferably 90% by weight to 100% by weight, particularly preferably 95% by weight to 100% by weight, and most preferably 98% by weight to 100% by weight.
  • the equivalent ratio of NCO group to OH group in the urethane prepolymer P and the polyfunctional isocyanate compound B is preferably 1.0 to 2.0, more preferably 1.1 to 1. It is 9, more preferably 1.2 to 1.8, and particularly preferably 1.2 to 1.7.
  • the content ratio of the polyfunctional isocyanate compound B in the urethane-based pressure-sensitive adhesive composition is preferably 2.5 parts by weight to 40 parts by weight, and more preferably 4 parts by weight to 30 parts by weight with respect to 100 parts by weight of the urethane prepolymer. It is a part by weight, more preferably 5 parts by weight to 20 parts by weight, and particularly preferably 6 parts by weight to 15 parts by weight.
  • the urethane-based pressure-sensitive adhesive constituting the urethane-based pressure-sensitive adhesive layer is produced by a one-shot method for producing a urethane pressure-sensitive adhesive by directly reacting a polyol with a polyfunctional isocyanate without using a urethane prepolymer. It is not a urethane-based pressure-sensitive adhesive, but a urethane-based pressure-sensitive adhesive produced by a prepolymer method for producing a urethane pressure-sensitive adhesive by reacting urethane prepolymer P with a polyfunctional isocyanate compound B.
  • the surface protective film of the present invention has a urethane-based pressure-sensitive adhesive layer composed of a urethane-based pressure-sensitive adhesive produced by the prepolymer method in this way, the urethane-based pressure-sensitive adhesive layer can be thickened, for example.
  • the step can be well followed.
  • Urethane prepolymer P is typically a polyurethane polyol, preferably an organic polyisosianate compound (p3) containing a polyester polyol (p1) and a polyether polyol (p2) in the presence or absence of a catalyst. ).
  • a urethane prepolymer available as a commercially available product may be adopted.
  • the urethane prepolymer P may be of only one type or may be two or more types.
  • the number average molecular weight Mn of the urethane prepolymer P is preferably 1000 to 100,000.
  • polyester polyol (p1) any suitable polyester polyol can be used as long as the effect of the present invention is not impaired.
  • examples of such a polyester polyol (p1) include a polyester polyol obtained by reacting an acid component with a glycol component.
  • the acid component include terephthalic acid, adipic acid, azelaic acid, sebatic acid, phthalic anhydride, isophthalic acid, and trimellitic acid.
  • the glycol component include ethylene glycol, propylene glycol, diethylene glycol, butylene glycol, 1,6-hexane glycol, 3-methyl-1,5-pentanediol, 3,3'-dimethylol heptane, and polyoxyethylene glycol.
  • polyester polyol (p1) examples include polyester polyols obtained by ring-opening polymerization of lactones such as polycaprolactone, poly ( ⁇ -methyl- ⁇ -valerolactone) and polyvalerolactone. ..
  • the molecular weight of the polyester polyol (p1) can be from low molecular weight to high molecular weight.
  • the number average molecular weight is preferably 500 to 5000. If the number average molecular weight is less than 500, the reactivity becomes high and gelation may easily occur. If the number average molecular weight exceeds 5000, the reactivity may be lowered, and further, the cohesive force of the polyurethane polyol itself may be reduced.
  • the amount of the polyester polyol (p1) used is preferably 10 mol% to 90 mol% in the polyol constituting the urethane prepolymer P (typically, a polyurethane polyol).
  • any suitable polyether polyol can be used as long as the effect of the present invention is not impaired.
  • examples of such a polyether polyol (p2) include ethylene oxide, propylene oxide, butylene oxide, and tetrahydrofuran using a low molecular weight polyol such as water, propylene glycol, ethylene glycol, glycerin, and trimethylolpropane as an initiator.
  • examples thereof include polyether polyols obtained by polymerizing an oxylan compound.
  • Examples of such a polyether polyol (p2) include a polyether polyol having two or more functional groups such as polypropylene glycol, polyethylene glycol, and polytetramethylene glycol.
  • the molecular weight of the polyether polyol (p2) can be from low molecular weight to high molecular weight.
  • the number average molecular weight is preferably 1000 to 5000. If the number average molecular weight is less than 1000, the reactivity becomes high and gelation may easily occur. If the number average molecular weight exceeds 5000, the reactivity may be low, and the cohesive force of the polyurethane polyol itself may be low.
  • the amount of the polyether polyol (p2) used is preferably 20 mol% to 80 mol% in the polyol constituting the urethane prepolymer P (typically, a polyurethane polyol).
  • polyether polyols are, if necessary, glycols such as ethylene glycol, 1,4-butanediol, neopentyl glycol, butylethylpentanediol, glycerin, trimethylolpropane, and pentaerythritol.
  • glycols such as ethylene glycol, 1,4-butanediol, neopentyl glycol, butylethylpentanediol, glycerin, trimethylolpropane, and pentaerythritol.
  • polyvalent amines such as ethylenediamine, N-aminoethylethanolamine, isophoronediamine, and xylylenediamine.
  • polyether polyol (p2) only a bifunctional polyether polyol may be used, or a polyether having a number average molecular weight of 1000 to 5000 and having at least 3 or more hydroxyl groups in one molecule. Part or all of the polyol may be used. When a part or all of the polyether polyol (p2) having an average molecular weight of 1000 to 5000 and having at least 3 or more hydroxyl groups in one molecule is used, the balance between adhesive strength and removability is balanced. Can be good. In such a polyether polyol (p2), if the number average molecular weight is less than 1000, the reactivity becomes high and there is a possibility that gelation is likely to occur.
  • polyether polyol (p2) when the number average molecular weight exceeds 5000, the reactivity becomes low, and further, the cohesive force of the urethane prepolymer P (typically, polyurethane polyol) itself becomes strong. It may become smaller.
  • the number average molecular weight of such a polyether polyol (p2) is more preferably 2500 to 3500.
  • any suitable organic polyisocyanate compound can be used as long as the effect of the present invention is not impaired.
  • examples of such an organic polyisocyanate compound (p3) include aromatic polyisocyanates, aliphatic polyisocyanates, aromatic aliphatic polyisocyanates, and alicyclic polyisocyanates.
  • aromatic polyisocyanate examples include 1,3-phenylenediocyanate, 4,4'-diphenyldiisocyanate, 1,4-phenylenediocyanate, 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, and 2,6.
  • -Toluene diisocyanate, 4,4'-toluene diisocyanate, 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate benzene, dianisidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4', 4 ′′ -triphenylmethane triisocyanate can be mentioned.
  • aliphatic polyisocyanate examples include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylenediocyanate, 1,3-butylenediocyanate, and dodecamethylene diisocyanate. Examples thereof include 2,4,4-trimethylhexamethylene diisocyanate.
  • aromatic aliphatic polyisocyanate examples include ⁇ , ⁇ '-diisocyanate-1,3-dimethylbenzene, ⁇ , ⁇ '-diisocyanate-1,4-dimethylbenzene, ⁇ , ⁇ '-diisocyanate-1,4-diethylbenzene. , 1,4-Tetramethylxylylene diisocyanate, 1,3-tetramethylxylylene diisocyanate.
  • Examples of the alicyclic polyisocyanate include 3-isocyanate methyl-3,5,5-trimethylcyclohexylisocyanate, 1,3-cyclopentanediisocyanate, 1,3-cyclohexanediisocyanate, 1,4-cyclohexanediisocyanate, and methyl-2. , 4-Cyclohexanediisocyanate, methyl-2,6-cyclohexanediisocyanate, 4,4'-methylenebis (cyclohexylisocyanate), 1,4-bis (isocyanatemethyl) cyclohexane, 1,4-bis (isocyanatemethyl) cyclohexane. ..
  • organic polyisocyanate compound (p3) a trimethylolpropane adduct body, a biuret body reacted with water, and a trimer having an isocyanurate ring can be used in combination.
  • any suitable catalyst can be used as long as the effect of the present invention is not impaired.
  • examples of such a catalyst include tertiary amine compounds and organometallic compounds.
  • tertiary amine compound examples include triethylamine, triethylenediamine, and 1,8-diazabicyclo (5,4,0) -undecene-7 (DBU).
  • organometallic compound examples include tin-based compounds and non-tin-based compounds.
  • tin-based compound examples include dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin dimalate, dibutyltin dilaurate (DBTDL), dibutyltin diacetate, dibutyltin sulfide, tributyltin sulfide, tributyltin oxide, and tributyl.
  • Examples thereof include tin acetate, triethyl tin ethoxide, tributyl tin ethoxide, dioctyl tin oxide, tributyl tin chloride, tributyl tin trichloroacetate and tin 2-ethylhexanoate.
  • non-tin compound examples include titanium compounds such as dibutyl titanium dichloride, tetrabutyl titanate, and butoxytitanium trichloride; lead compounds such as lead oleate, lead 2-ethylhexanoate, lead benzoate, and lead naphthenate.
  • titanium compounds such as dibutyl titanium dichloride, tetrabutyl titanate, and butoxytitanium trichloride
  • lead compounds such as lead oleate, lead 2-ethylhexanoate, lead benzoate, and lead naphthenate.
  • Iron-based compounds such as iron 2-ethylhexanoate and iron acetylacetonate
  • Cobalt-based compounds such as cobalt benzoate and cobalt 2-ethylhexanoate
  • Zinc-based compounds such as zinc naphthenate and zinc 2-ethylhexanoate
  • Zylon-based compounds such as zirconium naphth
  • a catalyst When a catalyst is used in producing a urethane prepolymer P (typically a polyurethane polyol), its reactivity in a system in which two types of polyols, a polyester polyol (p1) and a polyether polyol (p2), are present. Due to the difference in the above, problems such as gelation and turbidity of the reaction solution are likely to occur in a single catalyst system. Therefore, by using two types of catalysts when obtaining the urethane prepolymer P (typically, polyurethane polyol), the reaction rate, the selectivity of the catalyst, and the like can be easily controlled, and these problems can be solved.
  • Examples of the combination of such two types of catalysts include tertiary amine / organic metal-based, tin-based / non-tin-based, and tin-based / tin-based, preferably tin-based / tin-based, and more preferably.
  • the tin 2-ethylhexanoate / dibutyltin dilaurate is preferably less than 1 and more preferably 0.2 to 0.6 by weight. When the compounding ratio is 1 or more, gelation may easily occur due to the balance of catalytic activity.
  • the amount of the catalyst used is polyester polyol (a1), polyether polyol (a2), and organic polyisosianate compound (a3). ), It is preferably 0.01% by weight to 1.0% by weight.
  • the reaction temperature is preferably less than 100 ° C, more preferably 85 ° C to 95 ° C. If the temperature is 100 ° C. or higher, it may be difficult to control the reaction rate and the crosslinked structure, and it may be difficult to obtain a urethane prepolymer P (typically, a polyurethane polyol) having a predetermined molecular weight.
  • urethane prepolymer P typically, polyurethane polyol
  • the reaction temperature is preferably 100 ° C. or higher, more preferably 110 ° C. or higher.
  • the urethane prepolymer P typically, polyurethane polyol
  • a method for producing a urethane prepolymer P for example, 1) a polyester polyol (p1), a polyether polyol (p2), a catalyst, and an organic polyisocyanate compound (p3) are put into a total volume flask. Examples thereof include a method of charging, 2) a method of charging a polyester polyol (p1), a polyether polyol (p2), and a catalyst into a flask and adding an organic polyisocyanate compound (p3) by dropping.
  • the method 2) is preferable in controlling the reaction.
  • any suitable solvent can be used as long as the effect of the present invention is not impaired.
  • a solvent include methyl ethyl ketone, ethyl acetate, toluene, xylene, and acetone.
  • toluene is preferable.
  • polyol A examples include polyester polyols, polyether polyols, polycaprolactone polyols, polycarbonate polyols, and castor oil-based polyols.
  • the polyol A is more preferably a polyester polyol or a polyether polyol.
  • the polyester polyol can be obtained, for example, by an esterification reaction between a polyol component and an acid component.
  • polyol component examples include ethylene glycol, diethylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, and 2-butyl-2-ethyl-1.
  • 3-Propanediol 2,4-diethyl-1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 2-methyl
  • Examples thereof include -1,8-octanediol, 1,8-decanediol, octadecanediol, glycerin, trimethylolpropane, pentaerythritol, hexanetriol and polypropylene glycol.
  • the acid component examples include succinic acid, methylsuccinic acid, adipic acid, piceric acid, azelaic acid, sebacic acid, 1,12-dodecanedioic acid, 1,14-tetradecanedioic acid, dimer acid, 2-methyl-1, 4-Cyclohexanedicarboxylic acid, 2-ethyl-1,4-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, isophthalic acid, terephthalic acid, 1,4-naphthalenedicarboxylic acid, 4,4'-biphereldicarboxylic acid , These acid anhydrides.
  • polyether polyol examples include water, low molecular weight polyols (propylene glycol, ethylene glycol, glycerin, trimethylolpropane, pentaerythritol, etc.), bisphenols (bisphenol A, etc.), dihydroxybenzene (catechol, resorcin, hydroquinone, etc.), etc.
  • polyether polyols obtained by addition polymerization of alkylene oxides such as ethylene oxide, propylene oxide and butylene oxide.
  • specific examples thereof include polyethylene glycol, polypropylene glycol and polytetramethylene glycol.
  • polycaprolactone polyol examples include a caprolactone-based polyester diol obtained by ring-opening polymerization of a cyclic ester monomer such as ⁇ -caprolactone and ⁇ -valerolactone.
  • polycarbonate polyol examples include a polycarbonate polyol obtained by subjecting the above-mentioned polyol component and phosgen to a polycondensation reaction; the above-mentioned polyol component and dimethyl carbonate, diethyl carbonate, diprovyl carbonate, diisopropyl carbonate, dibutyl carbonate, ethylbutyl carbonate, ethylene carbonate, Polycarbonate polyol obtained by ester exchange condensation with carbonic acid diesters such as propylene carbonate, diphenyl carbonate, dibenzyl carbonate; copolymerized polycarbonate polyol obtained by using two or more of the above polyol components in combination; containing various polycarbonate polyols and a carboxyl group.
  • a polycarbonate polyol obtained by subjecting the above-mentioned polyol component and phosgen to a polycondensation reaction
  • Polycarbonate polyol obtained by esterifying a compound Polycarbonate polyol obtained by etherifying a various polycarbonate polyols and a hydroxyl group-containing compound; Obtaining by an ester exchange reaction between various polycarbonate polyols and an ester compound.
  • Polycarbonate-based polycarbonate polyol obtained by a polycondensation reaction between the various polycarbonate polyols and a dicarboxylic acid compound Examples thereof include a copolymerized polyether polycarbonate polyol obtained by copolymerizing and alkylene oxide.
  • castor oil-based polyol examples include castor oil-based polyol obtained by reacting castor oil fatty acid with the above-mentioned polyol component. Specific examples thereof include castor oil-based polyols obtained by reacting castor oil fatty acid with polypropylene glycol.
  • the polyol A contains a first polyol A1 having a number average molecular weight Mn of 5000 to 20000 and a second polyol A2 having a number average molecular weight Mn of 300 to 4999.
  • the effect of the present invention can be further exhibited by the polyol A containing the first polyol A1 having a number average molecular weight Mn of 5000 to 20000 and the second polyol A2 having a number average molecular weight Mn of 300 to 4999.
  • the first polyol A1 may be only one kind or two or more kinds.
  • the second polyol A2 may be only one kind or two or more kinds.
  • the content ratio of the total amount of the first polyol A1 and the second polyol A2 in the polyol A is preferably 80% by weight to 100% by weight, more preferably, in that the effect of the present invention can be more exhibited. It is 90% by weight to 100% by weight, more preferably 95% by weight to 100% by weight, particularly preferably 98% by weight to 100% by weight, and most preferably substantially 100% by weight.
  • the number average molecular weight Mn of the first polyol A1 is 5000 to 20000, preferably 6000 to 18000, more preferably 7000 to 16000, still more preferably 8000 to 15000, and particularly preferably 9000 to 14000. Is. When the number average molecular weight Mn of the first polyol A1 is within the above range, the effect of the present invention can be more exhibited.
  • the number average molecular weight Mn of the second polyol A2 is 300 to 4999, preferably 350 to 4500, more preferably 400 to 4000, still more preferably 500 to 3800, and particularly preferably 700 to 3500. Is. When the number average molecular weight Mn of the second polyol A2 is within the above range, the effect of the present invention can be more exhibited.
  • the weight ratio of the first polyol A1 to the second polyol A2 is preferably 1.0 ⁇ (A1 / A2) ⁇ 3.5, more preferably 1.0 ⁇ (A1 / A2) ⁇ 3. It is 0, more preferably 1.0 ⁇ (A1 / A2) ⁇ 2.5, and particularly preferably 1.0 ⁇ (A1 / A2) ⁇ 2.0. If the weight ratio of the first polyol A1 and the second polyol A2 is within the above range, the effect of the present invention can be more exhibited.
  • the first polyol A1 has preferably 3 to 6 OH groups, more preferably 3 to 5 groups, and further, in that the effect of the present invention can be more exhibited.
  • the number is preferably 3 to 4, and particularly preferably 3.
  • the first polyol A1 contains triol having 3 OH groups, preferably 50% by weight to 100% by weight, and more preferably 70% by weight to 100% by weight, in that the effect of the present invention can be more exhibited. It contains% by weight, more preferably 90% by weight to 100% by weight, particularly preferably 95% by weight to 100% by weight, and most preferably substantially 100% by weight.
  • the second polyol A2 has preferably 3 to 6 OH groups, more preferably 3 to 5 groups, and further, in that the effect of the present invention can be more exhibited.
  • the number is preferably 3 to 4, and particularly preferably 3.
  • the second polyol A2 contains triol having 3 OH groups in an amount of preferably 50% by weight to 100% by weight, more preferably 70% by weight to 100% by weight, in that the effect of the present invention can be more exhibited. It contains% by weight, more preferably 90% by weight to 100% by weight, particularly preferably 95% by weight to 100% by weight, and most preferably substantially 100% by weight.
  • the polyfunctional isocyanate compound B may be only one kind or two or more kinds.
  • polyfunctional isocyanate compound B any suitable polyfunctional isocyanate compound that can be used for the urethanization reaction can be adopted.
  • examples of such a polyfunctional isocyanate compound B include a polyfunctional aliphatic isocyanate compound, a polyfunctional alicyclic isocyanate, and a polyfunctional aromatic isocyanate compound.
  • polyfunctional aliphatic isocyanate compound examples include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,3-butylenediocyanate, dodecamethylene diisocyanate, 2,4.
  • polyfunctional aliphatic isocyanate compound examples include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,3-butylenediocyanate, dodecamethylene diisocyanate, 2,4.
  • Examples thereof include 4-trimethylhexamethylene diisocyanate.
  • polyfunctional alicyclic isocyanate compound examples include 1,3-cyclopentene diisocyanate, 1,3-cyclohexanediisocyanate, 1,4-cyclohexanediisocyanate, isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, and hydrogenated xylylene diisocyanate.
  • examples thereof include hydrogenated tolylene diisocyanate and hydrogenated tetramethylxylylene diisocyanate.
  • polyfunctional aromatic diisocyanate compound examples include phenylenediocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 2,2'-diphenylmethane diisocyanate, and 4,4'-diphenylmethane diisocyanate, 4 , 4'-toluene diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalenediocyanate, xylylene diisocyanate.
  • polyfunctional isocyanate compound B examples include a trimethylolpropane adduct body of various polyfunctional isocyanate compounds as described above, a biuret body reacted with water, and a trimer having an isocyanurate ring. Moreover, you may use these together.
  • the urethane-based pressure-sensitive adhesive composition may contain any suitable other components as long as the effects of the present invention are not impaired.
  • suitable other components include resin components other than urethane prepolymer P and polyol A, cross-linking agents other than polyfunctional isocyanate compound B, cross-linking retarders, ionic compounds, fluorine-based additives, and silicone-based additives.
  • the content ratio of the ionic compound any appropriate content ratio can be adopted as long as the effect of the present invention is not impaired.
  • the content ratio of the ionic compound to the total amount of the urethane prepolymer P and the polyol A is preferably 0.05% by weight or more, more preferably, in terms of further improving the antistatic performance of the surface protective film of the present invention. Is 0.10% by weight to 50% by weight, more preferably 0.20% by weight to 30% by weight, particularly preferably 0.30% by weight to 10% by weight, and most preferably 0.50% by weight. % To 1% by weight.
  • the antistatic performance of the surface protective film of the present invention can be further improved. If the content ratio of the ionic compound to the total amount of the urethane prepolymer P and the polyol A is too small outside the above range, it may not be possible to impart sufficient antistatic performance to the surface protective film of the present invention. If the content ratio of the ionic compound to the total amount of the urethane prepolymer P and the polyol A is too large outside the above range, contamination of the adherend may increase.
  • any appropriate ionic compound can be adopted as long as the effect of the present invention is not impaired.
  • the ionic compound may be only one kind or two or more kinds.
  • the ionic compound is preferably an ionic compound containing at least one selected from an onium cation and a metal cation and a fluoroorganic anion, and an ionic group-containing silicone oligomer, in that the effects of the present invention can be further exhibited.
  • An ionic compound containing at least one selected from an onium cation and a metal cation and a fluoroorganic anion is more preferable in that the appearance of the pressure-sensitive adhesive layer can be improved.
  • the ionic compound may be an ionic liquid.
  • the ionic liquid means a molten salt (ionic compound) that exhibits a liquid at 25 ° C.
  • any appropriate ionic group-containing silicone oligomer can be adopted as long as the effect of the present invention is not impaired.
  • the ionic group-containing silicone oligomer include the trade name “X-40-2450” manufactured by Shin-Etsu Chemical Co., Ltd.
  • any appropriate onium cation can be adopted as long as the effect of the present invention is not impaired.
  • Such onium cations are preferably selected from ammonium cations (nitrogen-containing onium cations), sulfonium cations (sulfur-containing onium cations), and phosphorus-containing onium cations (phosphonium cations) in that the effects of the present invention can be further exhibited. At least one selected, more preferably an ammonium cation.
  • any suitable metal cation can be adopted as long as the effect of the present invention is not impaired.
  • Such metal cations are preferably alkali metal cations such as Li cations, Na cations and K cations in that the effects of the present invention can be further exhibited.
  • any suitable fluoroorganic anion can be adopted as long as the effect of the present invention is not impaired.
  • the fluoroorganic anion may be completely fluorinated (perfluoro) or partially fluorinated.
  • fluoroorganic anions examples include fluorinated arylsulfonates, perfluoroalkanesulfonates, bis (fluorosulfonyl) imides, bis (perfluoroalkanesulfonyl) imides, cyanoperfluoroalkanesulfonylamides, and bis (cyano).
  • perfluoroalkylsulfonate perfluoroalkylsulfonate, bis (fluorosulfonyl) imide, and bis (perfluoroalkanesulfonyl) imide are preferable in that the effects of the present invention can be more exhibited, and more specifically.
  • Is for example, trifluoromethanesulfonate, pentafluoroethanesulfonate, heptafluoropropanesulfonate, nonafluorobutanesulfonate, bis (fluorosulfonyl) imide, bis (trifluoromethanesulfonyl) imide, preferably bis (fluorosulfonyl) imide, It is a bis (trifluoromethanesulfonyl) imide.
  • the ionic compound is more preferably an ionic compound composed of an onium cation and a fluoroorganic anion in that the effects of the present invention can be more exhibited.
  • the onium cation preferably has at least one selected from the structures represented by the general formulas (1) to (4).
  • R a represents a hydrocarbon group having 4 to 20 carbon atoms and may contain a heteroatom
  • Rb and Rc represent hydrogen or a hydrocarbon group having 1 to 16 carbon atoms, which are the same or different, and are heteroatoms. May include. However, when the nitrogen atom contains a double bond, there is no Rc.
  • Rd represents a hydrocarbon group having 2 to 20 carbon atoms and may contain a heteroatom
  • Re, Rf, and Rg are the same or different from hydrogen or 1 carbon atom. It represents 16 hydrocarbon groups and may contain heteroatoms.
  • Rh represents a hydrocarbon group having 2 to 20 carbon atoms and may contain a heteroatom
  • Ri, Rj, and Rk are the same or different from hydrogen or 1 carbon atom. It represents 16 hydrocarbon groups and may contain heteroatoms.
  • Z represents a nitrogen atom, a sulfur atom, or a phosphorus atom
  • Rl, Rm, Rn, and Ro represent a hydrocarbon group having 1 to 20 carbon atoms, which is the same or different, and is hetero. It may contain atoms. However, when Z is a sulfur atom, there is no Ro.
  • Examples of the cation structure represented by the general formula (1) include a pyridinium cation structure, a pyrrolidinium cation structure, a piperidinium cation structure, a cation structure having a pyrroline skeleton, and a cation structure having a pyrrole skeleton.
  • cation represented by the general formula (1) include, for example, 1-ethylpyridinium cation, 1-butylpyridinium cation, 1-hexylpyridinium cation, 1-ethyl-3-methylpyridinium cation, 1-butyl.
  • 1-ethylpyridinium cation, 1-butylpyridinium cation, 1-hexylpyridinium cation, 1-ethyl-3-methylpyridinium cation, 1-ethylpyridinium cation are preferable in that the effect of the present invention can be further exhibited.
  • -Pyridinium cations such as butyl-3-methylpyridinium cation, 1-hexyl-3-methylpyridinium cation, 1-butyl-4-methylpyridinium cation, 1-octyl-4-methylpyridinium cation; 1-ethyl-1- Methylpyrridinium cation, 1-methyl-1-propylpyrrolidinium cation, 1-methyl-1-butylpyrrolidinium cation, 1-methyl-1-pentylpyrrolidinium cation, 1-methyl-1-hexyl Pyridinium cation, 1-methyl-1-heptylpyrrolidinium cation, 1-ethyl-1-propylpyrrolidinium cation, 1-ethyl-1-butylpyrrolidinium cation, 1-ethyl-1-pentylpyrrolidinium Pyridinium cations such as nium cations, 1-ethyl-1-hex
  • Examples of the cation structure represented by the general formula (2) include an imidazolium cation structure, a tetrahydropyrimidinium cation structure, and a dihydropyrimidinium cation structure.
  • cation represented by the general formula (2) include, for example, 1,3-dimethylimidazolium cation, 1,3-diethylimidazolium cation, 1-ethyl-3-methylimidazolium cation, and 1-butyl.
  • 1,3-dimethylimidazolium cation, 1,3-diethylimidazolium cation, 1-ethyl-3-methylimidazolium cation, 1 are preferable in that the effect of the present invention can be further exhibited.
  • a cation having at least one selected from a CH-group) and an allyl group ( CH2 CH- CH2 -group).
  • Examples of the cation structure represented by the general formula (3) include a pyrazolium cation structure and a pyrazolinium cation structure.
  • cation represented by the general formula (3) include, for example, 1-methylpyrazolium cation, 3-methylpyrazolium cation, 1-ethyl-2-methylpyrazolinium cation, 1-ethyl-.
  • Examples of the cation structure represented by the general formula (4) include a tetraalkylammonium cation structure, a trialkylsulfonium cation structure, a tetraalkylphosphonium cation structure, and a part of the above alkyl groups is an alkenyl group, an alkoxyl group, or an epoxy group. Examples include those replaced with.
  • cation represented by the general formula (4) include, for example, tetramethylammonium cation, tetraethylammonium cation, tetrabutylammonium cation, tetrapentylammonium cation, tetrahexylammonium cation, tetraheptylammonium cation, and triethylmethylammonium.
  • Tributylethylammonium cation trimethylpropylammonium cation, trimethyldecylammonium cation, N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium cation, glycidyltrimethylammonium cation, diallyldimethylammonium cation, N, N-dimethyl-N-ethyl-N-propylammonium cation, N, N-dimethyl-N-ethyl-N-butylammonium cation, N, N-dimethyl-N-ethyl-N-pentylammonium cation, N, N- Dimethyl-N-ethyl-N-hexylammonium cation, N, N-dimethyl-N-ethyl-N-heptylammonium cation, N, N-dimethyl-N-ethyl-
  • the ionic compound is preferably an ionic compound containing at least one selected from the above onium cation and the above metal cation and the above fluoroorganic anion, and an ionic group-containing silicone oligomer, and more preferably the above. It is an ionic compound containing at least one selected from the above-mentioned onium cation and the above-mentioned metal cation and the above-mentioned fluoroorganic anion, and more preferably, it is an ionic compound containing the above-mentioned onium cation and the above-mentioned fluoroorganic anion.
  • the ionic compound is preferably preferably 1-hexylpyridinium bis (fluorosulfonyl) imide, 1-ethyl-3-methylpyridinium trifluoromethanesulfonate, 1 -Ethyl-3-methylpyridinium pentafluoroethanesulfonate, 1-ethyl-3-methylpyridinium heptafluoropropanesulfonate, 1-ethyl-3-methylpyridinium nonafluorobutane sulfonate, 1-butyl-3-methylpyridinium trifluoromethanesulfonate, 1-butyl-3-methylpyridinium bis (trifluoromethanesulfonyl) imide, 1-octyl-4-methylpyridinium bis (fluorosulfonyl) imide, 1-methyl-1-propylpyrrolidinium bis (trifluoromethanesulf
  • Riumbis (trifluoromethanesulfonyl) imide methyltrioctylammonium bis (trifluoromethanesulfonyl) imide, and trimethylpropylammonium bis (trifluoromethanesulfonyl) imide.
  • ionic compound a commercially available compound may be used, or a compound synthesized by any appropriate method may be used.
  • ionic liquids include halide methods, hydroxide methods, acid ester methods, complex formation methods, as described in "Ionic Liquids-Forefront and Future of Development-" (published by CMC Publishing). And may be synthesized by a neutralization method or the like.
  • fluorine-based additives When a fluorine-based additive is contained as another component, it is possible to further improve the light peelability and antistatic performance of the surface protective film according to the embodiment of the present invention.
  • any appropriate fluorine-based additive can be adopted as long as the effect of the present invention is not impaired.
  • the fluorine-based additive may be only one kind or two or more kinds.
  • the content ratio of the fluorine-based additive to the total amount of the urethane prepolymer P and the polyol A is preferably 0.01% by weight or more, more preferably 0.03% by weight to 30 parts by weight, and further preferably 0. It is 0.05 parts by weight to 10 parts by weight, and particularly preferably 0.05 parts by weight to 1 part by weight.
  • the content ratio of the fluorine-based additive to the total amount of the urethane prepolymer P and the polyol A is within the above range, it is possible to further improve the light peelability and antistatic performance of the surface protective film according to the embodiment of the present invention. Will be.
  • the content ratio of the total amount of the fluorine-based additive and the silicone-based additive described later to the total amount of the urethane prepolymer P and the polyol A is 0.01% by weight or more. , More preferably 0.03% by weight to 30 parts by weight, still more preferably 0.05 parts by weight to 10 parts by weight, and particularly preferably 0.05 parts by weight to 1 part by weight.
  • fluorine-based additive examples include at least one selected from a fluorine-containing compound, a hydroxyl group-containing fluorine-based compound, and a crosslinkable functional group-containing fluorine-based compound.
  • Examples of the fluorine-containing compound include a compound having a fluoroaliphatic hydrocarbon skeleton, a fluorine-containing organic compound obtained by copolymerizing an organic compound and a fluorine-based compound, and a fluorine-containing compound containing an organic compound.
  • Examples of the fluoroaliphatic hydrocarbon skeleton include fluoroC1 to C10 alkanes such as fluoromethane, fluoroethane, fluoropropane, fluoroisopropane, fluorobutane, fluoroisobutane, fluorot-butane, fluoropentane, and fluorohexane. ..
  • the notation of "C1 to C10" means that the number of carbon atoms is 1 to 10.
  • a preferred embodiment of the fluorine-containing compound is an oligomer having a fluorine-containing group and a hydrophilic group and / or a lipophilic group (“specific fluorine-based compound”).
  • specific fluorine-based compound By adopting such a "specific fluorine-based compound", it is possible to improve the light peelability and antistatic performance of the surface protective film according to the embodiment of the present invention.
  • by using such a "specific fluorine-based compound” in combination with an ionic compound it is possible to further improve the light peelability and antistatic performance of the surface protective film according to the embodiment of the present invention.
  • the specific fluorine-based compound causes the ionic compound to be unevenly distributed on the surface side (the side to be bonded to the adherend) of the urethane-based pressure-sensitive adhesive layer.
  • Typical examples of the fluorine-containing group include a fluorine-containing alkyl group (for example, CF 3- , etc.) and / or a fluorine-containing alkylene group (for example, -CF 2 -CF 2- , etc.).
  • the hydrophilic group is a group having hydrophilicity, and hydrophilicity is a property generally known to those skilled in the art as having "hydrophilic" in English and having "affinity with water”.
  • a lipophilic group is a group having lipophilicity, and lipophilicity is a characteristic generally known to those skilled in the art as having "lipophilic" in English and "affinity with oil”. (For example, see McGraw-Hill Science and Technology Glossary (Revised 3rd Edition, Nikkan Kogyo Shimbun)).
  • the surface tension in the case of a 0.1% toluene solution is preferably 19.0 mN / m or more from the viewpoint of further improving the light peelability of the surface protective film according to the embodiment of the present invention. It is 26.0 mN / m (the surface tension of toluene is 27.9 mN / m). As described above, if the surface tension of the fluorine-containing compound in the case of a 0.1% toluene solution is within a narrow specific range of 19.0 mN / m to 26.0 mN / m, the surface protection according to the embodiment of the present invention. The light peelability of the film can be further improved.
  • the surface tension in the case of a 0.1% toluene solution is preferably 26.0 mN / m or more from the viewpoint of further improving the antistatic performance of the surface protective film according to the embodiment of the present invention. It is 28.0 mN / m (the surface tension of toluene is 27.9 mN / m). As described above, if the surface tension of the fluorine-containing compound in the case of a 0.1% toluene solution is within a narrow specific range of 26.0 mN / m to 28.0 mN / m, the surface protection according to the embodiment of the present invention. The antistatic performance of the film can be further improved.
  • Examples of commercially available fluorine-containing compounds include the following.
  • Mega Fuck Series manufactured by DIC Corporation Representatively, “Mega Fuck F-114", “Mega Fuck F-251”, “Mega Fuck F-253", “Mega Fuck F-281”, “Mega Fuck F-410", “Mega Fuck F-” 430 “,” Mega Fuck F-444 “,” Mega Fuck F-477 “,” Mega Fuck F-510 “,” Mega Fuck F-551-A “,” Mega Fuck F-553 “,” Mega Fuck F- 554 “,” Mega Fuck F-555-A “,” Mega Fuck F-556 “,” Mega Fuck F-557 “,” Mega Fuck F-558 “,” Mega Fuck F-559 “,” Mega Fuck F- 560 ”,“ Mega Fuck F-561 ”,“ Mega Fuck F-562 ”,“ Mega Fuck F-563 ”,“ Mega Fuck F-565 ”,“ Mega Fuck F-568 ”,“ Mega Fuck F-569 ” , “Mega Fuck F-570”, “Mega Fuck F-576”, “Mega Fuck R-01”, "
  • Footergent series made by Neos Co., Ltd . Representatively, "Futagent 100”, “Futagent 100C”, “Futagent 110", “Futagent 150”, “Futagent 150CH”, “Futagent 250”, “Futagent 400SW”, etc.
  • hydroxyl group-containing fluoropolymer for example, a conventionally known resin can be used.
  • a conventionally known resin can be used.
  • International Publication No. 94/06870 Pamphlet, JP-A-8-12921, JP-A-10-72569, JP-A-4-275379 examples thereof include the hydroxyl group-containing fluororesins described in Japanese Patent Publication No. 97/11130 Pamphlet, International Publication No. 96/26254 Pamphlet and the like.
  • examples of other hydroxyl group-containing fluororesins include fluoroolefins described in JP-A-8-231919, JP-A-10-265731, JP-A-10-204374, JP-A-8-12922, and the like.
  • Examples include polymers.
  • a copolymer of a compound having a fluorinated alkyl group in a hydroxyl group-containing compound, a fluorine-containing organic compound obtained by copolymerizing a fluorine-containing compound with a hydroxyl group-containing compound, a fluorine-containing compound containing a hydroxyl group-containing organic compound, and the like can be mentioned.
  • Examples of commercially available products such as the hydroxyl group-containing fluorine-based compound include the trade name "Lumiflon” (manufactured by Asahi Glass Co., Ltd.), the trade name “Cefral Coat” (manufactured by Central Glass Co., Ltd.), and the trade name "Zaflon”. (Manufactured by Toagosei Co., Ltd.), trade name “Zeffle” (manufactured by Daikin Industries, Ltd.), etc. can be mentioned.
  • Examples of the fluorinated compound containing a crosslinkable functional group include a carboxylic acid compound having a fluorinated alkyl group such as perfluorooctanoic acid and a compound having a fluorinated alkyl group in the crosslinkable functional group-containing compound.
  • Examples thereof include a polymer, a fluorine-containing organic compound obtained by copolymerizing a fluorine-containing compound with a crosslinkable functional group-containing compound, and a fluorine-containing compound containing a crosslinkable functional group-containing compound.
  • Examples of commercially available products such as crosslinkable functional group-containing fluorine-based compounds include trade names "Megafuck F-570”, “Megafuck RS-55”, “Megafuck RS-56", and “Megafuck”.
  • RS-72-K “ Mega Fuck RS-75 ”,“ Mega Fuck RS-76-E ”,“ Mega Fuck RS-76-NS ”,“ Mega Fuck RS-78 ”,“ Mega Fuck RS-90 ” (Manufactured by DIC Co., Ltd.) and the like.
  • fluorine-containing compounds available as commercially available products, those corresponding to the above-mentioned "oligomers having a fluorine-containing group and a hydrophilic group and / or a lipophilic group" are typically DIC Co., Ltd.
  • silicone-based additives When a silicone-based additive is included as another component, it is possible to further improve the light peelability of the surface protective film according to the embodiment of the present invention.
  • any suitable silicone-based additive can be adopted as long as the effect of the present invention is not impaired.
  • the silicone-based additive may be only one kind or two or more kinds.
  • the content ratio of the silicone-based additive to the total amount of the urethane prepolymer P and the polyol A is preferably 0.01% by weight or more, more preferably 0.015% by weight to 30 parts by weight, and further preferably 0. It is 0.02 parts by weight to 10 parts by weight, and particularly preferably 0.025 parts by weight to 1 part by weight.
  • the content ratio of the silicone-based additive to the total amount of the urethane prepolymer P and the polyol A is within the above range, it is possible to further improve the light peelability of the surface protective film according to the embodiment of the present invention.
  • the content ratio of the total amount of the above-mentioned fluorine-based additive and silicone-based additive to the total amount of the urethane prepolymer P and the polyol A is 0.01% by weight or more. , More preferably 0.03% by weight to 30 parts by weight, still more preferably 0.05 parts by weight to 10 parts by weight, and particularly preferably 0.05 parts by weight to 1 part by weight.
  • any suitable silicone-based additive can be adopted as long as the effect of the present invention is not impaired.
  • examples of such silicone-based additives include reactive silicone oil and non-reactive silicone oil.
  • the reactive silicone oil examples include a side chain type reactive silicone oil in which an organic group is bonded as a side chain to a Si atom used for a siloxane bond, and a double-ended type in which an organic group is bonded to Si atoms located at both ends of the structure.
  • Reactive silicone oil one-ended reactive silicone oil in which an organic group is bonded to only one of the Si atoms located at both ends of the structure, and organic groups bonded to the Si atom used for the siloxane bond as a side chain and both in the structure.
  • Examples thereof include side chain double-ended reactive silicone oil in which an organic group is bonded to a Si atom located at the terminal.
  • side chain reactive silicone oil examples include amino-modified type side-chain reactive silicone oil, epoxy-modified type side-chain reactive silicone oil, carbinol-modified type side-chain reactive silicone oil, and mercapto.
  • examples thereof include a modified type side chain reactive silicone oil, a carboxyl modified type side chain reactive silicone oil, and a methylhydrogen silicone oil type side chain reactive silicone oil.
  • examples of these commercially available products include various silicone oils commercially available as side chain reactive silicone oils manufactured by Shin-Etsu Chemical Co., Ltd.
  • Examples of the two-ended reactive silicone oil include an amino-modified type two-ended reactive silicone oil, an epoxy-modified type two-ended reactive silicone oil, a carbinol-modified type two-ended reactive silicone oil, and methacryl.
  • Modified type two-ended reactive silicone oil polyether modified type two-ended reactive silicone oil, Mercapto modified type two-ended reactive silicone oil, carboxyl-modified type two-ended reactive silicone oil, phenol-modified Type two-ended reactive silicone oil, silanol-terminated type two-ended reactive silicone oil, acrylic modified type two-ended reactive silicone oil, carboxylic acid anhydride-modified type two-ended reactive silicone oil. Be done.
  • Examples of these commercially available products include various silicone oils commercially available as double-ended reactive silicone oils manufactured by Shin-Etsu Chemical Co., Ltd.
  • both-terminal reactivity of carbinol-modified type such as "KF-6000", “KF-6001”, “KF-6002”, “KF-6003”, “KF-6028” manufactured by Shin-Etsu Chemical Co., Ltd.
  • Silicone oil can be preferably used.
  • Examples of the one-ended reactive silicone oil include one-ended reactive silicone oil of one-ended reactive modified type and one-ended reactive silicone oil of average one-ended carboxyl modified type.
  • Examples of these commercially available products include various silicone oils commercially available as one-ended reactive silicone oils manufactured by Shin-Etsu Chemical Co., Ltd.
  • carbinol-modified type one-ended reactive silicone oils such as "X-22-170BX”, “X-22-170DX”, and "X-22-4015" manufactured by Shin-Etsu Chemical Co., Ltd. can be preferably adopted. ..
  • side chain double-ended reactive silicone oil examples include side chain amino / double-ended methoxy-modified type side-chain double-ended reactive silicone oil and epoxy-modified type side-chain double-ended reactive silicone oil. .. Examples of these commercially available products include various silicone oils commercially available as side chain double-ended reactive silicone oils manufactured by Shin-Etsu Chemical Co., Ltd.
  • non-reactive silicone oil examples include a side chain type non-reactive silicone oil in which an organic group is bonded as a side chain to a Si atom used for a siloxane bond, and a side chain type non-reactive silicone oil in which an organic group is bonded to Si atoms located at both ends of the structure.
  • examples include terminal non-reactive silicone oils.
  • side chain non-reactive silicone oil examples include a polyether-modified type side-chain non-reactive silicone oil, an aralkyl-modified type side-chain non-reactive silicone oil, and a fluoroalkyl-modified type side chain non-reactive.
  • sexual silicone oil, long-chain alkyl-modified type side-chain non-reactive silicone oil, higher fatty acid ester-modified type side-chain non-reactive silicone oil, higher fatty acid-containing type side-chain non-reactive silicone oil, phenyl-modified Examples include side chain non-reactive silicone oils of the type. Examples of these commercially available products include various silicone oils commercially available as side chain type non-reactive silicone oils manufactured by Shin-Etsu Chemical Co., Ltd.
  • the HLB value is preferably 8 or more, more preferably 9 or more, still more preferably 10 or more in that the adhesive residue can be further reduced.
  • Examples of the double-ended non-reactive silicone oil include a polyether-modified type double-ended non-reactive silicone oil.
  • Examples of these commercially available products include various silicone oils commercially available as double-ended non-reactive silicone oils manufactured by Shin-Etsu Chemical Co., Ltd.
  • a polyether-modified type double-ended non-reactive silicone oil such as "KF-6004" manufactured by Shin-Etsu Chemical Co., Ltd. can be preferably adopted.
  • silicone-based additive in addition to the above, any conventionally known and suitable silicone-based additive can be adopted.
  • silicone-based additives include siloxane bond-containing polymers other than those described above, hydroxyl group-containing silicone compounds other than those described above, and crosslinkable functional group-containing silicone compounds other than those described above.
  • siloxane bond-containing polymers other than those described above include, for example, the brand name "LE-302” (manufactured by Kyoeisha Chemical Co., Ltd.) and the BYK series leveling agent manufactured by Big Chemie Japan Co., Ltd. ("BYK-300").
  • Examples of commercially available products of hydroxyl group-containing silicones other than those described above include “BYK-370”, “BYK-SILCLEAN3700”, and “BYK-SILCLEAN3720” manufactured by Big Chemie Japan Co., Ltd.
  • crosslinkable functional group-containing silicone compounds other than those described above include, for example, “BY16-855”, “SF8413", “BY16-839”, “SF8421” manufactured by Toray Dow Corning Co., Ltd. Examples thereof include “BY16-750", “BY16-880”, and “BY16-152C”.
  • the urethane-based pressure-sensitive adhesive composition may contain an antioxidant as another component from the viewpoint of suppressing deterioration of the urethane-based pressure-sensitive adhesive layer.
  • the antioxidant may be only one kind or two or more kinds.
  • any appropriate content ratio can be adopted as long as the effect of the present invention is not impaired.
  • a content ratio is preferably 0.01% by weight to 10% by weight or more, more preferably 0.05% by weight or more, as the content ratio of the antioxidant with respect to the total amount of the urethane prepolymer P and the polyol A. It is 5% by weight, more preferably 0.1% by weight to 3% by weight, and particularly preferably 0.2% by weight to 1% by weight.
  • antioxidant examples include a radical chain inhibitor, a peroxide decomposing agent, and the like.
  • radical chain inhibitor examples include phenol-based antioxidants and amine-based antioxidants.
  • peroxide decomposing agent examples include sulfur-based antioxidants and phosphorus-based antioxidants.
  • phenol-based antioxidant examples include monophenol-based antioxidants, bisphenol-based antioxidants, and polymer-type phenol-based antioxidants.
  • Examples of the monophenolic antioxidant include 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-4-ethylphenol, and stearin- ⁇ - ( 3,5-Di-t-butyl-4-hydroxyphenyl) propionate can be mentioned.
  • bisphenol-based antioxidant examples include 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2,2'-methylenebis (4-ethyl-6-t-butylphenol), and 4,4'.
  • -Thiobis (3-methyl-6-t-butylphenol), 4,4'-butylidenebis (3-methyl-6-t-butylphenol), 3,9-bis [1,1-dimethyl-2- [ ⁇ - ( ⁇ - ( 3-t-Butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl] 2,4,8,10-tetraoxaspiro [5,5] undecane can be mentioned.
  • Examples of the high molecular weight phenolic antioxidant include 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 1,3,5-trimethyl-2,4. 6-Tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, tetrakis- [methylene-3- (3', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane , Bis [3,3'-bis- (4'-hydroxy-3'-t-butylphenyl) butyric acid] glycol ester, 1,3,5-tris (3', 5'-di-t-butyl) -4'-Hydroxybenzyl) -S-triazine-2,4,6- (1H, 3H, 5H) trione, tocophenol can be mentioned.
  • sulfur-based antioxidant examples include dilauryl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate, and disstearyl 3,3'-thiodipropionate.
  • Examples of the phosphorus-based antioxidant include triphenylphosphine, diphenylisodecylphosphite, and phenyldiisodecylphosphite.
  • the urethane-based pressure-sensitive adhesive composition may contain an ultraviolet absorber as another component from the viewpoint of suppressing deterioration of the urethane-based pressure-sensitive adhesive layer.
  • the ultraviolet absorber may be only one kind or two or more kinds.
  • any appropriate content ratio can be adopted as long as the effect of the present invention is not impaired.
  • a content ratio is preferably 0.01% by weight to 10% by weight or more, more preferably 0.05% by weight or more, as the content ratio of the ultraviolet absorber with respect to the total amount of the urethane prepolymer P and the polyol A. It is 5% by weight, more preferably 0.1% by weight to 3% by weight, and particularly preferably 0.2% by weight to 1% by weight.
  • ultraviolet absorber examples include benzophenone-based ultraviolet absorbers, benzotriazole-based ultraviolet absorbers, salicylic acid-based ultraviolet absorbers, oxalic acid anilide-based ultraviolet absorbers, cyanoacrylate-based ultraviolet absorbers, and triazine-based ultraviolet absorbers. ..
  • benzophenone-based ultraviolet absorber examples include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, and 2,2'.
  • -Dihydroxy-4-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone, bis (2-methoxy-4-hydroxy-5-benzoylphenyl) ) Methane is mentioned.
  • benzotriazole-based ultraviolet absorber examples include 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-5'-tert-butylphenyl) benzotriazole, 2-( 2'-Hydroxy-3', 5'-di-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2 -(2'-Hydroxy-3', 5'-di-tert-butylphenyl) 5-chlorobenzotriazole, 2- (2'-hydroxy-3', 5'-di-tert-amylphenyl) benzotriazole, 2- (2'-Hydroxy-4'-octoxyphenyl) benzotriazole, 2- [2'-hydroxy-3'-(3'', 4', 5'', 6'', -tetrahydr
  • salicylic acid-based ultraviolet absorber examples include phenylsalicylate, p-tert-butylphenylsalicylate, and p-octylphenylsalicylate.
  • cyanoacrylate-based ultraviolet absorber examples include 2-ethylhexyl-2-cyano-3,3'-diphenylacrylate and ethyl-2-cyano-3,3'-diphenylacrylate.
  • the urethane-based pressure-sensitive adhesive composition may contain a light stabilizer as another component from the viewpoint of suppressing deterioration of the urethane-based pressure-sensitive adhesive layer.
  • the light stabilizer may be only one kind or two or more kinds.
  • any appropriate content ratio can be adopted as long as the effect of the present invention is not impaired.
  • a content ratio is preferably 0.01% by weight to 10% by weight or more, more preferably 0.05% by weight or more, as the content ratio of the light stabilizer with respect to the total amount of the urethane prepolymer P and the polyol A. It is 5% by weight, more preferably 0.1% by weight to 3% by weight, and particularly preferably 0.2% by weight to 1% by weight.
  • Examples of the light stabilizer include a hindered amine-based light stabilizer and an ultraviolet stabilizer.
  • hindered amine-based light stabilizer examples include [bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate] and bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate. , Methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacate.
  • ultraviolet stabilizer examples include nickel bis (octylphenyl) sulfide, [2,2'-thiobis (4-tert-octylphenolate)] -n-butylamine nickel, nickel complex-3,5-di-tert-.
  • examples thereof include butyl-4-hydroxybenzyl-phosphate monoethylate, nickel-dibutyldithiocarbamate, benzoate type quencher, and nickel-dibutyldithiocarbamate.
  • the urethane-based pressure-sensitive adhesive composition may contain a fatty acid ester as another component from the viewpoint of improving the wettability of the urethane-based pressure-sensitive adhesive layer.
  • the fatty acid ester may be only one kind or two or more kinds.
  • the number average molecular weight Mn of the fatty acid ester is preferably 200 to 400, more preferably 210 to 395, still more preferably 230 to 380, particularly preferably 240 to 360, and most preferably 250 to 350. Is.
  • the wetting rate can be further improved. If the number average molecular weight Mn of the fatty acid ester is too small, the wetting rate may not be improved even if the number of added portions is large. If the number average molecular weight Mn of the fatty acid ester is too large, the curability of the adhesive during drying deteriorates, which may adversely affect not only the wettability but also other adhesive properties.
  • any suitable fatty acid ester can be adopted as long as the effect of the present invention is not impaired.
  • fatty acid esters include polyoxyethylene bisphenol A lauric acid ester, butyl stearate, 2-ethylhexyl palmitate, 2-ethylhexyl stearate, monoglyceride behenic acid, cetyl 2-ethylhexanoate, and myristic acid.
  • the thickness of the base material layer is preferably 5 ⁇ m to 300 ⁇ m, more preferably 10 ⁇ m to 250 ⁇ m, further preferably 15 ⁇ m to 200 ⁇ m, and particularly preferably 20 ⁇ m to 150 ⁇ m.
  • the base material layer may be a single layer or a laminated body having two or more layers.
  • the base material layer may be a stretched one.
  • the material of the base material layer any appropriate material can be adopted depending on the application.
  • plastic, paper, metal film, non-woven fabric and the like can be mentioned. It is preferably plastic.
  • the base material layer may be composed of one kind of material, or may be made of two or more kinds of materials. For example, it may be composed of two or more kinds of plastics.
  • plastic examples include polyester-based resin, polyamide-based resin, and polyolefin-based resin.
  • polyester resin examples include polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate.
  • polyolefin-based resin examples include homopolymers of olefin monomers and copolymers of olefin monomers. Specific examples of the polyolefin-based resin include homopolypoly; a block-based, random-based, and graft-based propylene-based copolymer having an ethylene component as a copolymer; reactor TPO; low density, high density, and linear. Low-density, ultra-low-density, etc.
  • ethylene-based copolymers examples include butyl copolymers, ethylene / methacrylic acid copolymers, and ethylene-based copolymers such as ethylene / methyl methacrylate copolymers.
  • the substrate layer may contain any suitable additive, if desired.
  • additives that can be contained in the base material layer include antioxidants, ultraviolet absorbers, light stabilizers, antistatic agents, fillers, and pigments.
  • the type, number, and amount of additives that can be contained in the base material layer can be appropriately set according to the purpose.
  • the material of the base material layer is plastic, it is preferable to contain some of the above additives for the purpose of preventing deterioration and the like.
  • particularly preferable additives include antioxidants, ultraviolet absorbers, light stabilizers and fillers.
  • any suitable antioxidant can be adopted.
  • antioxidants include phenol-based antioxidants, phosphorus-based processing heat stabilizers, lactone-based processing heat stabilizers, sulfur-based heat-resistant stabilizers, phenol-phosphorus-based antioxidants, and the like.
  • the content ratio of the antioxidant is preferably 1% by weight or less, more preferably 1% by weight or less, based on the base resin of the base material layer (when the base material layer is a blend product, the blend product is the base resin). It is 0.5% by weight or less, more preferably 0.01% by weight to 0.2% by weight.
  • any appropriate ultraviolet absorber can be adopted.
  • examples of such an ultraviolet absorber include a benzotriazole-based ultraviolet absorber, a triazine-based ultraviolet absorber, and a benzophenone-based ultraviolet absorber.
  • the content ratio of the ultraviolet absorber is preferably 2% by weight or less with respect to the base resin forming the base material layer (when the base material layer is a blend product, the blend product is the base resin), and more. It is preferably 1% by weight or less, and more preferably 0.01% by weight to 0.5% by weight.
  • any appropriate light stabilizer can be adopted.
  • a light stabilizer include a hindered amine-based light stabilizer and a benzoate-based light stabilizer.
  • the content ratio of the light stabilizer is preferably 2% by weight or less with respect to the base resin forming the base material layer (when the base material layer is a blend product, the blend product is the base resin), and more. It is preferably 1% by weight or less, and more preferably 0.01% by weight to 0.5% by weight.
  • any suitable filler can be adopted.
  • a filler include an inorganic filler and the like.
  • Specific examples of the inorganic filler include carbon black, titanium oxide, zinc oxide and the like.
  • the content ratio of the filler is preferably 20% by weight or less, more preferably 20% by weight or less, based on the base resin forming the base material layer (when the base material layer is a blend product, the blend product is the base resin). Is 10% by weight or less, more preferably 0.01% by weight to 10% by weight.
  • an inorganic type such as a surfactant, an inorganic salt, a polyhydric alcohol, a metal compound, and carbon, a low molecular weight type, and a high molecular weight type antistatic agent are also preferably mentioned for the purpose of imparting antistatic properties.
  • an inorganic type such as a surfactant, an inorganic salt, a polyhydric alcohol, a metal compound, and carbon, a low molecular weight type, and a high molecular weight type antistatic agent are also preferably mentioned for the purpose of imparting antistatic properties.
  • high molecular weight antistatic agents and carbon are preferable.
  • the surface protective film of the present invention can be produced by any suitable method.
  • a manufacturing method for example, (1) A method of applying a solution of a material for forming an adhesive layer or a thermal melt solution onto a base material layer, (2) A method of transferring the pressure-sensitive adhesive layer applied and formed in the form of a separator onto the base material layer according to the method. (3) A method of extruding a material for forming an adhesive layer onto a base material layer to form and apply the adhesive layer.
  • a method of extruding a base material layer and an adhesive layer in two or multiple layers (5) A method of laminating a single layer of an adhesive layer on a base material layer or a method of laminating two layers of an adhesive layer together with a laminating layer. (6) A method of laminating a pressure-sensitive adhesive layer and a base material layer forming material such as a film or a laminate layer in two or multiple layers. It can be carried out according to any suitable manufacturing method such as.
  • a roll coater method for example, a roll coater method, a comma coater method, a die coater method, a reverse coater method, a silk screen method, a gravure coater method, etc. can be used.
  • the surface protective film according to the embodiment of the present invention can be used for any suitable application.
  • the surface protective film of the present invention is preferably used for surface protection of optical members and electronic members, for example, because it has very little contamination on the adherend and is preferably excellent in wettability and reworkability.
  • the optical member include a touch panel using an LCD, an LCD, a color filter used for the LCD, a polarizing plate, and the like.
  • the attached surface protective film can be manually attached and peeled off many times. ..
  • the optical member according to the embodiment of the present invention is the one to which the surface protective film of the present invention is attached.
  • the electronic member according to the embodiment of the present invention is the one to which the surface protective film of the present invention is attached.
  • the load when the surface protective film was peeled from the glass was measured, and the average load at that time was taken as the adhesive force (peeling force) of the surface protective film against the glass.
  • a surface protective film is attached to the entire surface of a glass plate (made by Matsunami Glass, 1.35 mm x 10 cm x 10 cm) with a hand roller, stored in an atmosphere of temperature 23 ° C and humidity 55% RH for 24 hours, and then the peeling angle.
  • the surface protective film was peeled off at a speed of 180 degrees and 0.3 m / min, and the No. 19 mm wide No. was cut to a length of 150 mm.
  • a 31B tape manufactured by Nitto Denko Corporation, substrate thickness: 25 ⁇ m
  • This residual adhesive ratio is an index of how much the pressure-sensitive adhesive component of the surface protective film is transferred to the surface of the adherend and contaminated. It can be said that the higher the residual adhesion ratio value, the better the surface protection film without contaminating the adherend, and the lower the residual adhesion ratio value, the more the surface of the adherend is contaminated with an adhesive component or the like. ..
  • ⁇ Glass-resistant band voltage> The surface protective film from which the separator has been peeled off is cut into a size of 70 mm in width and 100 mm in length, and one end of the surface protective film is attached to the surface of glass (soda lime glass, manufactured by Matsunami Glass Ind.). It was crimped with a hand roller so as to protrude 30 mm from the end of the glass. This sample was left in an environment of 23 ° C. ⁇ 50% RH for 1 day, and then set in a predetermined position on a sample fixing table having a height of 20 mm.
  • the potential on the surface of the adherend generated at this time is fixed at a position 30 mm in height from the center of the adherend with a potential measuring instrument (manufactured by Sisid Electrostatic Co., Ltd., model "STATIRON DZ-4"). "Peeling band voltage” was measured. The measurement was performed in an environment of 23 ° C. and 50% RH.
  • the urethane adhesive composition is applied to the peeled surface of a polyester film (trade name: Diafoil MRF75, manufactured by Mitsubishi Chemical Corporation) having a thickness of 75 ⁇ m, one side of which is peeled with silicone, under the conditions of Examples and Comparative Examples. It was industrially dried to prepare a urethane-based pressure-sensitive adhesive layer. Next, a polyester film with a thickness of 75 ⁇ m (trade name: Diafoil MRE75, manufactured by Mitsubishi Chemical Corporation) whose one side was peeled off with silicone was applied to the surface of the urethane adhesive layer, and the peeled surface of the polyester film was urethane-based adhesive.
  • a polyester film with a thickness of 75 ⁇ m (trade name: Diafoil MRE75, manufactured by Mitsubishi Chemical Corporation) whose one side was peeled off with silicone was applied to the surface of the urethane adhesive layer, and the peeled surface of the polyester film was urethane-based adhesive.
  • the film was coated so as to be on the agent layer side, and aged at room temperature for 5 days. Two sheets of 50 mm ⁇ 50 mm thick paper with a hole of 20 mm ⁇ 20 mm were prepared, and a single sample was attached to one of them with one reciprocating hand roller, and then the other was attached.
  • the haze of the evaluation sample obtained as described above was measured with "HM-150N" manufactured by Murakami Color Technology Research Institute.
  • a urethane-based pressure-sensitive adhesive solution was applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 ⁇ m, manufactured by Mitsubishi Chemical Co., Ltd.), dried, and then dried. It was observed whether or not a pressure-sensitive adhesive layer having a thickness of 75 ⁇ m could be obtained.
  • ⁇ An adhesive layer having a thickness of 75 ⁇ m after drying could be formed.
  • X The pressure-sensitive adhesive layer having a thickness of 75 ⁇ m after drying could not be formed.
  • toluene was appropriately added dropwise in order to control the temperature during the polymerization and prevent the decrease in agitation due to the increase in viscosity.
  • the total amount of toluene dropped was 320 g.
  • the solid content concentration of the urethane prepolymer solution was 50% by weight. This urethane prepolymer was used in Examples and Comparative Examples.
  • Sanniks GP4000 Sanniks GP4000 (Sanyo Kasei Co., Ltd.)
  • RNA-based pressure-sensitive adhesive solution 0.03 part by weight of Nasem ferrous iron (manufactured by Nippon Kagaku Sangyo Co., Ltd.) was diluted with ethyl acetate so that the total solid content was 50% by weight to obtain a urethane-based pressure-sensitive adhesive solution. Then, the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 ⁇ m, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 ⁇ m, and the drying temperature is 130 ° C. , Cure and dry under the condition of drying time of 3 minutes to prepare a pressure-sensitive adhesive layer composed of the pressure-sensitive adhesive composition (1).
  • a base material made of polyester resin trade name "T100-75S", thickness 75 ⁇ m, manufactured by Mitsubishi Chemical Co., Ltd.
  • the surface of the obtained pressure-sensitive adhesive layer was treated with a silicone-treated release sheet (trade name "MRF25", thickness 25 ⁇ m, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 ⁇ m, one of which was treated with silicone.
  • the surfaces were bonded together to obtain a surface protective film (1). Aging was performed at room temperature for 5 days for evaluation. The release sheet was peeled off immediately before the evaluation. The results are shown in Table 1.
  • isocyanate compound Coronate HX: C / HX, manufactured by Nippon Polyurethane Co., Ltd.
  • Irganox 1010 manufactured by BASF
  • RNA-based pressure-sensitive adhesive solution 0.03 part by weight of Nasem ferrous iron (manufactured by Nippon Kagaku Sangyo Co., Ltd.) was diluted with ethyl acetate so that the total solid content was 50% by weight to obtain a urethane-based pressure-sensitive adhesive solution. Then, the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 ⁇ m, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 ⁇ m, and the drying temperature is 130 ° C. , Cure and dry under the condition of drying time of 3 minutes to prepare a pressure-sensitive adhesive layer composed of the pressure-sensitive adhesive composition (2).
  • a base material made of polyester resin trade name "T100-75S", thickness 75 ⁇ m, manufactured by Mitsubishi Chemical Co., Ltd.
  • the surface of the obtained pressure-sensitive adhesive layer was treated with a silicone-treated release sheet (trade name "MRF25", thickness 25 ⁇ m, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 ⁇ m, one of which was treated with silicone.
  • the surfaces were bonded together to obtain a surface protective film (2). Aging was performed at room temperature for 5 days for evaluation. The release sheet was peeled off immediately before the evaluation. The results are shown in Table 1.
  • urethane-based pressure-sensitive adhesive solution It was diluted with ethyl acetate so that the solid content was 50% by weight to obtain a urethane-based pressure-sensitive adhesive solution. Then, the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 ⁇ m, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 ⁇ m, and the drying temperature is 130 ° C. , Cure and dry under the condition of drying time of 3 minutes to prepare a pressure-sensitive adhesive layer composed of the pressure-sensitive adhesive composition (3).
  • the surface of the obtained pressure-sensitive adhesive layer was treated with a silicone-treated release sheet (trade name "MRF25", thickness 25 ⁇ m, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 ⁇ m, one of which was treated with silicone.
  • the surfaces were bonded together to obtain a surface protective film (3). Aging was performed at room temperature for 5 days for evaluation. The release sheet was peeled off immediately before the evaluation. The results are shown in Table 1.
  • urethane-based pressure-sensitive adhesive solution It was diluted with ethyl acetate so that the solid content was 50% by weight to obtain a urethane-based pressure-sensitive adhesive solution. Then, the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 ⁇ m, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 ⁇ m, and the drying temperature is 130 ° C. , Cure and dry under the condition of drying time of 3 minutes to prepare a pressure-sensitive adhesive layer composed of the pressure-sensitive adhesive composition (4).
  • the surface of the obtained pressure-sensitive adhesive layer was treated with a silicone-treated release sheet (trade name "MRF25", thickness 25 ⁇ m, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 ⁇ m, one of which was treated with silicone.
  • the surfaces were bonded together to obtain a surface protective film (4). Aging was performed at room temperature for 5 days for evaluation. The release sheet was peeled off immediately before the evaluation. The results are shown in Table 1.
  • urethane-based pressure-sensitive adhesive solution It was diluted with ethyl acetate so that the solid content was 50% by weight to obtain a urethane-based pressure-sensitive adhesive solution. Then, the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 ⁇ m, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 ⁇ m, and the drying temperature is 130 ° C. , Cure and dry under the condition of drying time of 3 minutes to prepare a pressure-sensitive adhesive layer composed of the pressure-sensitive adhesive composition (5).
  • a base material made of polyester resin (trade name "T100-75S", thickness 75 ⁇ m, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 ⁇ m, and the drying temperature is 130 ° C.
  • Cure and dry under the condition of drying time of 3 minutes to prepare a pressure-sensitive adhesive layer composed of the pressure-sensitive adhesive composition (5).
  • the surface of the obtained pressure-sensitive adhesive layer was treated with a silicone-treated release sheet (trade name "MRF25", thickness 25 ⁇ m, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 ⁇ m, one of which was treated with silicone.
  • the surfaces were bonded together to obtain a surface protective film (5). Aging was performed at room temperature for 5 days for evaluation. The release sheet was peeled off immediately before the evaluation. The results are shown in Table 1.
  • Sanniks GP3000 Sanniks GP3000
  • RNA-based pressure-sensitive adhesive solution 0.03 part by weight of Nasem ferrous iron (manufactured by Nippon Kagaku Sangyo Co., Ltd.) was diluted with ethyl acetate so that the total solid content was 50% by weight to obtain a urethane-based pressure-sensitive adhesive solution. Then, the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 ⁇ m, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 ⁇ m, and the drying temperature is 130 ° C. , Cure and dry under the condition of drying time of 3 minutes to prepare a pressure-sensitive adhesive layer composed of the pressure-sensitive adhesive composition (6).
  • a base material made of polyester resin trade name "T100-75S", thickness 75 ⁇ m, manufactured by Mitsubishi Chemical Co., Ltd.
  • the surface of the obtained pressure-sensitive adhesive layer was treated with a silicone-treated release sheet (trade name "MRF25", thickness 25 ⁇ m, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 ⁇ m, one of which was treated with silicone.
  • the surfaces were bonded together to obtain a surface protective film (6). Aging was performed at room temperature for 5 days for evaluation. The release sheet was peeled off immediately before the evaluation. The results are shown in Table 1.
  • Sanniks GP3000 Sanniks GP3000
  • RNA-based pressure-sensitive adhesive solution 0.03 part by weight of Nasem ferrous iron (manufactured by Nippon Kagaku Sangyo Co., Ltd.) was diluted with ethyl acetate so that the total solid content was 50% by weight to obtain a urethane-based pressure-sensitive adhesive solution. Then, the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 ⁇ m, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 ⁇ m, and the drying temperature is 130 ° C. , Cure and dry under the condition of drying time of 3 minutes to prepare a pressure-sensitive adhesive layer composed of the pressure-sensitive adhesive composition (7).
  • a base material made of polyester resin trade name "T100-75S", thickness 75 ⁇ m, manufactured by Mitsubishi Chemical Co., Ltd.
  • the surface of the obtained pressure-sensitive adhesive layer was treated with a silicone-treated release sheet (trade name "MRF25", thickness 25 ⁇ m, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 ⁇ m, one of which was treated with silicone.
  • the surfaces were bonded together to obtain a surface protective film (7). Aging was performed at room temperature for 5 days for evaluation. The release sheet was peeled off immediately before the evaluation. The results are shown in Table 1.
  • Sanniks GP3000 Sanniks GP3000
  • RNA-based pressure-sensitive adhesive solution 0.03 part by weight of Nasem ferrous iron (manufactured by Nippon Kagaku Sangyo Co., Ltd.) was diluted with ethyl acetate so that the total solid content was 50% by weight to obtain a urethane-based pressure-sensitive adhesive solution. Then, the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 ⁇ m, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 ⁇ m, and the drying temperature is 130 ° C. , Cure and dry under the condition of drying time of 3 minutes to prepare a pressure-sensitive adhesive layer composed of the pressure-sensitive adhesive composition (8).
  • a base material made of polyester resin trade name "T100-75S", thickness 75 ⁇ m, manufactured by Mitsubishi Chemical Co., Ltd.
  • the surface of the obtained pressure-sensitive adhesive layer was treated with a silicone-treated release sheet (trade name "MRF25", thickness 25 ⁇ m, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 ⁇ m, one of which was treated with silicone.
  • the surfaces were bonded together to obtain a surface protective film (8). Aging was performed at room temperature for 5 days for evaluation. The release sheet was peeled off immediately before the evaluation. The results are shown in Table 1.
  • Sanniks GP3000 Sanniks GP3000 (Sanyo Kasei Co., Ltd.)
  • RNA-based iron manufactured by Nippon Kagaku Sangyo Co., Ltd.
  • ethyl acetate ethyl acetate
  • the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 ⁇ m, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 ⁇ m, and the drying temperature is 130 ° C.
  • the surface of the obtained pressure-sensitive adhesive layer was treated with a silicone-treated release sheet (trade name "MRF25", thickness 25 ⁇ m, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 ⁇ m, one of which was treated with silicone.
  • the surfaces were bonded together to obtain a surface protective film (9). Aging was performed at room temperature for 5 days for evaluation. The release sheet was peeled off immediately before the evaluation. The results are shown in Table 1.
  • Sanniks GP3000 Sanniks GP3000 (Sanyo Kasei Co., Ltd.)
  • RNA-based iron manufactured by Nippon Kagaku Sangyo Co., Ltd.
  • ethyl acetate ethyl acetate
  • the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 ⁇ m, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 ⁇ m, and the drying temperature is 130 ° C.
  • the surface of the obtained pressure-sensitive adhesive layer was treated with a silicone-treated release sheet (trade name "MRF25", thickness 25 ⁇ m, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 ⁇ m, one of which was treated with silicone.
  • the surfaces were bonded together to obtain a surface protective film (10). Aging was performed at room temperature for 5 days for evaluation. The release sheet was peeled off immediately before the evaluation. The results are shown in Table 1.
  • Sanniks GP3000 Sanniks GP3000 (Sanyo Kasei Co., Ltd.)
  • RNA-based pressure-sensitive adhesive solution 0.03 part by weight of Nasem ferrous iron (manufactured by Nippon Kagaku Sangyo Co., Ltd.) was diluted with ethyl acetate so that the total solid content was 50% by weight to obtain a urethane-based pressure-sensitive adhesive solution. Then, the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 ⁇ m, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 ⁇ m, and the drying temperature is 130 ° C. , Cure and dry under the condition of drying time of 3 minutes to prepare a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition (11).
  • the surface of the obtained pressure-sensitive adhesive layer was treated with a silicone-treated release sheet (trade name "MRF25", thickness 25 ⁇ m, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 ⁇ m, one of which was treated with silicone.
  • the surfaces were bonded together to obtain a surface protective film (11). Aging was performed at room temperature for 5 days for evaluation. The release sheet was peeled off immediately before the evaluation. The results are shown in Table 1.
  • Chemical company, Mn 3000) 1.5 parts by weight, isocyanate compound (Coronate HX: C / HX, manufactured by Nippon Polyurethane Co., Ltd.) 3.5 parts by weight as a cross-linking agent, Irganox1010 (manufactured by BASF) 0 as an antioxidant.
  • a urethane-based pressure-sensitive adhesive solution is prepared. Obtained. Then, the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 ⁇ m, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 ⁇ m, and the drying temperature is 130 ° C. , Cure and dry under the condition of drying time of 3 minutes to prepare a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition (12).
  • the surface of the obtained pressure-sensitive adhesive layer was treated with a silicone-treated release sheet (trade name "MRF25", thickness 25 ⁇ m, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 ⁇ m, one of which was treated with silicone.
  • the surfaces were bonded together to obtain a surface protective film (12). Aging was performed at room temperature for 5 days for evaluation. The release sheet was peeled off immediately before the evaluation. The results are shown in Table 1.
  • RNA-based iron manufactured by Nippon Kagaku Sangyo Co., Ltd.
  • ethyl acetate ethyl acetate
  • the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 ⁇ m, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 ⁇ m, and the drying temperature is 130 ° C.
  • the surface of the obtained pressure-sensitive adhesive layer was treated with a silicone-treated release sheet (trade name "MRF25", thickness 25 ⁇ m, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 ⁇ m, one of which was treated with silicone.
  • the surfaces were bonded together to obtain a surface protective film (13). Aging was performed at room temperature for 5 days for evaluation. The release sheet was peeled off immediately before the evaluation. The results are shown in Table 1.
  • Sanniks GP3000 Sanniks GP3000
  • RNA-based iron manufactured by Nippon Kagaku Sangyo Co., Ltd.
  • ethyl acetate ethyl acetate
  • the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 ⁇ m, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 ⁇ m, and the drying temperature is 130 ° C.
  • the surface of the obtained pressure-sensitive adhesive layer was treated with a silicone-treated release sheet (trade name "MRF25", thickness 25 ⁇ m, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 ⁇ m, one of which was treated with silicone.
  • the surfaces were bonded together to obtain a surface protective film (14). Aging was performed at room temperature for 5 days for evaluation. The release sheet was peeled off immediately before the evaluation. The results are shown in Table 1.
  • Sanniks GP3000 Sanniks GP3000
  • RNA-based iron manufactured by Nippon Kagaku Sangyo Co., Ltd.
  • ethyl acetate ethyl acetate
  • the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 ⁇ m, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 ⁇ m, and the drying temperature is 130 ° C.
  • the surface of the obtained pressure-sensitive adhesive layer was treated with a silicone-treated release sheet (trade name "MRF25", thickness 25 ⁇ m, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 ⁇ m, one of which was treated with silicone.
  • the surfaces were bonded together to obtain a surface protective film (15). Aging was performed at room temperature for 5 days for evaluation. The release sheet was peeled off immediately before the evaluation. The results are shown in Table 1.
  • Mn 10000, manufactured by Asahi Glass Co., Ltd.
  • Sanniks GP3000 Sanniks GP3000 (Sanyo Kasei Co., Ltd.)
  • Lomethanesulfonyl) imide (AS110, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 0.05 parts by weight, isocyanate 1010 (manufactured by BASF) 0.5 parts by weight as an antioxidant, Nasem ferric iron (manufactured by Nippon Kagaku Sangyo Co., Ltd.) as a catalyst. ) 0.03 part by weight was diluted with ethyl acetate so that the total solid content was 50% by weight to obtain a urethane-based pressure-sensitive adhesive solution.
  • the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 ⁇ m, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 ⁇ m, and the drying temperature is 130 ° C. , Cure and dry under the condition of drying time of 3 minutes to prepare a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition (16).
  • a silicone-treated release sheet (trade name "MRF25”, thickness 25 ⁇ m, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 ⁇ m, one of which was treated with silicone.
  • the surfaces were bonded together to obtain a surface protective film (16). Aging was performed at room temperature for 5 days for evaluation.
  • the release sheet was peeled off immediately before the evaluation. The results are shown in Table 2.
  • Mn 10000, manufactured by Asahi Glass Co., Ltd.
  • Sanniks GP3000 Sanniks GP3000 (Sanyo Kasei Co., Ltd.)
  • Rometasulfonyl) imide (AS110, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 0.1 part by weight, isocyanate1010 (manufactured by BASF) 0.5 parts by weight as an antioxidant, Nasem ferric iron (manufactured by Nippon Kagaku Sangyo Co., Ltd.) as a catalyst. ) 0.03 part by weight was diluted with ethyl acetate so that the total solid content was 50% by weight to obtain a urethane-based pressure-sensitive adhesive solution.
  • the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 ⁇ m, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 ⁇ m, and the drying temperature is 130 ° C. , And dried under the condition of a drying time of 3 minutes to prepare a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition (17).
  • a silicone-treated release sheet (trade name "MRF25”, thickness 25 ⁇ m, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 ⁇ m, one of which was treated with silicone.
  • the surfaces were bonded together to obtain a surface protective film (17). Aging was performed at room temperature for 5 days for evaluation.
  • the release sheet was peeled off immediately before the evaluation. The results are shown in Table 2.
  • Lomethanesulfonyl) imide (AS110, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 0.5 parts by weight, as an antioxidant, Irganox1010 (manufactured by BASF) 0.5 parts by weight, as a catalyst, Nasem ferric iron (manufactured by Nippon Kagaku Sangyo Co., Ltd.) ) 0.03 part by weight was diluted with ethyl acetate so that the total solid content was 50% by weight to obtain a urethane-based pressure-sensitive adhesive solution.
  • AS110 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
  • Irganox1010 manufactured by BASF
  • Nasem ferric iron manufactured by Nippon Kagaku Sangyo Co., Ltd.
  • the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 ⁇ m, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 ⁇ m, and the drying temperature is 130 ° C. , Cure and dry under the condition of drying time of 3 minutes to prepare a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition (18).
  • a silicone-treated release sheet (trade name "MRF25”, thickness 25 ⁇ m, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 ⁇ m, one of which was treated with silicone.
  • the surfaces were bonded together to obtain a surface protective film (18). Aging was performed at room temperature for 5 days for evaluation.
  • the release sheet was peeled off immediately before the evaluation. The results are shown in Table 2.
  • Mn 10000, manufactured by Asahi Glass Co., Ltd.
  • Sanniks GP3000 Sanniks GP3000 (Sanyo Kasei Co., Ltd.)
  • Lomethanesulfonyl) imide (AS110, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 1.0 part by weight, isocyanate 1010 (manufactured by BASF) 0.5 parts by weight as an antioxidant, Nasem ferric iron (manufactured by Nippon Kagaku Sangyo Co., Ltd.) as a catalyst. ) 0.03 part by weight was diluted with ethyl acetate so that the total solid content was 50% by weight to obtain a urethane-based pressure-sensitive adhesive solution.
  • the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 ⁇ m, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 ⁇ m, and the drying temperature is 130 ° C. , Cure and dry under the condition of drying time of 3 minutes to prepare a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition (19).
  • a silicone-treated release sheet (trade name "MRF25”, thickness 25 ⁇ m, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 ⁇ m, one of which was treated with silicone.
  • the surfaces were bonded together to obtain a surface protective film (19). Aging was performed at room temperature for 5 days for evaluation.
  • the release sheet was peeled off immediately before the evaluation. The results are shown in Table 2.
  • a urethane-based pressure-sensitive adhesive solution was obtained.
  • the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 ⁇ m, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 ⁇ m, and the drying temperature is 130 ° C. , Cure and dry under the condition of drying time of 3 minutes to prepare a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition (20).
  • the surface of the obtained pressure-sensitive adhesive layer was treated with a silicone-treated release sheet (trade name "MRF25”, thickness 25 ⁇ m, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 ⁇ m, one of which was treated with silicone.
  • the surfaces were bonded together to obtain a surface protective film (20). Aging was performed at room temperature for 5 days for evaluation.
  • the release sheet was peeled off immediately before the evaluation. The results are shown in Table 2.
  • a urethane-based pressure-sensitive adhesive solution was obtained.
  • the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 ⁇ m, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 ⁇ m, and the drying temperature is 130 ° C. , Cure and dry under the condition of drying time of 3 minutes to prepare a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition (21).
  • the surface of the obtained pressure-sensitive adhesive layer was treated with a silicone-treated release sheet (trade name "MRF25”, thickness 25 ⁇ m, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 ⁇ m, one of which was treated with silicone.
  • the surfaces were bonded together to obtain a surface protective film (21). Aging was performed at room temperature for 5 days for evaluation.
  • the release sheet was peeled off immediately before the evaluation. The results are shown in Table 2.
  • Irganox 1010 manufactured by BASF
  • Nasem ferric iron manufactured by Nippon Kagaku Sangyo Co., Ltd.
  • a urethane-based pressure-sensitive adhesive solution was obtained.
  • the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 ⁇ m, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 ⁇ m, and the drying temperature is 130 ° C.
  • Mn 10000, manufactured by Asahi Glass Co., Ltd.
  • Sanniks GP3000 Sanniks GP3000 (Sanyo Kasei Co., Ltd.)
  • Lomethanesulfonyl) imide (AS110, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 0.5 parts by weight, as an antioxidant, Irganox1010 (manufactured by BASF) 0.5 parts by weight, as a catalyst, Nasem ferric iron (manufactured by Nippon Kagaku Sangyo Co., Ltd.) ) 0.03 part by weight was diluted with ethyl acetate so that the total solid content was 50% by weight to obtain a urethane-based pressure-sensitive adhesive solution.
  • AS110 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
  • Irganox1010 manufactured by BASF
  • Nasem ferric iron manufactured by Nippon Kagaku Sangyo Co., Ltd.
  • the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 ⁇ m, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 ⁇ m, and the drying temperature is 130 ° C. , Cure and dry under the condition of drying time of 3 minutes to prepare a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition (23).
  • a silicone-treated release sheet (trade name "MRF25”, thickness 25 ⁇ m, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 ⁇ m, one of which was treated with silicone.
  • the surfaces were bonded together to obtain a surface protective film (23). Aging was performed at room temperature for 5 days for evaluation.
  • the release sheet was peeled off immediately before the evaluation. The results are shown in Table 2.
  • Sanniks GP3000 Sanniks GP3000 (Sanyo Kasei Co., Ltd.)
  • isocyanate compound Coronate
  • Lomethansulfonyl) imide (AS110, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 0.05 parts by weight, fluoropolymer Megafuck F-477 (manufactured by DIC) 0.1 parts by weight, Irganox 1010 (manufactured by BASF) as an antioxidant. ) 0.5 parts by weight, 0.03 parts by weight of Nasem ferrous iron (manufactured by Nippon Kagaku Sangyo Co., Ltd.) as a catalyst, diluted with ethyl acetate so that the total solid content is 50% by weight, urethane-based pressure-sensitive adhesive A solution was obtained.
  • the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 ⁇ m, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 ⁇ m, and the drying temperature is 130 ° C. , Cure and dry under the condition of drying time of 3 minutes to prepare a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition (24).
  • a silicone-treated release sheet (trade name "MRF25”, thickness 25 ⁇ m, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 ⁇ m, one of which was treated with silicone.
  • the surfaces were bonded together to obtain a surface protective film (24). Aging was performed at room temperature for 5 days for evaluation.
  • the release sheet was peeled off immediately before the evaluation. The results are shown in Table 3.
  • Mn 10000, manufactured by Asahi Glass Co., Ltd.
  • Sanniks GP3000 Sanniks GP3000 (Sanyo Kasei Co., Ltd.)
  • romethanesulfonyl) imide AS110, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
  • DIC methyl methyl acetate
  • Irganox1010 manufactured by BASF
  • the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 ⁇ m, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 ⁇ m, and the drying temperature is 130 ° C. , Cure and dry under the condition of drying time of 3 minutes to prepare a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition (25).
  • a silicone-treated release sheet (trade name "MRF25”, thickness 25 ⁇ m, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 ⁇ m, one of which was treated with silicone.
  • the surfaces were bonded together to obtain a surface protective film (25). Aging was performed at room temperature for 5 days for evaluation.
  • the release sheet was peeled off immediately before the evaluation. The results are shown in Table 3.
  • Mn 10000, manufactured by Asahi Glass Co., Ltd.
  • Sanniks GP3000 Sanniks GP3000 (Sanyo Kasei Co., Ltd.)
  • Romethanesulfonyl) imide (AS110, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 0.5 parts by weight, fluoropolymer Megafuck F-477 (manufactured by DIC) 0.1 parts by weight, Irganox 1010 (manufactured by BASF) as an antioxidant. ) 0.5 parts by weight, 0.03 parts by weight of Nasem ferrous iron (manufactured by Nippon Kagaku Sangyo Co., Ltd.) as a catalyst is diluted with ethyl acetate so that the total solid content is 50% by weight, and a urethane-based pressure-sensitive adhesive is used. A solution was obtained.
  • the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 ⁇ m, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 ⁇ m, and the drying temperature is 130 ° C. , Cure and dry under the condition of drying time of 3 minutes to prepare a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition (26).
  • a silicone-treated release sheet (trade name "MRF25”, thickness 25 ⁇ m, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 ⁇ m, one of which was treated with silicone.
  • the surfaces were bonded together to obtain a surface protective film (26). Aging was performed at room temperature for 5 days for evaluation.
  • the release sheet was peeled off immediately before the evaluation. The results are shown in Table 3.
  • Mn 10000, manufactured by Asahi Glass Co., Ltd.
  • Sanniks GP3000 Sanniks GP3000 (Sanyo Kasei Co., Ltd.)
  • Rometasulfonyl) imide (AS110, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 1.0 part by weight, fluorine-based oligomer Megafuck F-477 (manufactured by DIC) 0.1 part by weight, as an antioxidant, Irganox 1010 (manufactured by BASF) ) 0.5 parts by weight, 0.03 parts by weight of Nasem ferrous iron (manufactured by Nippon Kagaku Sangyo Co., Ltd.) as a catalyst is diluted with ethyl acetate so that the total solid content is 50% by weight, and a urethane-based pressure-sensitive adhesive is used. A solution was obtained.
  • the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 ⁇ m, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 ⁇ m, and the drying temperature is 130 ° C. , And dried under the condition of a drying time of 3 minutes to prepare a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition (27).
  • a silicone-treated release sheet (trade name "MRF25”, thickness 25 ⁇ m, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 ⁇ m, one of which was treated with silicone.
  • the surfaces were bonded together to obtain a surface protective film (27). Aging was performed at room temperature for 5 days for evaluation.
  • the release sheet was peeled off immediately before the evaluation. The results are shown in Table 3.
  • Mn 10000, manufactured by Asahi Glass Co., Ltd.
  • Sanniks GP3000 Sanniks GP3000 (Sanyo Kasei Co., Ltd.)
  • Romethanesulfonyl) imide (AS110, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 0.5 parts by weight, fluoropolymer Megafuck F-477 (manufactured by DIC) 0.05 parts by weight, Irganox 1010 (manufactured by BASF) as an antioxidant. ) 0.5 parts by weight, 0.03 parts by weight of Nasem ferrous iron (manufactured by Nippon Kagaku Sangyo Co., Ltd.) as a catalyst is diluted with ethyl acetate so that the total solid content is 50% by weight, and a urethane-based pressure-sensitive adhesive is used. A solution was obtained.
  • the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 ⁇ m, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 ⁇ m, and the drying temperature is 130 ° C. , Cure and dry under the condition of drying time of 3 minutes to prepare a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition (28).
  • a silicone-treated release sheet (trade name "MRF25”, thickness 25 ⁇ m, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 ⁇ m, one of which was treated with silicone.
  • the surfaces were bonded together to obtain a surface protective film (28). Aging was performed at room temperature for 5 days for evaluation.
  • the release sheet was peeled off immediately before the evaluation. The results are shown in Table 3.
  • Mn 10000, manufactured by Asahi Glass Co., Ltd.
  • Sanniks GP3000 Sanniks GP3000 (Sanyo Kasei Co., Ltd.)
  • Romethanesulfonyl) imide (AS110, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 0.5 parts by weight, fluorinated oligomer Megafuck F-477 (manufactured by DIC) 0.5 parts by weight, as an antioxidant, Irganox 1010 (manufactured by BASF) ) 0.5 parts by weight, 0.03 parts by weight of Nasem ferrous iron (manufactured by Nippon Kagaku Sangyo Co., Ltd.) as a catalyst is diluted with ethyl acetate so that the total solid content is 50% by weight, and a urethane-based pressure-sensitive adhesive is used. A solution was obtained.
  • the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 ⁇ m, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 ⁇ m, and the drying temperature is 130 ° C. , Cure and dry under the condition of drying time of 3 minutes to prepare a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition (29).
  • a silicone-treated release sheet (trade name "MRF25”, thickness 25 ⁇ m, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 ⁇ m, one of which was treated with silicone.
  • the surfaces were bonded together to obtain a surface protective film (29). Aging was performed at room temperature for 5 days for evaluation.
  • the release sheet was peeled off immediately before the evaluation. The results are shown in Table 3.
  • Mn 10000, manufactured by Asahi Glass Co., Ltd.
  • Sanniks GP3000 Sanniks GP3000 (Sanyo Kasei Co., Ltd.)
  • Rometasulfonyl) imide (AS110, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 0.5 part by weight, fluoropolymer Megafuck F-477 (manufactured by DIC) 1.0 part by weight, Irganox1010 (manufactured by BASF) as an antioxidant. ) 0.5 parts by weight, 0.03 parts by weight of Nasem ferrous iron (manufactured by Nippon Kagaku Sangyo Co., Ltd.) as a catalyst is diluted with ethyl acetate so that the total solid content is 50% by weight, and a urethane-based pressure-sensitive adhesive is used. A solution was obtained.
  • the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 ⁇ m, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 ⁇ m, and the drying temperature is 130 ° C. , Cure and dry under the condition of drying time of 3 minutes to prepare a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition (30).
  • a silicone-treated release sheet (trade name "MRF25”, thickness 25 ⁇ m, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 ⁇ m, one of which was treated with silicone.
  • the surfaces were bonded together to obtain a surface protective film (30). Aging was performed at room temperature for 5 days for evaluation.
  • the release sheet was peeled off immediately before the evaluation. The results are shown in Table 3.
  • romethanesulfonyl) imide AS110, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
  • fluorinated oligomer Megafuck F-477 manufactured by DIC
  • Irganox1010 manufactured by BASF
  • a catalyst diluted with ethyl acetate so that the total solid content is 50% by weight, urethane-based pressure-sensitive adhesive A solution was obtained.
  • the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 ⁇ m, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 ⁇ m, and the drying temperature is 130 ° C. , Cure and dry under the condition of drying time of 3 minutes to prepare a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition (31).
  • a silicone-treated release sheet (trade name "MRF25”, thickness 25 ⁇ m, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 ⁇ m, one of which was treated with silicone.
  • the surfaces were bonded together to obtain a surface protective film (31). Aging was performed at room temperature for 5 days for evaluation.
  • the release sheet was peeled off immediately before the evaluation. The results are shown in Table 3.
  • Mn 10000, manufactured by Asahi Glass Co., Ltd.
  • Sanniks GP3000 Sanniks GP3000 (Sanyo Kasei Co., Ltd.)
  • Rometasulfonyl) imide (AS110, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 0.5 parts by weight, fluoropolymer Megafuck F-563 (manufactured by DIC) 0.05 parts by weight, Irganox 1010 (manufactured by BASF) as an antioxidant. ) 0.5 parts by weight, 0.03 parts by weight of Nasem ferrous iron (manufactured by Nippon Kagaku Sangyo Co., Ltd.) as a catalyst is diluted with ethyl acetate so that the total solid content is 50% by weight, and a urethane-based pressure-sensitive adhesive is used. A solution was obtained.
  • the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 ⁇ m, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 ⁇ m, and the drying temperature is 130 ° C. , Cure and dry under the condition of drying time of 3 minutes to prepare a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition (32).
  • a silicone-treated release sheet (trade name "MRF25”, thickness 25 ⁇ m, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 ⁇ m, one of which was treated with silicone.
  • the surfaces were bonded together to obtain a surface protective film (32). Aging was performed at room temperature for 5 days for evaluation.
  • the release sheet was peeled off immediately before the evaluation. The results are shown in Table 3.
  • Mn 10000, manufactured by Asahi Glass Co., Ltd.
  • Sanniks GP3000 Sanniks GP3000 (Sanyo Kasei Co., Ltd.)
  • Rometasulfonyl) imide (AS110, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 0.5 parts by weight, fluoropolymer Megafuck F-563 (manufactured by DIC) 0.1 parts by weight, Irganox1010 (manufactured by BASF) as an antioxidant. ) 0.5 parts by weight, 0.03 parts by weight of Nasem ferrous iron (manufactured by Nippon Kagaku Sangyo Co., Ltd.) as a catalyst is diluted with ethyl acetate so that the total solid content is 50% by weight, and a urethane-based pressure-sensitive adhesive is used. A solution was obtained.
  • the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 ⁇ m, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 ⁇ m, and the drying temperature is 130 ° C. , And dried under the condition of a drying time of 3 minutes to prepare a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition (33).
  • a silicone-treated release sheet (trade name "MRF25”, thickness 25 ⁇ m, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 ⁇ m, one of which was treated with silicone.
  • the surfaces were bonded together to obtain a surface protective film (33). Aging was performed at room temperature for 5 days for evaluation.
  • the release sheet was peeled off immediately before the evaluation. The results are shown in Table 3.
  • Mn 10000, manufactured by Asahi Glass Co., Ltd.
  • Sanniks GP3000 Sanniks GP3000 (Sanyo Kasei Co., Ltd.)
  • Rometasulfonyl) imide (AS110, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 0.5 parts by weight, fluoropolymer Megafuck F-563 (manufactured by DIC) 0.5 parts by weight, Irganox1010 (manufactured by BASF) as an antioxidant. ) 0.5 parts by weight, 0.03 parts by weight of Nasem ferrous iron (manufactured by Nippon Kagaku Sangyo Co., Ltd.) as a catalyst is diluted with ethyl acetate so that the total solid content is 50% by weight, and a urethane-based pressure-sensitive adhesive is used. A solution was obtained.
  • the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 ⁇ m, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 ⁇ m, and the drying temperature is 130 ° C. , Cure and dry under the condition of drying time of 3 minutes to prepare a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition (34).
  • a silicone-treated release sheet (trade name "MRF25”, thickness 25 ⁇ m, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 ⁇ m, one of which was treated with silicone.
  • the surfaces were bonded together to obtain a surface protective film (34). Aging was performed at room temperature for 5 days for evaluation.
  • the release sheet was peeled off immediately before the evaluation. The results are shown in Table 3.
  • Sanniks GP3000 Sanniks GP3000 (Sanyo Kasei Co., Ltd.)
  • isocyanate compound Coronate
  • romethanesulfonyl) imide AS110, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
  • fluorinated oligomer Megafuck F-563 manufactured by DIC
  • Irganox1010 manufactured by BASF
  • a catalyst diluted with ethyl acetate so that the total solid content is 50% by weight, urethane-based pressure-sensitive adhesive A solution was obtained.
  • the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 ⁇ m, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 ⁇ m, and the drying temperature is 130 ° C. , Cure and dry under the condition of drying time of 3 minutes to prepare a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition (35).
  • a silicone-treated release sheet (trade name "MRF25”, thickness 25 ⁇ m, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 ⁇ m, one of which was treated with silicone.
  • the surfaces were bonded together to obtain a surface protective film (35). Aging was performed at room temperature for 5 days for evaluation.
  • the release sheet was peeled off immediately before the evaluation. The results are shown in Table 3.
  • Mn 10000, manufactured by Asahi Glass Co., Ltd.
  • Sanniks GP3000 Sanniks GP3000 (Sanyo Kasei Co., Ltd.)
  • Rometasulfonyl) imide (AS110, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 0.5 parts by weight, fluoropolymer Megafuck F-569 (manufactured by DIC) 0.5 parts by weight, Irganox 1010 (manufactured by BASF) as an antioxidant. ) 0.5 parts by weight, 0.03 parts by weight of Nasem ferrous iron (manufactured by Nippon Kagaku Sangyo Co., Ltd.) as a catalyst is diluted with ethyl acetate so that the total solid content is 50% by weight, and a urethane-based pressure-sensitive adhesive is used. A solution was obtained.
  • the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 ⁇ m, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 ⁇ m, and the drying temperature is 130 ° C. , Cure and dry under the condition of drying time of 3 minutes to prepare a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition (36).
  • a silicone-treated release sheet (trade name "MRF25”, thickness 25 ⁇ m, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 ⁇ m, one of which was treated with silicone.
  • the surfaces were bonded together to obtain a surface protective film (36). Aging was performed at room temperature for 5 days for evaluation.
  • the release sheet was peeled off immediately before the evaluation. The results are shown in Table 3.
  • Sanniks GP3000 Sanniks GP3000 (Sanyo Kasei Co., Ltd.)
  • isocyanate compound Coronate
  • Rometasulfonyl) imide (AS110, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 0.5 parts by weight, fluoropolymer Megafuck F-552 (manufactured by DIC) 0.5 parts by weight, Irganox1010 (manufactured by BASF) as an antioxidant. ) 0.5 parts by weight, 0.03 parts by weight of Nasem ferrous iron (manufactured by Nippon Kagaku Sangyo Co., Ltd.) as a catalyst, diluted with ethyl acetate so that the total solid content is 50% by weight, urethane-based pressure-sensitive adhesive A solution was obtained.
  • the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 ⁇ m, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 ⁇ m, and the drying temperature is 130 ° C. , Cure and dry under the condition of drying time of 3 minutes to prepare a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition (37).
  • a silicone-treated release sheet (trade name "MRF25”, thickness 25 ⁇ m, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 ⁇ m, one of which was treated with silicone.
  • the surfaces were bonded together to obtain a surface protective film (37). Aging was performed at room temperature for 5 days for evaluation.
  • the release sheet was peeled off immediately before the evaluation. The results are shown in Table 3.
  • Sanniks GP3000 Sanniks GP3000 (Sanyo Kasei Co., Ltd.)
  • isocyanate compound Coronate
  • Rometasulfonyl) imide (AS110, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 0.5 parts by weight, fluoropolymer Megafuck F-559 (manufactured by DIC) 0.5 parts by weight, Irganox1010 (manufactured by BASF) as an antioxidant. ) 0.5 parts by weight, 0.03 parts by weight of Nasem ferrous iron (manufactured by Nippon Kagaku Sangyo Co., Ltd.) as a catalyst, diluted with ethyl acetate so that the total solid content is 50% by weight, urethane-based pressure-sensitive adhesive A solution was obtained.
  • the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 ⁇ m, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 ⁇ m, and the drying temperature is 130 ° C. , Cure and dry under the condition of drying time of 3 minutes to prepare a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition (38).
  • a silicone-treated release sheet (trade name "MRF25”, thickness 25 ⁇ m, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 ⁇ m, one of which was treated with silicone.
  • the surfaces were bonded together to obtain a surface protective film (38). Aging was performed at room temperature for 5 days for evaluation.
  • the release sheet was peeled off immediately before the evaluation. The results are shown in Table 3.
  • Mn 10000, manufactured by Asahi Glass Co., Ltd.
  • Sanniks GP3000 Sanniks GP3000 (Sanyo Kasei Co., Ltd.)
  • Rometasulfonyl) imide (AS110, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 0.5 parts by weight, fluoropolymer Megafuck F-556 (manufactured by DIC) 0.5 parts by weight, Irganox 1010 (manufactured by BASF) as an antioxidant. ) 0.5 parts by weight, 0.03 parts by weight of Nasem ferrous iron (manufactured by Nippon Kagaku Sangyo Co., Ltd.) as a catalyst is diluted with ethyl acetate so that the total solid content is 50% by weight, and a urethane-based pressure-sensitive adhesive is used. A solution was obtained.
  • the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 ⁇ m, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 ⁇ m, and the drying temperature is 130 ° C. , And dried under the condition of a drying time of 3 minutes to prepare a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition (39).
  • a silicone-treated release sheet (trade name "MRF25”, thickness 25 ⁇ m, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 ⁇ m, one of which was treated with silicone.
  • the surfaces were bonded together to obtain a surface protective film (39). Aging was performed at room temperature for 5 days for evaluation.
  • the release sheet was peeled off immediately before the evaluation. The results are shown in Table 3.
  • isocyanate compound (Coronate HX: C / HX, manufactured by Nippon Polyurethane Co., Ltd.) 10.2 parts by weight as a cross-linking agent, 1-ethyl-3-methylimidazolium bis (trifluo) as an ionic compound Lomethanesulfonyl) imide (AS110, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 0.5 parts by weight, hydroxyl group-containing reactive silicone oil X-22-4015 (manufactured by Shinetsu Chemical Industry Co., Ltd.) 0.1 parts by weight, as an antioxidant.
  • isocyanate compound Coronate HX: C / HX, manufactured by Nippon Polyurethane Co., Ltd.
  • 1-ethyl-3-methylimidazolium bis (trifluo) as an ionic compound Lomethanesulfonyl) imide (AS110, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
  • Irganox 1010 manufactured by BASF
  • 0.5 parts by weight and 0.03 part by weight of Nasem ferric iron manufactured by Nippon Kagaku Sangyo Co., Ltd.
  • Urethane-based pressure-sensitive adhesive solution was obtained.
  • the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 ⁇ m, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 ⁇ m, and the drying temperature is 130 ° C.
  • the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 ⁇ m, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 ⁇ m, and the drying temperature is 130 ° C. , Cure and dry under the condition of drying time of 3 minutes to prepare a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition (41).
  • a silicone-treated release sheet (trade name "MRF25”, thickness 25 ⁇ m, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 ⁇ m, one of which was treated with silicone.
  • the surfaces were bonded together to obtain a surface protective film (41). Aging was performed at room temperature for 5 days for evaluation.
  • the release sheet was peeled off immediately before the evaluation. The results are shown in Table 4.
  • the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 ⁇ m, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 ⁇ m, and the drying temperature is 130 ° C. , And dried under the condition of a drying time of 3 minutes to prepare a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition (42).
  • a silicone-treated release sheet (trade name "MRF25”, thickness 25 ⁇ m, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 ⁇ m, one of which was treated with silicone.
  • the surfaces were bonded together to obtain a surface protective film (42). Aging was performed at room temperature for 5 days for evaluation.
  • the release sheet was peeled off immediately before the evaluation. The results are shown in Table 4.
  • the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 ⁇ m, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 ⁇ m, and the drying temperature is 130 ° C. , Cure and dry under the condition of drying time of 3 minutes to prepare a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition (43).
  • a silicone-treated release sheet (trade name "MRF25”, thickness 25 ⁇ m, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 ⁇ m, one of which was treated with silicone.
  • the surfaces were bonded together to obtain a surface protective film (43). Aging was performed at room temperature for 5 days for evaluation.
  • the release sheet was peeled off immediately before the evaluation. The results are shown in Table 4.
  • the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 ⁇ m, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 ⁇ m, and the drying temperature is 130 ° C. , Cure and dry under the condition of drying time of 3 minutes to prepare a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition (44).
  • a silicone-treated release sheet (trade name "MRF25”, thickness 25 ⁇ m, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 ⁇ m, one of which was treated with silicone.
  • the surfaces were bonded together to obtain a surface protective film (44). Aging was performed at room temperature for 5 days for evaluation.
  • the release sheet was peeled off immediately before the evaluation. The results are shown in Table 4.
  • the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 ⁇ m, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 ⁇ m, and the drying temperature is 130 ° C. , Cure and dry under the condition of drying time of 3 minutes to prepare a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition (45).
  • a silicone-treated release sheet (trade name "MRF25”, thickness 25 ⁇ m, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 ⁇ m, one of which was treated with silicone.
  • the surfaces were bonded together to obtain a surface protective film (45). Aging was performed at room temperature for 5 days for evaluation.
  • the release sheet was peeled off immediately before the evaluation. The results are shown in Table 4.
  • the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 ⁇ m, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 ⁇ m, and the drying temperature is 130 ° C. , And dried under the condition of a drying time of 3 minutes to prepare a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition (46).
  • a silicone-treated release sheet (trade name "MRF25”, thickness 25 ⁇ m, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 ⁇ m, one of which was treated with silicone.
  • the surfaces were bonded together to obtain a surface protective film (46). Aging was performed at room temperature for 5 days for evaluation.
  • the release sheet was peeled off immediately before the evaluation. The results are shown in Table 4.
  • the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 ⁇ m, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 ⁇ m, and the drying temperature is 130 ° C. , And dried under the condition of a drying time of 3 minutes to prepare a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition (47).
  • a silicone-treated release sheet (trade name "MRF25”, thickness 25 ⁇ m, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 ⁇ m, one of which was treated with silicone.
  • the surfaces were bonded together to obtain a surface protective film (47). Aging was performed at room temperature for 5 days for evaluation.
  • the release sheet was peeled off immediately before the evaluation. The results are shown in Table 4.
  • the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 ⁇ m, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 ⁇ m, and the drying temperature is 130 ° C. , Cure and dry under the condition of drying time of 3 minutes to prepare a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition (48).
  • a silicone-treated release sheet (trade name "MRF25”, thickness 25 ⁇ m, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 ⁇ m, one of which was treated with silicone.
  • the surfaces were bonded together to obtain a surface protective film (48). Aging was performed at room temperature for 5 days for evaluation.
  • the release sheet was peeled off immediately before the evaluation. The results are shown in Table 4.
  • the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 ⁇ m, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 ⁇ m, and the drying temperature is 130 ° C. , Cure and dry under the condition of drying time of 3 minutes to prepare a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition (49).
  • a silicone-treated release sheet (trade name "MRF25”, thickness 25 ⁇ m, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 ⁇ m, one of which was treated with silicone.
  • the surfaces were bonded together to obtain a surface protective film (49). Aging was performed at room temperature for 5 days for evaluation.
  • the release sheet was peeled off immediately before the evaluation. The results are shown in Table 4.
  • the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 ⁇ m, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 ⁇ m, and the drying temperature is 130 ° C. , Cure and dry under the condition of drying time of 3 minutes to prepare a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition (50).
  • a silicone-treated release sheet (trade name "MRF25”, thickness 25 ⁇ m, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 ⁇ m, one of which was treated with silicone.
  • the surfaces were bonded together to obtain a surface protective film (50). Aging was performed at room temperature for 5 days for evaluation.
  • the release sheet was peeled off immediately before the evaluation. The results are shown in Table 4.
  • the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 ⁇ m, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 ⁇ m, and the drying temperature is 130 ° C. , Cure and dry under the condition of drying time of 3 minutes to prepare a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition (51).
  • a silicone-treated release sheet (trade name "MRF25”, thickness 25 ⁇ m, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 ⁇ m, one of which was treated with silicone.
  • the surfaces were bonded together to obtain a surface protective film (51). Aging was performed at room temperature for 5 days for evaluation.
  • the release sheet was peeled off immediately before the evaluation. The results are shown in Table 4.
  • urethane-based pressure-sensitive adhesive solution Diluted with ethyl acetate so that the total solid content was 50% by weight to obtain a urethane-based pressure-sensitive adhesive solution. Then, the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 ⁇ m, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 ⁇ m, and the drying temperature is 130 ° C. , Cure and dry under the condition of drying time of 3 minutes to prepare a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition (52).
  • the surface of the obtained pressure-sensitive adhesive layer was treated with a silicone-treated release sheet (trade name "MRF25", thickness 25 ⁇ m, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 ⁇ m, one of which was treated with silicone.
  • the surfaces were bonded together to obtain a surface protective film (52). Aging was performed at room temperature for 5 days for evaluation. The release sheet was peeled off immediately before the evaluation. The results are shown in Table 4.
  • the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 ⁇ m, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 ⁇ m, and the drying temperature is 130 ° C. , Cure and dry under the condition of drying time of 3 minutes to prepare a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition (C1).
  • a silicone-treated release sheet (trade name "MRF25”, thickness 25 ⁇ m, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 ⁇ m, one of which was treated with silicone.
  • the surfaces were bonded together to obtain a surface protective film (C1). Aging was performed at room temperature for 5 days for evaluation.
  • the release sheet was peeled off immediately before the evaluation. The results are shown in Table 5.
  • [Comparative Example 2] 50 parts by weight of urethane prepolymer, 35 parts by weight of Preminol S3011 (Mn 10000, manufactured by Asahi Glass Co., Ltd.), which is a polyol having 3 hydroxyl groups, and Sanniks GP3000 (Sanyo Kasei Co., Ltd.), which is a polyol having 3 hydroxyl groups.
  • isocyanate compound Coronate HX: C / HX, Japan
  • polyurethane manufactured by Polyurethane
  • Irganox1010 manufactured by BASF
  • Nasem ferrous iron manufactured by Nippon Kagaku
  • urethane-based pressure-sensitive adhesive solution It was diluted with ethyl acetate so that the solid content was 50% by weight to obtain a urethane-based pressure-sensitive adhesive solution. Then, the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 ⁇ m, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 ⁇ m, and the drying temperature is 130 ° C. , Cure and dry under the condition of drying time of 3 minutes to prepare a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition (C2).
  • the surface of the obtained pressure-sensitive adhesive layer was treated with a silicone-treated release sheet (trade name "MRF25", thickness 25 ⁇ m, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 ⁇ m, one of which was treated with silicone.
  • the surfaces were bonded together to obtain a surface protective film (C2). Aging was performed at room temperature for 5 days for evaluation. The release sheet was peeled off immediately before the evaluation. The results are shown in Table 5.
  • Sanniks GP3000 Sanniks GP3000 (Sanyo Kasei Co., Ltd.)
  • RNA-based pressure-sensitive adhesive solution 0.03 part by weight of Nasem ferrous iron (manufactured by Nippon Kagaku Sangyo Co., Ltd.) was diluted with ethyl acetate so that the total solid content was 50% by weight to obtain a urethane-based pressure-sensitive adhesive solution. Then, the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 ⁇ m, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 ⁇ m, and the drying temperature is 130 ° C. , Cure and dry under the condition of drying time of 3 minutes to prepare a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition (C3).
  • a base material made of polyester resin trade name "T100-75S", thickness 75 ⁇ m, manufactured by Mitsubishi Chemical Co., Ltd.
  • the surface of the obtained pressure-sensitive adhesive layer was treated with a silicone-treated release sheet (trade name "MRF25", thickness 25 ⁇ m, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 ⁇ m, one of which was treated with silicone.
  • the surfaces were bonded together to obtain a surface protective film (C3). Aging was performed at room temperature for 5 days for evaluation. The release sheet was peeled off immediately before the evaluation. The results are shown in Table 5.
  • urethane-based pressure-sensitive adhesive solution It was diluted with ethyl acetate so that the solid content was 50% by weight to obtain a urethane-based pressure-sensitive adhesive solution. Then, the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 ⁇ m, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 ⁇ m, and the drying temperature is 130 ° C. , Cure and dry under the condition of drying time of 3 minutes to prepare a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition (C4).
  • a base material made of polyester resin trade name "T100-75S", thickness 75 ⁇ m, manufactured by Mitsubishi Chemical Co., Ltd.
  • the surface of the obtained pressure-sensitive adhesive layer was treated with a silicone-treated release sheet (trade name "MRF25", thickness 25 ⁇ m, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 ⁇ m, one of which was treated with silicone.
  • the surfaces were bonded together to obtain a surface protective film (C4). Aging was performed at room temperature for 5 days for evaluation. The release sheet was peeled off immediately before the evaluation. The results are shown in Table 5.
  • Mn 3000
  • isocyanate compound (Coronate HX: C / HX, manufactured by Nippon Polyurethane Co., Ltd.) 11.3 parts by weight as a cross-linking agent, Irganox 1010 (manufactured by BASF) 0.5 parts by weight as an antioxidant.
  • a catalyst 0.03 part by weight of Nasem ferrous iron (manufactured by Nippon Kagaku Sangyo Co., Ltd.) was diluted with ethyl acetate so that the total solid content was 50% by weight to obtain a urethane-based pressure-sensitive adhesive solution.
  • the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 ⁇ m, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 ⁇ m, and the drying temperature is 130 ° C. , Cure and dry under the condition of drying time of 3 minutes to prepare a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition (C5).
  • the surface of the obtained pressure-sensitive adhesive layer was treated with silicone on a release sheet (trade name "MRF25", thickness 25 ⁇ m, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 ⁇ m, one of which was treated with silicone. The surfaces were bonded together to obtain a surface protective film (C5). Aging was performed at room temperature for 5 days for evaluation. The release sheet was peeled off immediately before the evaluation. The results are shown in Table 5.
  • a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition (C7).
  • the surface of the obtained pressure-sensitive adhesive layer was treated with a silicone-treated release sheet (trade name "MRF25", thickness 25 ⁇ m, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 ⁇ m, one of which was treated with silicone.
  • the surfaces were bonded together to obtain a surface protective film (C7). Aging was performed at room temperature for 5 days for evaluation. The release sheet was peeled off immediately before the evaluation. The results are shown in Table 5.
  • [Comparative Example 8] 10 parts by weight of urethane prepolymer, 90 parts by weight of Preminol S3011 (Mn 10000, manufactured by Asahi Glass Co., Ltd.), which is a polyol having three hydroxyl groups as a polyol, and an isocyanate compound (Coronate HX: C / HX, Polyurethane Japan) as a cross-linking agent. ) 8.5 parts by weight, Irganox 1010 (manufactured by BASF) 0.5 parts by weight as an antioxidant, and 0.03 parts by weight of Nasem ferrous iron (manufactured by Nippon Kagaku Sangyo Co., Ltd.) as a catalyst, as a whole solid content.
  • Irganox 1010 manufactured by BASF
  • Nasem ferrous iron manufactured by Nippon Kagaku Sangyo Co., Ltd.
  • urethane-based pressure-sensitive adhesive solution was diluted with ethyl acetate so as to be 50% by weight to obtain a urethane-based pressure-sensitive adhesive solution. Then, the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 ⁇ m, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 ⁇ m, and the drying temperature is 130 ° C. , Cure and dry under the condition of drying time of 3 minutes to prepare a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition (C8).
  • a base material made of polyester resin (trade name "T100-75S", thickness 75 ⁇ m, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 ⁇ m, and the drying temperature is 130 ° C.
  • Cure and dry under the condition of drying time of 3 minutes to prepare a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition (C8).
  • the surface of the obtained pressure-sensitive adhesive layer was treated with a silicone-treated release sheet (trade name "MRF25", thickness 25 ⁇ m, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 ⁇ m, one of which was treated with silicone.
  • the surfaces were bonded together to obtain a surface protective film (C8). Aging was performed at room temperature for 5 days for evaluation. The release sheet was peeled off immediately before the evaluation. The results are shown in Table 5.
  • RNA-based pressure-sensitive adhesive solution 0.03 part by weight of Nasem ferrous iron (manufactured by Nippon Kagaku Sangyo Co., Ltd.) was diluted with ethyl acetate so that the total solid content was 50% by weight to obtain a urethane-based pressure-sensitive adhesive solution. Then, the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 ⁇ m, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 ⁇ m, and the drying temperature is 130 ° C. , Cure and dry under the condition of drying time of 3 minutes to prepare a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition (C9).
  • a base material made of polyester resin trade name "T100-75S", thickness 75 ⁇ m, manufactured by Mitsubishi Chemical Co., Ltd.
  • the surface of the obtained pressure-sensitive adhesive layer was treated with a silicone-treated release sheet (trade name "MRF25", thickness 25 ⁇ m, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 ⁇ m, one of which was treated with silicone.
  • the surfaces were bonded together to obtain a surface protective film (C9). Aging was performed at room temperature for 5 days for evaluation. The release sheet was peeled off immediately before the evaluation. The results are shown in Table 5.
  • Sanniks GP3000 Sanniks GP3000 (Sanyo Kasei Co., Ltd.)
  • RNA-based iron manufactured by Nippon Kagaku Sangyo Co., Ltd.
  • ethyl acetate ethyl acetate
  • the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 ⁇ m, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 ⁇ m, and the drying temperature is 130 ° C.
  • the surface of the obtained pressure-sensitive adhesive layer was treated with a silicone-treated release sheet (trade name "MRF25", thickness 25 ⁇ m, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 ⁇ m, one of which was treated with silicone.
  • the surfaces were bonded together to obtain a surface protective film (C10). Aging was performed at room temperature for 5 days for evaluation. The release sheet was peeled off immediately before the evaluation. The results are shown in Table 5.
  • Example 53 to 104 For each of the surface protective films with separators obtained in Examples 1 to 52, the separator was peeled off and attached to a polarizing plate (manufactured by Nitto Denko Corporation, trade name "TEG1465DUHC”) which is an optical member, and the surface protective film was attached. An optical member to which was attached was obtained.
  • a polarizing plate manufactured by Nitto Denko Corporation, trade name "TEG1465DUHC”
  • Examples 105 to 156 For each of the surface protective films with separators obtained in Examples 1 to 52, the separator was peeled off and attached to a conductive film (manufactured by Nitto Denko Corporation, trade name "Electrica V270L-TFMP") which is an electronic member. , An electronic member to which a surface protective film was attached was obtained.
  • a conductive film manufactured by Nitto Denko Corporation, trade name "Electrica V270L-TFMP”
  • the surface protective film of the present invention can be used for any suitable application.
  • the surface protective film of the present invention is preferably used for surface protection of optical members and electronic members.

Abstract

Provided is a surface protective film capable of increasing the film thickness of an adhesive layer, demonstrating easy peelability, and realizing low haze. Also provided is an optical member and an electronic member having such surface protective film attached thereto.　A surface protective film according to an embodiment of the present invention includes a urethane adhesive layer. The urethane adhesive layer is composed of a urethane adhesive formed of a urethane adhesive composition. The urethane adhesive composition includes a urethane prepolymer P, a polyol A, and a multifunctional isocyanate compound B. The weight ratio between P and A is P/A = (50 to 99)/(1 to 50). The polyol A includes a first polyol A1 having a number average molecular weight Mn of 5,000 to 20,000, and a second polyol A2 having a number average molecular weight Mn of 300 to 4,999. The weight ratio between A1 and A2 satisfies 1.0 ≤ (A1/A2) ≤ 3.5.

Description

表面保護フィルムSurface protection film
　本発明は表面保護フィルムに関する。 The present invention relates to a surface protective film.
　光学部材や電子部材は、加工、組立、検査、輸送などの際の表面の傷付き防止のために、表面保護フィルムが貼着される。このような表面保護フィルムは、表面保護の必要がなくなった時点で、光学部材や電子部材から剥離される（特許文献１）。 A surface protective film is attached to the optical member and electronic member to prevent surface scratches during processing, assembly, inspection, transportation, etc. Such a surface protective film is peeled off from an optical member or an electronic member when the need for surface protection is eliminated (Patent Document 1).
　このような表面保護フィルムが貼着された光学部材や電子部材において、上記のように表面保護フィルムを剥離しようとする際には、表面保護フィルムと光学部材や電子部材との界面でのみスムーズに剥離できることが重要である。また有機ＥＬディスプレイなど、段差の大きいディスプレイを保護する際には、その段差に追従できるよう、粘着剤層の厚膜化が必要とされている。 In an optical member or an electronic member to which such a surface protective film is attached, when the surface protective film is to be peeled off as described above, it is smooth only at the interface between the surface protective film and the optical member or the electronic member. It is important to be able to peel off. Further, when protecting a display having a large step such as an organic EL display, it is necessary to thicken the adhesive layer so as to follow the step.
　表面保護フィルムが備える粘着剤層としては各種粘着剤から構成される粘着剤層が知られている。リワーク性、濡れ性、透明性に優れるという点で、光学部材や電子部材に貼着される表面保護フィルムが備える粘着剤層としては、ウレタン系粘着剤から構成されるウレタン系粘着剤層が好ましく採用されている。 As the pressure-sensitive adhesive layer provided in the surface protective film, a pressure-sensitive adhesive layer composed of various pressure-sensitive adhesives is known. A urethane-based pressure-sensitive adhesive layer composed of a urethane-based pressure-sensitive adhesive is preferable as the pressure-sensitive adhesive layer provided on the surface protective film attached to the optical member or the electronic member in terms of excellent reworkability, wettability, and transparency. It has been adopted.
　ウレタン系粘着剤の製造方法としては、ウレタンプレポリマーを用いずに、ポリオールと多官能イソシアネートをダイレクトに反応させてウレタン粘着剤を製造するワンショット法と、ウレタンプレポリマーと多官能イソシアネートを反応させてウレタン粘着剤を製造するプレポリマー法との、２種類の製造方法が存在する。 As a method for producing a urethane-based pressure-sensitive adhesive, a one-shot method for producing a urethane pressure-sensitive adhesive by directly reacting a polyol with a polyfunctional isocyanate without using a urethane prepolymer, and a reaction between the urethane prepolymer and the polyfunctional isocyanate are performed. There are two types of manufacturing methods, the prepolymer method for manufacturing urethane pressure-sensitive adhesives.
　ワンショット法では、数平均分子量が１００００付近のポリオールを用いるため、多官能イソシアネートとの反応でダイレクトに硬化させることによって架橋密度が高くなり、軽剥離性を確保し得る。一方、ワンショット法では、粘着剤溶液の粘度が低いため、厚膜化には適していない(特許文献２）。 In the one-shot method, since a polyol having a number average molecular weight of around 10,000 is used, the crosslink density is increased by direct curing by reaction with polyfunctional isocyanate, and light peelability can be ensured. On the other hand, the one-shot method is not suitable for thickening the film because the viscosity of the pressure-sensitive adhesive solution is low (Patent Document 2).
　プレポリマー法では、粘着剤溶液の粘度が高いため、厚膜化には適している。一方、プレポリマー法では、多官能イソシアネートとの反応で硬化させることによって得られる粘着剤の架橋密度が低いため、軽剥離性を確保し難い。このため、数平均分子量が３００以下のポリオールを併用することによって軽剥離性を確保する技術が報告されている（特許文献３）。 The prepolymer method has a high viscosity of the adhesive solution, so it is suitable for thickening the film. On the other hand, in the prepolymer method, it is difficult to secure light peelability because the crosslink density of the pressure-sensitive adhesive obtained by curing by reaction with polyfunctional isocyanate is low. Therefore, a technique for ensuring light exfoliation by using a polyol having a number average molecular weight of 300 or less in combination has been reported (Patent Document 3).
　しかしながら、ウレタンプレポリマーと数平均分子量が３００以下のポリオールを併用すると、両者の分子量が大きく乖離しているため、相溶性が悪くなってしまい、粘着剤のヘイズ値が大きくなってしまうという問題が生じる。粘着剤のヘイズ値が大きくなってしまうと、表面保護フィルムの品質低下を招くだけでなく、例えば、光学部材や電子部材に貼り合わされる表面保護フィルムにおいては、検査性の低下に繋がってしまう。 However, when urethane prepolymer and a polyol having a number average molecular weight of 300 or less are used in combination, there is a problem that the molecular weights of the two are greatly different from each other, so that the compatibility is deteriorated and the haze value of the adhesive is increased. Occurs. If the haze value of the pressure-sensitive adhesive becomes large, not only the quality of the surface protective film deteriorates, but also, for example, in the surface protective film bonded to the optical member or the electronic member, the inspectability is deteriorated.
特開２０１６－１７１０９号公報Japanese Unexamined Patent Publication No. 2016-17109 特許５５０１４８９号公報Japanese Patent No. 5501489 特開２０１８－６２５９５号公報Japanese Unexamined Patent Publication No. 2018-62595
　本発明の課題は、粘着剤層の厚膜化が可能であり、軽剥離性を発現でき、低ヘイズを実現できる、表面保護フィルムを提供することにある。また、そのような表面保護フィルムが貼着された光学部材および電子部材を提供することにある。 An object of the present invention is to provide a surface protective film capable of thickening the pressure-sensitive adhesive layer, exhibiting light peelability, and achieving low haze. Another object of the present invention is to provide an optical member and an electronic member to which such a surface protective film is attached.
　本発明の実施形態による表面保護フィルムは、
　ウレタン系粘着剤層を含む表面保護フィルムであって、
　該ウレタン系粘着剤層は、ウレタン系粘着剤組成物から形成されるウレタン系粘着剤から構成され、
　該ウレタン系粘着剤組成物が、ウレタンプレポリマーＰとポリオールＡと多官能イソシアネート化合物Ｂを含み、
　該ウレタンプレポリマーＰと該ポリオールＡの重量比が、Ｐ：Ａ＝（５０～９９）：（１～５０）であり、
　該ポリオールＡは、数平均分子量Ｍｎが５０００～２００００の第１のポリオールＡ１と数平均分子量Ｍｎが３００～４９９９の第２のポリオールＡ２を含み、
　該第１のポリオールＡ１と該第２のポリオールＡ２との重量比率が、１．０≦（Ａ１／Ａ２）≦３．５である。 The surface protective film according to the embodiment of the present invention is
A surface protective film containing a urethane-based adhesive layer,
The urethane-based pressure-sensitive adhesive layer is composed of a urethane-based pressure-sensitive adhesive formed from a urethane-based pressure-sensitive adhesive composition.
The urethane-based pressure-sensitive adhesive composition contains a urethane prepolymer P, a polyol A, and a polyfunctional isocyanate compound B.
The weight ratio of the urethane prepolymer P to the polyol A is P: A = (50 to 99) :( 1 to 50).
The polyol A contains a first polyol A1 having a number average molecular weight Mn of 5000 to 20000 and a second polyol A2 having a number average molecular weight Mn of 300 to 4999.
The weight ratio of the first polyol A1 to the second polyol A2 is 1.0 ≦ (A1 / A2) ≦ 3.5.
　１つの実施形態においては、上記ウレタン系粘着剤組成物がイオン性化合物を含み、上記ウレタンプレポリマーＰと上記ポリオールＡの合計量に対する該イオン性化合物の含有割合が、０．０５重量％以上である。 In one embodiment, the urethane-based pressure-sensitive adhesive composition contains an ionic compound, and the content ratio of the ionic compound to the total amount of the urethane prepolymer P and the polyol A is 0.05% by weight or more. be.
　１つの実施形態においては、上記ウレタン系粘着剤組成物がフッ素系添加剤およびシリコーン系添加剤からなる群から選ばれる少なくとも１種を含み、上記ウレタンプレポリマーＰと上記ポリオールＡの合計量に対する該フッ素系添加剤および該シリコーン系添加剤の合計量の含有割合が、０．０１重量％以上である。 In one embodiment, the urethane-based pressure-sensitive adhesive composition comprises at least one selected from the group consisting of a fluorine-based additive and a silicone-based additive, and the urethane prepolymer P and the polyol A are added to the total amount. The content ratio of the total amount of the fluorine-based additive and the silicone-based additive is 0.01% by weight or more.
　１つの実施形態においては、上記第１のポリオールＡ１と上記第２のポリオールＡ２との重量比率が、１．０≦（Ａ１／Ａ２）≦２．０である。 In one embodiment, the weight ratio of the first polyol A1 to the second polyol A2 is 1.0 ≦ (A1 / A2) ≦ 2.0.
　１つの実施形態においては、上記ウレタン系粘着剤層をガラス板に貼り合わせて２３℃で３０分後に、該ガラス板から剥離角度１８０度、剥離速度３００ｍｍ／分によって剥離した際の剥離力が、０．５ｇｆ／２５ｍｍ～２．０ｇｆ／２５ｍｍである。 In one embodiment, the peeling force when the urethane-based pressure-sensitive adhesive layer is bonded to a glass plate and peeled from the glass plate at 23 ° C. for 30 minutes at a peeling angle of 180 degrees and a peeling speed of 300 mm / min is determined. It is 0.5 gf / 25 mm to 2.0 gf / 25 mm.
　１つの実施形態においては、上記ウレタン系粘着剤層をガラス板に貼り合わせて２３℃で２４時間後に該ガラス板から剥離角度１８０度、剥離速度０．３ｍ／分によって剥離した後の、該ガラス板に対する残留接着率が、８０％以上である。 In one embodiment, the urethane adhesive layer is attached to a glass plate and peeled from the glass plate at 23 ° C. for 24 hours at a peeling angle of 180 degrees and a peeling speed of 0.3 m / min, and then the glass is peeled off. The residual adhesion rate to the plate is 80% or more.
　本発明の実施形態による光学部材は、本発明の実施形態による表面保護フィルムが貼着されたものである。 The optical member according to the embodiment of the present invention is the one to which the surface protective film according to the embodiment of the present invention is attached.
　本発明の実施形態による電子部材は、本発明の実施形態による表面保護フィルムが貼着されたものである。 The electronic member according to the embodiment of the present invention has a surface protective film according to the embodiment of the present invention attached.
　本発明によれば、粘着剤層の厚膜化が可能であり、軽剥離性を発現でき、低ヘイズを実現できる、表面保護フィルムを提供することができる。また、そのような表面保護フィルムが貼着された光学部材および電子部材を提供することができる。 According to the present invention, it is possible to provide a surface protective film capable of thickening the pressure-sensitive adhesive layer, exhibiting light peelability, and realizing low haze. Further, it is possible to provide an optical member and an electronic member to which such a surface protective film is attached.
本発明の好ましい実施形態による表面保護フィルムの概略断面図である。FIG. 3 is a schematic cross-sectional view of a surface protective film according to a preferred embodiment of the present invention.
≪≪１．表面保護フィルム≫≫
　本発明の実施形態による表面保護フィルムは、ウレタン系粘着剤層を含む。ウレタン系粘着剤層の粘着面側には、本発明の効果を損なわない範囲で、任意の適切な、離型性を有する剥離ライナーが貼り合わせられていてもよい。 ≪≪1. Surface protection film ≫≫
The surface protective film according to the embodiment of the present invention includes a urethane-based pressure-sensitive adhesive layer. An arbitrary appropriate release liner having releasability may be attached to the adhesive surface side of the urethane-based pressure-sensitive adhesive layer as long as the effects of the present invention are not impaired.
　本発明の実施形態による表面保護フィルムは、好ましくは、基材層とウレタン系粘着剤層とを有する。基材層は、１層のみであってもよいし、２層以上であってもよい。ウレタン系粘着剤層は、１層のみであってもよいし、２層以上であってもよい。本発明の表面保護フィルムは、基材層とウレタン系粘着剤層の他に、本発明の効果を損なわない範囲で、任意の適切なその他の層を有していても良い。 The surface protective film according to the embodiment of the present invention preferably has a base material layer and a urethane-based pressure-sensitive adhesive layer. The base material layer may be only one layer or two or more layers. The urethane-based pressure-sensitive adhesive layer may be only one layer or may be two or more layers. The surface protective film of the present invention may have any suitable other layer in addition to the base material layer and the urethane-based pressure-sensitive adhesive layer as long as the effects of the present invention are not impaired.
　図１は、本発明の好ましい実施形態による表面保護フィルムの概略断面図である。表面保護フィルム１０は、基材層１と粘着剤層２を備える。本発明の表面保護フィルムは、例えば、剥離ライナーなど、必要に応じて、任意の適切な他の層をさらに有していてもよい（図示せず）。 FIG. 1 is a schematic cross-sectional view of a surface protective film according to a preferred embodiment of the present invention. The surface protective film 10 includes a base material layer 1 and an adhesive layer 2. The surface protective film of the present invention may further have any suitable other layer, for example, a release liner, if necessary (not shown).
　基材層１の粘着剤層２を付設しない面に対しては、巻戻しが容易な巻回体の形成などを目的として、例えば、基材層に、脂肪酸アミド、ポリエチレンイミン、長鎖アルキル系添加剤等を添加して離型処理を行ったり、シリコーン系、長鎖アルキル系、フッ素系などの任意の適切な剥離剤からなるコート層を設けたりすることができる。 For the surface of the base material layer 1 to which the pressure-sensitive adhesive layer 2 is not attached, for the purpose of forming a wound body that can be easily rewound, for example, a fatty acid amide, polyethyleneimine, or a long-chain alkyl system is applied to the base material layer. It is possible to add an additive or the like to perform a mold release treatment, or to provide a coat layer made of any suitable release agent such as silicone-based, long-chain alkyl-based, and fluorine-based.
　ウレタン系粘着剤層の粘着面側に備え得る剥離ライナーとしては、例えば、紙やプラスチックフィルム等の基材（ライナー基材）の表面がシリコーン処理された剥離ライナー、紙やプラスチックフィルム等の基材（ライナー基材）の表面がポリオレフィン系樹脂によりラミネートされた剥離ライナーが挙げられる。 Examples of the release liner that can be provided on the adhesive surface side of the urethane adhesive layer include a release liner in which the surface of a substrate (liner substrate) such as paper or plastic film is treated with silicone, or a substrate such as paper or plastic film. Examples thereof include a release liner in which the surface of the (liner base material) is laminated with a polyolefin resin.
　剥離ライナーが備える基材としてのプラスチックフィルムとしては、例えば、ポリエチレンフィルム、ポリプロピレンフィルム、ポリブテンフィルム、ポリブタジエンフィルム、ポリメチルペンテンフィルム、ポリ塩化ビニルフィルム、塩化ビニル共重合体フィルム、ポリエチレンテレフタレートフィルム、ポリブチレンテレフタレートフィルム、ポリウレタンフィルム、エチレン－酢酸ビニル共重合体フィルムなどが挙げられる。 Examples of the plastic film as the base material of the release liner include polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate film, and polybutylene. Examples thereof include a terephthalate film, a polyurethane film, and an ethylene-vinyl acetate copolymer film.
　剥離ライナーの厚みは、好ましくは１μｍ～５００μｍであり、より好ましくは３μｍ～４５０μｍであり、さらに好ましくは５μｍ～４００μｍであり、特に好ましくは１０μｍ～３００μｍである。 The thickness of the release liner is preferably 1 μm to 500 μm, more preferably 3 μm to 450 μm, further preferably 5 μm to 400 μm, and particularly preferably 10 μm to 300 μm.
　本発明の実施形態による表面保護フィルムの厚みは、用途に応じて、任意の適切な厚みに設定し得る。代表的には、好ましくは１０μｍ～３００μｍであり、より好ましくは１５μｍ～２５０μｍであり、さらに好ましくは２０μｍ～２００μｍであり、特に好ましくは２５μｍ～１５０μｍである。 The thickness of the surface protective film according to the embodiment of the present invention can be set to an arbitrary appropriate thickness depending on the intended use. Typically, it is preferably 10 μm to 300 μm, more preferably 15 μm to 250 μm, still more preferably 20 μm to 200 μm, and particularly preferably 25 μm to 150 μm.
　本発明の実施形態による表面保護フィルムにおいては、ウレタン系粘着剤層の厚膜化が可能である。したがって、本発明の表面保護フィルムに含まれるウレタン系粘着剤層の厚みは、好ましくは１μｍ～１５０μｍであり、より好ましくは５μｍ～１５０μｍであり、さらに好ましくは１０μｍ～１５０μｍであり、さらに好ましくは２０μｍ～１５０μｍであり、さらに好ましくは３０μｍ～１５０μｍであり、さらに好ましくは４０μｍ～１５０μｍであり、さらに好ましくは５０μｍ～１５０μｍであり、特に好ましくは６０μｍ～１５０μｍであり、最も好ましくは６５μｍ～１５０μｍである。このようにウレタン系粘着剤層の厚膜化が可能となれば、本発明の実施形態による表面保護フィルムは、例えば、有機ＥＬディスプレイなど、段差の大きいディスプレイを保護する際に、その段差に良好に追従し得る。 In the surface protective film according to the embodiment of the present invention, the urethane-based pressure-sensitive adhesive layer can be thickened. Therefore, the thickness of the urethane-based pressure-sensitive adhesive layer contained in the surface protective film of the present invention is preferably 1 μm to 150 μm, more preferably 5 μm to 150 μm, still more preferably 10 μm to 150 μm, still more preferably 20 μm. It is ~ 150 μm, more preferably 30 μm to 150 μm, still more preferably 40 μm to 150 μm, still more preferably 50 μm to 150 μm, particularly preferably 60 μm to 150 μm, and most preferably 65 μm to 150 μm. If the urethane-based pressure-sensitive adhesive layer can be thickened in this way, the surface protective film according to the embodiment of the present invention is good for the step when protecting a display having a large step such as an organic EL display. Can follow.
　本発明の実施形態による表面保護フィルムは、軽剥離性を発現し得る。本発明の表面保護フィルムは、それが含むウレタン系粘着剤層をガラス板に貼り合わせて２３℃で３０分後に、該ガラス板から剥離角度１８０度、剥離速度３００ｍｍ／分によって剥離した際の剥離力が、好ましくは０．５ｇｆ／２５ｍｍ～５．０ｇｆ／２５ｍｍであり、より好ましくは０．５ｇｆ／２５ｍｍ～４．０ｇｆ／２５ｍｍであり、さらに好ましくは０．５ｇｆ／２５ｍｍ～３．０ｇｆ／２５ｍｍであり、特に好ましくは０．５ｇｆ／２５ｍｍ～２．５ｇｆ／２５ｍｍであり、最も好ましくは０．５ｇｆ／２５ｍｍ～２．０ｇｆ／２５ｍｍである。上記剥離力が上記範囲内にあれば、本発明の実施形態による表面保護フィルムは、優れた軽剥離性を発現し得る。 The surface protective film according to the embodiment of the present invention can exhibit light peelability. The surface protective film of the present invention is peeled off when the urethane adhesive layer contained therein is bonded to a glass plate and peeled off from the glass plate at a peeling angle of 180 degrees and a peeling speed of 300 mm / min after 30 minutes at 23 ° C. The force is preferably 0.5 gf / 25 mm to 5.0 gf / 25 mm, more preferably 0.5 gf / 25 mm to 4.0 gf / 25 mm, and even more preferably 0.5 gf / 25 mm to 3.0 gf / 25 mm. It is particularly preferably 0.5 gf / 25 mm to 2.5 gf / 25 mm, and most preferably 0.5 gf / 25 mm to 2.0 gf / 25 mm. When the peeling force is within the above range, the surface protective film according to the embodiment of the present invention can exhibit excellent light peeling property.
　本発明の実施形態による表面保護フィルムは、低ヘイズを実現し得る。本発明の表面保護フィルムは、それが含むウレタン系粘着剤層のヘイズが、好ましくは４．５％以下であり、より好ましくは４．０％以下であり、さらに好ましくは３．５％以下であり、特に好ましくは３．０％以下であり、最も好ましくは２．５％以下である。上記ヘイズが上記範囲内にあれば、本発明の実施形態による表面保護フィルムは、優れた低ヘイズを実現でき、例えば、優れた検査性を発現し得る。 The surface protective film according to the embodiment of the present invention can realize low haze. The surface protective film of the present invention has a haze of the urethane-based pressure-sensitive adhesive layer contained therein, preferably 4.5% or less, more preferably 4.0% or less, still more preferably 3.5% or less. Yes, particularly preferably 3.0% or less, and most preferably 2.5% or less. When the haze is within the above range, the surface protective film according to the embodiment of the present invention can realize excellent low haze, and can exhibit excellent inspectability, for example.
　本発明の実施形態による表面保護フィルムは、それが含むウレタン系粘着剤層をガラス板に貼り合わせて２３℃で２４時間後に該ガラス板から剥離角度１８０度、剥離速度０．３ｍ／分によって剥離した後の、該ガラス板に対する残留接着率が、好ましくは６０％以上であり、より好ましくは７０％以上であり、さらに好ましくは８０％以上であり、特に好ましくは８５％以上であり、最も好ましくは９０％以上である。上記残留接着率が上記範囲内にあれば、本発明の実施形態による表面保護フィルムは、糊残り性を低減し得る。 The surface protective film according to the embodiment of the present invention is peeled from the glass plate at a peeling angle of 180 degrees and a peeling speed of 0.3 m / min 24 hours after the urethane adhesive layer contained therein is attached to the glass plate at 23 ° C. The residual adhesion ratio to the glass plate is preferably 60% or more, more preferably 70% or more, further preferably 80% or more, particularly preferably 85% or more, and most preferably. Is 90% or more. When the residual adhesive ratio is within the above range, the surface protective film according to the embodiment of the present invention can reduce the adhesive residue property.
　本発明の実施形態による表面保護フィルムは、それが含むウレタン系粘着剤層をガラス板に貼り合わせて２３℃で２４時間後に該ガラス板から剥離角度１５０度、剥離速度３０ｍ／分によって剥離した際の剥離帯電圧が、好ましくは１５ｋＶ以下であり、より好ましくは１０ｋＶ以下であり、さらに好ましくは５ｋＶ以下であり、特に好ましくは２ｋＶ以下であり、最も好ましくは１ｋＶ以下である。上記剥離帯電圧が上記範囲内にあれば、本発明の実施形態による表面保護フィルムは、剥離の際の帯電を効果的に防止し得る。 The surface protective film according to the embodiment of the present invention is obtained when the urethane adhesive layer contained therein is attached to a glass plate and peeled from the glass plate at 23 ° C. for 24 hours at a peeling angle of 150 degrees and a peeling speed of 30 m / min. The peeling band voltage is preferably 15 kV or less, more preferably 10 kV or less, further preferably 5 kV or less, particularly preferably 2 kV or less, and most preferably 1 kV or less. When the peeling band voltage is within the above range, the surface protective film according to the embodiment of the present invention can effectively prevent charging at the time of peeling.
≪１－１．ウレタン系粘着剤層≫
　ウレタン系粘着剤層はウレタン系粘着剤から構成される。ウレタン系粘着剤は、ウレタン系粘着剤組成物から形成される。すなわち、ウレタン系粘着剤組成物から形成されるウレタン系粘着剤が層形状を構成することによって粘着剤層となる。 << 1-1. Urethane adhesive layer ≫
The urethane-based pressure-sensitive adhesive layer is composed of a urethane-based pressure-sensitive adhesive. The urethane-based pressure-sensitive adhesive is formed from a urethane-based pressure-sensitive adhesive composition. That is, the urethane-based pressure-sensitive adhesive formed from the urethane-based pressure-sensitive adhesive composition forms a layer shape to form a pressure-sensitive adhesive layer.
　ウレタン系粘着剤は、ウレタン系粘着剤組成物から形成されるものとして規定し得る。これは、ウレタン系粘着剤は、ウレタン系粘着剤組成物が、加熱や紫外線照射などによって架橋反応などを起こすことにより、ウレタン系粘着剤となるため、ウレタン系粘着剤をその構造により直接特定することが不可能であり、また、およそ実際的でないという事情（「不可能・非実際的事情」）が存在するため、「ウレタン系粘着剤組成物から形成されるもの」との規定により、ウレタン系粘着剤を「物」として妥当に特定したものである。 The urethane-based pressure-sensitive adhesive can be defined as being formed from a urethane-based pressure-sensitive adhesive composition. This is because the urethane-based pressure-sensitive adhesive becomes a urethane-based pressure-sensitive adhesive when the urethane-based pressure-sensitive adhesive composition causes a cross-linking reaction or the like by heating or irradiation with ultraviolet rays, so that the urethane-based pressure-sensitive adhesive is directly specified by its structure. Since there are circumstances in which it is impossible and almost impractical (“impossible / impractical circumstances”), urethane is stipulated as “formed from a urethane-based pressure-sensitive adhesive composition”. The system adhesive is properly specified as a "thing".
　ウレタン系粘着剤層の厚みとしては、前述したように、本発明の表面保護フィルムにおいては、ウレタン系粘着剤層の厚膜化が可能であるため、好ましくは１μｍ～１５０μｍであり、より好ましくは５μｍ～１５０μｍであり、さらに好ましくは１０μｍ～１５０μｍであり、さらに好ましくは２０μｍ～１５０μｍであり、さらに好ましくは３０μｍ～１５０μｍであり、さらに好ましくは４０μｍ～１５０μｍであり、さらに好ましくは５０μｍ～１５０μｍであり、特に好ましくは６０μｍ～１５０μｍであり、最も好ましくは６５μｍ～１５０μｍである。このようにウレタン系粘着剤層の厚膜化が可能となれば、本発明の実施形態による表面保護フィルムは、例えば、有機ＥＬディスプレイなど、段差の大きいディスプレイを保護する際に、その段差に良好に追従し得る。 As described above, the thickness of the urethane-based pressure-sensitive adhesive layer is preferably 1 μm to 150 μm, more preferably, because the surface protective film of the present invention can be made thicker. It is 5 μm to 150 μm, more preferably 10 μm to 150 μm, still more preferably 20 μm to 150 μm, still more preferably 30 μm to 150 μm, still more preferably 40 μm to 150 μm, still more preferably 50 μm to 150 μm. Particularly preferably, it is 60 μm to 150 μm, and most preferably 65 μm to 150 μm. If the urethane-based pressure-sensitive adhesive layer can be thickened in this way, the surface protective film according to the embodiment of the present invention is good for the step when protecting a display having a large step such as an organic EL display. Can follow.
　ウレタン系粘着剤は、ウレタン系粘着剤組成物から形成される。このような形成方法としては、本発明の効果を損なわない範囲で、任意の適切な形成方法を採用し得る。このような形成方法としては、例えば、ウレタン系粘着剤組成物を任意の適切な基材フィルム（例えば、本発明の実施形態による表面保護フィルムにおける基材層）に直接付与して乾燥または硬化させる方法（直接法）、ウレタン系粘着剤組成物を剥離ライナーの表面（剥離面）に付与して乾燥または硬化させることで該表面上に形成したウレタン系粘着剤層を基材フィルム（例えば、本発明の実施形態による表面保護フィルムにおける基材層）に貼り合わせて該ウレタン系粘着剤層を転写する方法（転写法）が挙げられる。粘着剤層の投錨性の観点から、代表的には、直接法を好ましく採用し得る。 The urethane-based pressure-sensitive adhesive is formed from a urethane-based pressure-sensitive adhesive composition. As such a forming method, any appropriate forming method can be adopted as long as the effect of the present invention is not impaired. As such a forming method, for example, the urethane-based pressure-sensitive adhesive composition is directly applied to an arbitrary suitable base film (for example, the base layer in the surface protection film according to the embodiment of the present invention) and dried or cured. Method (direct method), a urethane-based pressure-sensitive adhesive composition formed on the surface (peeling surface) of a release liner by applying the urethane-based pressure-sensitive adhesive composition to the surface (peeling surface) and drying or curing the urethane-based pressure-sensitive adhesive layer is formed on a base film (for example, a book). A method (transfer method) of transferring the urethane-based pressure-sensitive adhesive layer by adhering it to a base material layer in the surface protective film according to the embodiment of the present invention can be mentioned. From the viewpoint of anchoring property of the pressure-sensitive adhesive layer, the direct method can be preferably adopted as a representative.
　このようなウレタン系粘着剤層の付与（代表的には塗布）の方法としては、例えば、ロールコート法、グラビアコート法、リバースコート法、キスコート法、ディップロールコート法、バーコート法、ロールブラッシュ法、スプレーコート法、ナイフコート法、エアーナイフコート法、スプレーコート法、コンマコート法、ダイレクトコート法、ダイコーターによるコート法等の、従来公知の各種方法を適宜採用することができる。 Examples of the method for applying (typically applying) the urethane adhesive layer include a roll coat method, a gravure coat method, a reverse coat method, a kiss coat method, a dip roll coat method, a bar coat method, and a roll brush. Various conventionally known methods such as a method, a spray coating method, a knife coating method, an air knife coating method, a spray coating method, a comma coating method, a direct coating method, and a coating method using a die coater can be appropriately adopted.
　ウレタン系粘着剤組成物の乾燥は、必要に応じて加熱下で（例えば、６０℃～１５０℃程度に加熱することにより）行うことができる。ウレタン系粘着剤組成物を硬化させる手段としては、例えば、紫外線、レーザー線、α線、β線、γ線、Ｘ線、電子線を適宜採用することができる。 The urethane-based pressure-sensitive adhesive composition can be dried under heating (for example, by heating to about 60 ° C to 150 ° C), if necessary. As a means for curing the urethane-based pressure-sensitive adhesive composition, for example, ultraviolet rays, laser rays, α-rays, β-rays, γ-rays, X-rays, and electron beams can be appropriately adopted.
　ウレタン系粘着剤組成物は、ウレタンプレポリマーＰとポリオールＡと多官能イソシアネート化合物Ｂを含む。 The urethane-based pressure-sensitive adhesive composition contains a urethane prepolymer P, a polyol A, and a polyfunctional isocyanate compound B.
　ウレタン系粘着剤組成物中の、ウレタンプレポリマーＰとポリオールＡと多官能イソシアネート化合物Ｂの合計量の重量割合は、好ましくは５０重量％～１００重量％であり、より好ましくは７０重量％～１００重量％であり、さらに好ましくは９０重量％～１００重量％であり、特に好ましくは９５重量％～１００重量％であり、最も好ましくは９８重量％～１００重量％である。ウレタン系粘着剤組成物中の、ウレタンプレポリマーＰとポリオールＡの合計量の重量割合を、上記範囲内に調整することにより、本発明の表面保護フィルムは、本発明の効果を効果的に発現し得る。 The weight ratio of the total amount of the urethane prepolymer P, the polyol A and the polyfunctional isocyanate compound B in the urethane pressure-sensitive adhesive composition is preferably 50% by weight to 100% by weight, more preferably 70% by weight to 100% by weight. It is by weight%, more preferably 90% by weight to 100% by weight, particularly preferably 95% by weight to 100% by weight, and most preferably 98% by weight to 100% by weight. By adjusting the weight ratio of the total amount of the urethane prepolymer P and the polyol A in the urethane-based pressure-sensitive adhesive composition within the above range, the surface protective film of the present invention effectively exhibits the effects of the present invention. Can be.
　ウレタン系粘着剤組成物中の、ウレタンプレポリマーＰとポリオールＡの重量比は、好ましくはＰ：Ａ＝（５０～９９）：（１～５０）であり、より好ましくは（５０～９０）：（１０～５０）であり、さらに好ましくは（５０～８０）：（２０～５０）であり、特に好ましくは（５０～７０）：（３０～５０）である。ウレタン系粘着剤組成物中の、ウレタンプレポリマーＰとポリオールＡの重量比を、上記範囲内に調整することにより、本発明の表面保護フィルムは、本発明の効果を効果的に発現し得る。 The weight ratio of the urethane prepolymer P to the polyol A in the urethane-based pressure-sensitive adhesive composition is preferably P: A = (50 to 99) :( 1 to 50), and more preferably (50 to 90) :. It is (10 to 50), more preferably (50 to 80) :( 20 to 50), and particularly preferably (50 to 70) :( 30 to 50). By adjusting the weight ratio of the urethane prepolymer P and the polyol A in the urethane-based pressure-sensitive adhesive composition within the above range, the surface protective film of the present invention can effectively exhibit the effects of the present invention.
　ウレタンプレポリマーＰと多官能イソシアネート化合物Ｂにおける、ＮＣＯ基とＯＨ基の当量比は、ＮＣＯ基／ＯＨ基として、好ましくは１．０～２．０であり、より好ましくは１．１～１．９であり、さらに好ましくは１．２～１．８であり、特に好ましくは１．２～１．７である。ＮＣＯ基／ＯＨ基の当量比を上記範囲内に調整することにより、本発明の実施形態による表面保護フィルムは、表面段差の大きい被着体に貼り合わせる場合であっても、濡れ性により優れ、さらに、段差追従性により優れるためにより十分に高い密着率が達成できる。 The equivalent ratio of NCO group to OH group in the urethane prepolymer P and the polyfunctional isocyanate compound B is preferably 1.0 to 2.0, more preferably 1.1 to 1. It is 9, more preferably 1.2 to 1.8, and particularly preferably 1.2 to 1.7. By adjusting the equivalent ratio of NCO group / OH group within the above range, the surface protective film according to the embodiment of the present invention is excellent in wettability even when it is attached to an adherend having a large surface step. Further, since it is superior in step followability, a sufficiently high adhesion rate can be achieved.
　ウレタン系粘着剤組成物中の多官能イソシアネート化合物Ｂの含有割合は、ウレタンプレポリマーＰ１００重量部に対して、好ましくは２．５重量部～４０重量部であり、より好ましくは４重量部～３０重量部であり、さらに好ましくは５重量部～２０重量部であり、特に好ましくは６重量部～１５重量部である。多官能イソシアネート化合物Ｂの含有割合を上記範囲内に調整することにより、本発明の実施形態による表面保護フィルムは、表面段差の大きい被着体に貼り合わせる場合であっても、濡れ性により優れ、さらに、段差追従性により優れるためにより十分に高い密着率が達成できる。 The content ratio of the polyfunctional isocyanate compound B in the urethane-based pressure-sensitive adhesive composition is preferably 2.5 parts by weight to 40 parts by weight, and more preferably 4 parts by weight to 30 parts by weight with respect to 100 parts by weight of the urethane prepolymer. It is a part by weight, more preferably 5 parts by weight to 20 parts by weight, and particularly preferably 6 parts by weight to 15 parts by weight. By adjusting the content ratio of the polyfunctional isocyanate compound B within the above range, the surface protective film according to the embodiment of the present invention is excellent in wettability even when it is attached to an adherend having a large surface step. Further, since it is superior in step followability, a sufficiently high adhesion rate can be achieved.
　本発明において、ウレタン系粘着剤層を構成するウレタン系粘着剤は、ウレタンプレポリマーを用いずに、ポリオールと多官能イソシアネートをダイレクトに反応させてウレタン粘着剤を製造するワンショット法で製造されるウレタン系粘着剤ではなく、ウレタンプレポリマーＰと多官能イソシアネート化合物Ｂを反応させてウレタン粘着剤を製造するプレポリマー法で製造されるウレタン系粘着剤である。本発明の表面保護フィルムは、このようにプレポリマー法で製造されるウレタン系粘着剤で構成されるウレタン系粘着剤層を有するので、ウレタン系粘着剤層の厚膜化が可能となり、例えば、有機ＥＬディスプレイなど、段差の大きいディスプレイを保護する際に、その段差に良好に追従し得る。 In the present invention, the urethane-based pressure-sensitive adhesive constituting the urethane-based pressure-sensitive adhesive layer is produced by a one-shot method for producing a urethane pressure-sensitive adhesive by directly reacting a polyol with a polyfunctional isocyanate without using a urethane prepolymer. It is not a urethane-based pressure-sensitive adhesive, but a urethane-based pressure-sensitive adhesive produced by a prepolymer method for producing a urethane pressure-sensitive adhesive by reacting urethane prepolymer P with a polyfunctional isocyanate compound B. Since the surface protective film of the present invention has a urethane-based pressure-sensitive adhesive layer composed of a urethane-based pressure-sensitive adhesive produced by the prepolymer method in this way, the urethane-based pressure-sensitive adhesive layer can be thickened, for example. When protecting a display having a large step such as an organic EL display, the step can be well followed.
＜１－１－１．ウレタンプレポリマーＰ＞
　ウレタンプレポリマーＰは、代表的にはポリウレタンポリオールであり、好ましくは、ポリエステルポリオール（ｐ１）と、ポリエーテルポリオール（ｐ２）とを、触媒存在下または無触媒下で、有機ポリイソシアネ－ト化合物（ｐ３）と反応させてなるものである。なお、ウレタンプレポリマーＰは、市販品として入手可能なウレタンプレポリマーを採用してもよい。 <1-1-1. Urethane prepolymer P>
The urethane prepolymer P is typically a polyurethane polyol, preferably an organic polyisosianate compound (p3) containing a polyester polyol (p1) and a polyether polyol (p2) in the presence or absence of a catalyst. ). As the urethane prepolymer P, a urethane prepolymer available as a commercially available product may be adopted.
　ウレタンプレポリマーＰは、１種のみであっても良いし、２種以上であってもよい。 The urethane prepolymer P may be of only one type or may be two or more types.
　ウレタンプレポリマーＰの数平均分子量Ｍｎは、好ましくは１０００～１０００００である。 The number average molecular weight Mn of the urethane prepolymer P is preferably 1000 to 100,000.
　ポリエステルポリオール（ｐ１）としては、本発明の効果を損なわない範囲で、任意の適切なポリエステルポリオールを用い得る。このようなポリエステルポリオール（ｐ１）として、例えば、酸成分とグリコール成分とを反応させて得られるポリエステルポリオールが挙げられる。酸成分としては、例えば、テレフタル酸、アジピン酸、アゼライン酸、セバチン酸、無水フタル酸、イソフタル酸、トリメリット酸が挙げられる。グリコール成分としては、例えば、エチレングリコール、プロピレングリコール、ジエチレングリコール、ブチレングリコール、１，６－ヘキサングリコール、３－メチル－１，５－ペンタンジオール、３，３’－ジメチロールヘプタン、ポリオキシエチレングリコール、ポリオキシプロピレングリコール、１，４－ブタンジオール、ネオペンチルグリコール、ブチルエチルペンタンジオール、ポリオール成分としてグリセリン、トリメチロールプロパン、ペンタエリスリトールが挙げられる。ポリエステルポリオール（ｐ１）としては、これらの他に、例えば、ポリカプロラクトン、ポリ（β－メチル－γ－バレロラクトン）、ポリバレロラクトン等のラクトン類を開環重合して得られるポリエステルポリオールが挙げられる。 As the polyester polyol (p1), any suitable polyester polyol can be used as long as the effect of the present invention is not impaired. Examples of such a polyester polyol (p1) include a polyester polyol obtained by reacting an acid component with a glycol component. Examples of the acid component include terephthalic acid, adipic acid, azelaic acid, sebatic acid, phthalic anhydride, isophthalic acid, and trimellitic acid. Examples of the glycol component include ethylene glycol, propylene glycol, diethylene glycol, butylene glycol, 1,6-hexane glycol, 3-methyl-1,5-pentanediol, 3,3'-dimethylol heptane, and polyoxyethylene glycol. Examples thereof include polyoxypropylene glycol, 1,4-butanediol, neopentyl glycol, butylethylpentanediol, and polyol components such as glycerin, trimethylolpropane, and pentaerythritol. Examples of the polyester polyol (p1) include polyester polyols obtained by ring-opening polymerization of lactones such as polycaprolactone, poly (β-methyl-γ-valerolactone) and polyvalerolactone. ..
　ポリエステルポリオール（ｐ１）の分子量としては、低分子量から高分子量まで使用可能である。ポリエステルポリオール（ｐ１）の分子量としては、数平均分子量が、好ましくは５００～５０００である。数平均分子量が５００未満では、反応性が高くなり、ゲル化しやすくなるおそれがある。数平均分子量が５０００を超えると、反応性が低くなり、さらには、ポリウレタンポリオール自体の凝集力が小さくなるおそれがある。ポリエステルポリオール（ｐ１）の使用量は、ウレタンプレポリマーＰ（代表的には、ポリウレタンポリオール）を構成するポリオール中、好ましくは１０モル％～９０モル％である。 The molecular weight of the polyester polyol (p1) can be from low molecular weight to high molecular weight. As the molecular weight of the polyester polyol (p1), the number average molecular weight is preferably 500 to 5000. If the number average molecular weight is less than 500, the reactivity becomes high and gelation may easily occur. If the number average molecular weight exceeds 5000, the reactivity may be lowered, and further, the cohesive force of the polyurethane polyol itself may be reduced. The amount of the polyester polyol (p1) used is preferably 10 mol% to 90 mol% in the polyol constituting the urethane prepolymer P (typically, a polyurethane polyol).
　ポリエーテルポリオール（ｐ２）としては、本発明の効果を損なわない範囲で、任意の適切なポリエーテルポリオールを用い得る。このようなポリエーテルポリオール（ｐ２）としては、例えば、水、プロピレングリコール、エチレングリコール、グリセリン、トリメチロールプロパン等の低分子量ポリオールを開始剤として用いて、エチレンオキシド、プロピレンオキシド、ブチレンオキシド、テトラヒドロフラン等のオキシラン化合物を重合させることにより得られるポリエーテルポリオールが挙げられる。このようなポリエーテルポリオール（ｐ２）としては、例えば、ポリプロピレングリコール、ポリエチレングリコール、ポリテトラメチレングリコール等の官能基数が２以上のポリエーテルポリオールが挙げられる。 As the polyether polyol (p2), any suitable polyether polyol can be used as long as the effect of the present invention is not impaired. Examples of such a polyether polyol (p2) include ethylene oxide, propylene oxide, butylene oxide, and tetrahydrofuran using a low molecular weight polyol such as water, propylene glycol, ethylene glycol, glycerin, and trimethylolpropane as an initiator. Examples thereof include polyether polyols obtained by polymerizing an oxylan compound. Examples of such a polyether polyol (p2) include a polyether polyol having two or more functional groups such as polypropylene glycol, polyethylene glycol, and polytetramethylene glycol.
　ポリエーテルポリオール（ｐ２）の分子量としては、低分子量から高分子量まで使用可能である。ポリエーテルポリオール（ｐ２）の分子量としては、数平均分子量が、好ましくは１０００～５０００である。数平均分子量が１０００未満では、反応性が高くなり、ゲル化しやすくなるおそれがある。数平均分子量が５０００を超えると、反応性が低くなり、さらにはポリウレタンポリオール自体の凝集力が小さくなるおそれがある。ポリエーテルポリオール（ｐ２）の使用量は、ウレタンプレポリマーＰ（代表的には、ポリウレタンポリオール）を構成するポリオール中、好ましくは２０モル％～８０モル％である。 The molecular weight of the polyether polyol (p2) can be from low molecular weight to high molecular weight. As the molecular weight of the polyether polyol (p2), the number average molecular weight is preferably 1000 to 5000. If the number average molecular weight is less than 1000, the reactivity becomes high and gelation may easily occur. If the number average molecular weight exceeds 5000, the reactivity may be low, and the cohesive force of the polyurethane polyol itself may be low. The amount of the polyether polyol (p2) used is preferably 20 mol% to 80 mol% in the polyol constituting the urethane prepolymer P (typically, a polyurethane polyol).
　ポリエーテルポリオール（ｐ２）は、必要に応じてその一部を、例えば、エチレングリコール、１，４－ブタンジオール、ネオペンチルグリコール、ブチルエチルペンタンジオール、グリセリン、トリメチロールプロパン、ペンタエリスリトール等のグリコール類や、エチレンジアミン、Ｎ－アミノエチルエタノールアミン、イソホロンジアミン、キシリレンジアミン等の多価アミン類に置き換えて併用することができる。 Some of the polyether polyols (p2) are, if necessary, glycols such as ethylene glycol, 1,4-butanediol, neopentyl glycol, butylethylpentanediol, glycerin, trimethylolpropane, and pentaerythritol. Alternatively, it can be used in combination with polyvalent amines such as ethylenediamine, N-aminoethylethanolamine, isophoronediamine, and xylylenediamine.
　ポリエーテルポリオール（ｐ２）としては、２官能性のポリエーテルポリオールのみを用いても良いし、数平均分子量が１０００～５０００であり、且つ、１分子中に少なくとも３個以上の水酸基を有するポリエーテルポリオールを一部もしくは全部用いても良い。ポリエーテルポリオール（ｐ２）として、平均分子量が１０００～５０００であり、且つ、１分子中に少なくとも３個以上の水酸基を有するポリエーテルポリオールを一部もしくは全部用いると、粘着力と再剥離性のバランスが良好となり得る。このようなポリエーテルポリオール（ｐ２）においては、数平均分子量が１０００未満では、反応性が高くなり、ゲル化しやすくなるおそれがある。また、このようなポリエーテルポリオール（ｐ２）においては、数平均分子量が５０００を超えると、反応性が低くなり、さらには、ウレタンプレポリマーＰ（代表的には、ポリウレタンポリオール）自体の凝集力が小さくなるおそれがある。このようなポリエーテルポリオール（ｐ２）の数平均分子量は、より好ましくは２５００～３５００である。 As the polyether polyol (p2), only a bifunctional polyether polyol may be used, or a polyether having a number average molecular weight of 1000 to 5000 and having at least 3 or more hydroxyl groups in one molecule. Part or all of the polyol may be used. When a part or all of the polyether polyol (p2) having an average molecular weight of 1000 to 5000 and having at least 3 or more hydroxyl groups in one molecule is used, the balance between adhesive strength and removability is balanced. Can be good. In such a polyether polyol (p2), if the number average molecular weight is less than 1000, the reactivity becomes high and there is a possibility that gelation is likely to occur. Further, in such a polyether polyol (p2), when the number average molecular weight exceeds 5000, the reactivity becomes low, and further, the cohesive force of the urethane prepolymer P (typically, polyurethane polyol) itself becomes strong. It may become smaller. The number average molecular weight of such a polyether polyol (p2) is more preferably 2500 to 3500.
　有機ポリイソシアネート化合物（ｐ３）としては、本発明の効果を損なわない範囲で、任意の適切な有機ポリイソシアネート化合物を用い得る。このような有機ポリイソシアネート化合物（ｐ３）としては、例えば、芳香族ポリイソシアネート、脂肪族ポリイソシアネート、芳香脂肪族ポリイソシアネート、脂環族ポリイソシアネートが挙げられる。 As the organic polyisocyanate compound (p3), any suitable organic polyisocyanate compound can be used as long as the effect of the present invention is not impaired. Examples of such an organic polyisocyanate compound (p3) include aromatic polyisocyanates, aliphatic polyisocyanates, aromatic aliphatic polyisocyanates, and alicyclic polyisocyanates.
　芳香族ポリイソシアネートとしては、例えば、１，３－フェニレンジイソシアネート、４，４’－ジフェニルジイソシアネート、１，４－フェニレンジイソシアネート、４，４’－ジフェニルメタンジイソシアネート、２，４－トリレンジイソシアネート、２，６－トリレンジイソシアネート、４，４’－トルイジンジイソシアネート、２，４，６－トリイソシアネートトルエン、１，３，５－トリイソシアネートベンゼン、ジアニシジンジイソシアネート、４，４’－ジフェニルエーテルジイソシアネート、４，４’，４”－トリフェニルメタントリイソシアネートが挙げられる。 Examples of the aromatic polyisocyanate include 1,3-phenylenediocyanate, 4,4'-diphenyldiisocyanate, 1,4-phenylenediocyanate, 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, and 2,6. -Toluene diisocyanate, 4,4'-toluene diisocyanate, 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate benzene, dianisidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4', 4 ″ -triphenylmethane triisocyanate can be mentioned.
　脂肪族ポリイソシアネートとしては、例えば、トリメチレンジイソシアネート、テトラメチレンジイソシアネート、ヘキサメチレンジイソシアネート、ペンタメチレンジイソシアネート、１，２－プロピレンジイソシアネート、２，３－ブチレンジイソシアネート、１，３－ブチレンジイソシアネート、ドデカメチレンジイソシアネート、２，４，４－トリメチルヘキサメチレンジイソシアネートが挙げられる。 Examples of the aliphatic polyisocyanate include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylenediocyanate, 1,3-butylenediocyanate, and dodecamethylene diisocyanate. Examples thereof include 2,4,4-trimethylhexamethylene diisocyanate.
　芳香脂肪族ポリイソシアネートとしては、例えば、ω，ω’－ジイソシアネート－１，３－ジメチルベンゼン、ω，ω’－ジイソシアネート－１，４－ジメチルベンゼン、ω，ω’－ジイソシアネート－１，４－ジエチルベンゼン、１，４－テトラメチルキシリレンジイソシアネート、１，３－テトラメチルキシリレンジイソシアネートが挙げられる。 Examples of the aromatic aliphatic polyisocyanate include ω, ω'-diisocyanate-1,3-dimethylbenzene, ω, ω'-diisocyanate-1,4-dimethylbenzene, ω, ω'-diisocyanate-1,4-diethylbenzene. , 1,4-Tetramethylxylylene diisocyanate, 1,3-tetramethylxylylene diisocyanate.
　脂環族ポリイソシアネートとしては、例えば、３－イソシアネートメチル－３，５，５－トリメチルシクロヘキシルイソシアネート、１，３－シクロペンタンジイソシアネート、１，３－シクロヘキサンジイソシアネート、１，４－シクロヘキサンジイソシアネート、メチル－２，４－シクロヘキサンジイソシアネート、メチル－２，６－シクロヘキサンジイソシアネート、４，４’－メチレンビス（シクロヘキシルイソシアネート）、１，４－ビス（イソシアネートメチル）シクロヘキサン、１，４－ビス（イソシアネートメチル）シクロヘキサンが挙げられる。 Examples of the alicyclic polyisocyanate include 3-isocyanate methyl-3,5,5-trimethylcyclohexylisocyanate, 1,3-cyclopentanediisocyanate, 1,3-cyclohexanediisocyanate, 1,4-cyclohexanediisocyanate, and methyl-2. , 4-Cyclohexanediisocyanate, methyl-2,6-cyclohexanediisocyanate, 4,4'-methylenebis (cyclohexylisocyanate), 1,4-bis (isocyanatemethyl) cyclohexane, 1,4-bis (isocyanatemethyl) cyclohexane. ..
　有機ポリイソシアネート化合物（ｐ３）としては、トリメチロールプロパンアダクト体、水と反応したビュウレット体、イソシアヌレート環を有する３量体を併用することができる。 As the organic polyisocyanate compound (p3), a trimethylolpropane adduct body, a biuret body reacted with water, and a trimer having an isocyanurate ring can be used in combination.
　ウレタンプレポリマーＰ（代表的には、ポリウレタンポリオール）を製造する際に用い得る触媒としては、本発明の効果を損なわない範囲で、任意の適切な触媒を用い得る。このような触媒としては、例えば、３級アミン系化合物、有機金属系化合物が挙げられる。 As the catalyst that can be used in producing the urethane prepolymer P (typically, polyurethane polyol), any suitable catalyst can be used as long as the effect of the present invention is not impaired. Examples of such a catalyst include tertiary amine compounds and organometallic compounds.
　３級アミン系化合物としては、例えば、トリエチルアミン、トリエチレンジアミン、１，８－ジアザビシクロ（５，４，０）－ウンデセン－７（ＤＢＵ）が挙げられる。 Examples of the tertiary amine compound include triethylamine, triethylenediamine, and 1,8-diazabicyclo (5,4,0) -undecene-7 (DBU).
　有機金属系化合物としては、例えば、錫系化合物、非錫系化合物が挙げられる。 Examples of the organometallic compound include tin-based compounds and non-tin-based compounds.
　錫系化合物としては、例えば、ジブチル錫ジクロライド、ジブチル錫オキサイド、ジブチル錫ジブロマイド、ジブチル錫ジマレエート、ジブチル錫ジラウレート（ＤＢＴＤＬ）、ジブチル錫ジアセテート、ジブチル錫スルファイド、トリブチル錫スルファイド、トリブチル錫オキサイド、トリブチル錫アセテート、トリエチル錫エトキサイド、トリブチル錫エトキサイド、ジオクチル錫オキサイド、トリブチル錫クロライド、トリブチル錫トリクロロアセテート、２－エチルヘキサン酸錫が挙げられる。 Examples of the tin-based compound include dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin dimalate, dibutyltin dilaurate (DBTDL), dibutyltin diacetate, dibutyltin sulfide, tributyltin sulfide, tributyltin oxide, and tributyl. Examples thereof include tin acetate, triethyl tin ethoxide, tributyl tin ethoxide, dioctyl tin oxide, tributyl tin chloride, tributyl tin trichloroacetate and tin 2-ethylhexanoate.
　非錫系化合物としては、例えば、ジブチルチタニウムジクロライド、テトラブチルチタネート、ブトキシチタニウムトリクロライドなどのチタン系化合物；オレイン酸鉛、２－エチルヘキサン酸鉛、安息香酸鉛、ナフテン酸鉛などの鉛系化合物；２－エチルヘキサン酸鉄、鉄アセチルアセトネートなどの鉄系化合物；安息香酸コバルト、２－エチルヘキサン酸コバルトなどのコバルト系化合物；ナフテン酸亜鉛、２－エチルヘキサン酸亜鉛などの亜鉛系化合物；ナフテン酸ジルコニウムなどのジルコニウム系化合物；が挙げられる。 Examples of the non-tin compound include titanium compounds such as dibutyl titanium dichloride, tetrabutyl titanate, and butoxytitanium trichloride; lead compounds such as lead oleate, lead 2-ethylhexanoate, lead benzoate, and lead naphthenate. Iron-based compounds such as iron 2-ethylhexanoate and iron acetylacetonate; Cobalt-based compounds such as cobalt benzoate and cobalt 2-ethylhexanoate; Zinc-based compounds such as zinc naphthenate and zinc 2-ethylhexanoate; Zylon-based compounds such as zirconium naphthenate;
　ウレタンプレポリマーＰ（代表的には、ポリウレタンポリオール）を製造する際に触媒を使用する場合、ポリエステルポリオール（ｐ１）とポリエーテルポリオール（ｐ２）の２種類のポリオールが存在する系では、その反応性の相違のため、単独の触媒の系では、ゲル化したり反応溶液が濁ったりするという問題が生じやすい。そこで、ウレタンプレポリマーＰ（代表的には、ポリウレタンポリオール）を得る際に２種類の触媒を用いることにより、反応速度、触媒の選択性等が制御しやすくなり、これらの問題を解決し得る。このような２種類の触媒の組み合わせとしては、例えば、３級アミン／有機金属系、錫系／非錫系、錫系／錫系が挙げられ、好ましくは錫系／錫系であり、より好ましくはジブチル錫ジラウレートと２－エチルヘキサン酸錫の組み合わせである。その配合比は、重量比で、２－エチルヘキサン酸錫／ジブチル錫ジラウレートが、好ましくは１未満であり、より好ましくは０．２～０．６である。配合比が１以上では、触媒活性のバランスによりゲル化しやすくなるおそれがある。 When a catalyst is used in producing a urethane prepolymer P (typically a polyurethane polyol), its reactivity in a system in which two types of polyols, a polyester polyol (p1) and a polyether polyol (p2), are present. Due to the difference in the above, problems such as gelation and turbidity of the reaction solution are likely to occur in a single catalyst system. Therefore, by using two types of catalysts when obtaining the urethane prepolymer P (typically, polyurethane polyol), the reaction rate, the selectivity of the catalyst, and the like can be easily controlled, and these problems can be solved. Examples of the combination of such two types of catalysts include tertiary amine / organic metal-based, tin-based / non-tin-based, and tin-based / tin-based, preferably tin-based / tin-based, and more preferably. Is a combination of dibutyltin dilaurate and tin 2-ethylhexanoate. As for the compounding ratio, the tin 2-ethylhexanoate / dibutyltin dilaurate is preferably less than 1 and more preferably 0.2 to 0.6 by weight. When the compounding ratio is 1 or more, gelation may easily occur due to the balance of catalytic activity.
　ウレタンプレポリマーＰ（代表的には、ポリウレタンポリオール）を製造する際に触媒を使用する場合、触媒の使用量は、ポリエステルポリオール（ａ１）とポリエーテルポリオール（ａ２）と有機ポリイソシアネ－ト化合物（ａ３）の合計量に対して、好ましくは０．０１重量％～１．０重量％である。 When a catalyst is used in producing urethane prepolymer P (typically, polyurethane polyol), the amount of the catalyst used is polyester polyol (a1), polyether polyol (a2), and organic polyisosianate compound (a3). ), It is preferably 0.01% by weight to 1.0% by weight.
　ウレタンプレポリマーＰ（代表的には、ポリウレタンポリオール）を製造する際に触媒を使用する場合、反応温度は、好ましくは１００℃未満であり、より好ましくは８５℃～９５℃である。１００℃以上になると反応速度、架橋構造の制御が困難となるおそれがあり、所定の分子量を有するウレタンプレポリマーＰ（代表的には、ポリウレタンポリオール）が得難くなるおそれがある。 When a catalyst is used in producing the urethane prepolymer P (typically, polyurethane polyol), the reaction temperature is preferably less than 100 ° C, more preferably 85 ° C to 95 ° C. If the temperature is 100 ° C. or higher, it may be difficult to control the reaction rate and the crosslinked structure, and it may be difficult to obtain a urethane prepolymer P (typically, a polyurethane polyol) having a predetermined molecular weight.
　ウレタンプレポリマーＰ（代表的には、ポリウレタンポリオール）を製造する際には、触媒を用いなくても良い。その場合は、反応温度が、好ましくは１００℃以上であり、より好ましくは１１０℃以上である。また、無触媒下でウレタンプレポリマーＰ（代表的には、ポリウレタンポリオール）を得る際は、３時間以上反応させることが好ましい。 When producing urethane prepolymer P (typically, polyurethane polyol), it is not necessary to use a catalyst. In that case, the reaction temperature is preferably 100 ° C. or higher, more preferably 110 ° C. or higher. Further, when the urethane prepolymer P (typically, polyurethane polyol) is obtained without a catalyst, it is preferable to react for 3 hours or more.
　ウレタンプレポリマーＰ（代表的には、ポリウレタンポリオール）を製造する方法としては、例えば、１）ポリエステルポリオール（ｐ１）、ポリエーテルポリオール（ｐ２）、触媒、有機ポリイソシアネート化合物（ｐ３）を全量フラスコに仕込む方法、２）ポリエステルポリオール（ｐ１）、ポリエーテルポリオール（ｐ２）、触媒をフラスコに仕込んで有機ポリイソシアネ－ト化合物（ｐ３）を滴下する添加する方法が挙げられる。ウレタンプレポリマーＰ（代表的には、ポリウレタンポリオール）を製造する方法として、反応を制御する上では、２）の方法が好ましい。 As a method for producing a urethane prepolymer P (typically, a polyurethane polyol), for example, 1) a polyester polyol (p1), a polyether polyol (p2), a catalyst, and an organic polyisocyanate compound (p3) are put into a total volume flask. Examples thereof include a method of charging, 2) a method of charging a polyester polyol (p1), a polyether polyol (p2), and a catalyst into a flask and adding an organic polyisocyanate compound (p3) by dropping. As a method for producing a urethane prepolymer P (typically, a polyurethane polyol), the method 2) is preferable in controlling the reaction.
　ウレタンプレポリマーＰ（代表的には、ポリウレタンポリオール）を製造する際には、本発明の効果を損なわない範囲で、任意の適切な溶剤を用い得る。このような溶剤としては、例えば、メチルエチルケトン、酢酸エチル、トルエン、キシレン、アセトンが挙げられる。これらの溶剤の中でも、好ましくはトルエンである。 When producing urethane prepolymer P (typically, polyurethane polyol), any suitable solvent can be used as long as the effect of the present invention is not impaired. Examples of such a solvent include methyl ethyl ketone, ethyl acetate, toluene, xylene, and acetone. Among these solvents, toluene is preferable.
＜１－１－２．ポリオールＡ＞ <1-1-2. Polyol A>
　ポリオールＡとしては、例えば、ポリエステルポリオール、ポリエーテルポリオール、ポリカプロラクトンポリオール、ポリカーボネートポリオール、ひまし油系ポリオールが挙げられる。ポリオールＡとしては、より好ましくは、ポリエステルポリオール、ポリエーテルポリオールである。 Examples of the polyol A include polyester polyols, polyether polyols, polycaprolactone polyols, polycarbonate polyols, and castor oil-based polyols. The polyol A is more preferably a polyester polyol or a polyether polyol.
　ポリエステルポリオールとしては、例えば、ポリオール成分と酸成分とのエステル化反応によって得ることができる。 The polyester polyol can be obtained, for example, by an esterification reaction between a polyol component and an acid component.
　ポリオール成分としては、例えば、エチレングリコール、ジエチレングリコール、１，３－ブタンジオール、１，４－ブタンジオール、ネオペンチルグリコール、３－メチル－１，５－ペンタンジオール、２－ブチル－２－エチル－１，３－プロパンジオール、２，４－ジエチル－１，５－ペンタンジオール、１，２－ヘキサンジオール、１，６－ヘキサンジオール、１，８－オクタンジオール、１，９－ノナンジオール、２－メチル－１，８－オクタンジオール、１，８－デカンジオール、オクタデカンジオール、グリセリン、トリメチロールプロパン、ペンタエリスリトール、ヘキサントリオール、ポリプロピレングリコールが挙げられる。 Examples of the polyol component include ethylene glycol, diethylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, and 2-butyl-2-ethyl-1. , 3-Propanediol, 2,4-diethyl-1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 2-methyl Examples thereof include -1,8-octanediol, 1,8-decanediol, octadecanediol, glycerin, trimethylolpropane, pentaerythritol, hexanetriol and polypropylene glycol.
　酸成分としては、例えば、コハク酸、メチルコハク酸、アジピン酸、ピメリック酸、アゼライン酸、セバシン酸、１，１２－ドデカン二酸、１，１４－テトラデカン二酸、ダイマー酸、２－メチル－１，４－シクロヘキサンジカルボン酸、２－エチル－１，４－シクロヘキサンジカルボン酸、テレフタル酸、イソフタル酸、フタル酸、イソフタル酸、テレフタル酸、１，４－ナフタレンジカルボン酸、４，４’－ビフェエルジカルボン酸、これらの酸無水物が挙げられる。 Examples of the acid component include succinic acid, methylsuccinic acid, adipic acid, piceric acid, azelaic acid, sebacic acid, 1,12-dodecanedioic acid, 1,14-tetradecanedioic acid, dimer acid, 2-methyl-1, 4-Cyclohexanedicarboxylic acid, 2-ethyl-1,4-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, isophthalic acid, terephthalic acid, 1,4-naphthalenedicarboxylic acid, 4,4'-biphereldicarboxylic acid , These acid anhydrides.
　ポリエーテルポリオールとしては、例えば、水、低分子ポリオール（プロピレングリコール、エチレングリコール、グリセリン、トリメチロールプロパン、ペンタエリスリトールなど）、ビスフェノール類（ビスフェノールＡなど）、ジヒドロキシベンゼン（カテコール、レゾルシン、ハイドロキノンなど）などを開始剤として、エチレンオキサイド、プロピレンオキサイド、ブチレンオキサイドなどのアルキレンオキサイドを付加重合させることによって得られるポリエーテルポリオールが挙げられる。具体的には、例えば、ポリエチレングリコール、ポリプロピレングリコール、ポリテトラメチレングリコールなどが挙げられる。 Examples of the polyether polyol include water, low molecular weight polyols (propylene glycol, ethylene glycol, glycerin, trimethylolpropane, pentaerythritol, etc.), bisphenols (bisphenol A, etc.), dihydroxybenzene (catechol, resorcin, hydroquinone, etc.), etc. Examples thereof include polyether polyols obtained by addition polymerization of alkylene oxides such as ethylene oxide, propylene oxide and butylene oxide. Specific examples thereof include polyethylene glycol, polypropylene glycol and polytetramethylene glycol.
　ポリカプロラクトンポリオールとしては、例えば、ε－カプロラクトン、σ－バレロラクトンなどの環状エステルモノマーの開環重合により得られるカプロラクトン系ポリエステルジオールが挙げられる。 Examples of the polycaprolactone polyol include a caprolactone-based polyester diol obtained by ring-opening polymerization of a cyclic ester monomer such as ε-caprolactone and σ-valerolactone.
　ポリカーボネートポリオールとしては、例えば、上記ポリオール成分とホスゲンとを重縮合反応させて得られるポリカーボネートポリオール；上記ポリオール成分と、炭酸ジメチル、炭酸ジエチル、炭酸ジプロビル、炭酸ジイソプロピル、炭酸ジブチル、エチルブチル炭酸、エチレンカーボネート、プロピレンカーボネート、炭酸ジフェニル、炭酸ジベンジル等の炭酸ジエステル類とをエステル交換縮合させて得られるポリカーボネートポリオール；上記ポリオール成分を２種以上併用して得られる共重合ポリカーボネートポリオール；上記各種ポリカーボネートポリオールとカルボキシル基含有化合物とをエステル化反応させて得られるポリカーボネートポリオール；上記各種ポリカーボネートポリオールとヒドロキシル基含有化合物とをエーテル化反応させて得られるポリカーボネートポリオール；上記各種ポリカーボネートポリオールとエステル化合物とをエステル交換反応させて得られるポリカーボネートポリオール；上記各種ポリカーボネートポリオールとヒドロキシル基含有化合物とをエステル交換反応させて得られるポリカーボネートポリオール；上記各種ポリカーボネートポリオールとジカルボン酸化合物とを重縮合反応させて得られるポリエステル系ポリカーボネートポリオール；上記各種ポリカーボネートポリオールとアルキレンオキサイドとを共重合させて得られる共重合ポリエーテル系ポリカーボネートポリオール；が挙げられる。 Examples of the polycarbonate polyol include a polycarbonate polyol obtained by subjecting the above-mentioned polyol component and phosgen to a polycondensation reaction; the above-mentioned polyol component and dimethyl carbonate, diethyl carbonate, diprovyl carbonate, diisopropyl carbonate, dibutyl carbonate, ethylbutyl carbonate, ethylene carbonate, Polycarbonate polyol obtained by ester exchange condensation with carbonic acid diesters such as propylene carbonate, diphenyl carbonate, dibenzyl carbonate; copolymerized polycarbonate polyol obtained by using two or more of the above polyol components in combination; containing various polycarbonate polyols and a carboxyl group. Polycarbonate polyol obtained by esterifying a compound; Polycarbonate polyol obtained by etherifying a various polycarbonate polyols and a hydroxyl group-containing compound; Obtaining by an ester exchange reaction between various polycarbonate polyols and an ester compound. Polycarbonate polyol; Polycarbonate polyol obtained by performing an ester exchange reaction between the various polycarbonate polyols and a hydroxyl group-containing compound; Polycarbonate-based polycarbonate polyol obtained by a polycondensation reaction between the various polycarbonate polyols and a dicarboxylic acid compound; Examples thereof include a copolymerized polyether polycarbonate polyol obtained by copolymerizing and alkylene oxide.
　ひまし油系ポリオールとしては、例えば、ひまし油脂肪酸と上記ポリオール成分とを反応させて得られるひまし油系ポリオールが挙げられる。具体的には、例えば、ひまし油脂肪酸とポリプロピレングリコールとを反応させて得られるひまし油系ポリオールが挙げられる。 Examples of the castor oil-based polyol include castor oil-based polyol obtained by reacting castor oil fatty acid with the above-mentioned polyol component. Specific examples thereof include castor oil-based polyols obtained by reacting castor oil fatty acid with polypropylene glycol.
　ポリオールＡは、数平均分子量Ｍｎが５０００～２００００の第１のポリオールＡ１と数平均分子量Ｍｎが３００～４９９９の第２のポリオールＡ２を含む。ポリオールＡが、数平均分子量Ｍｎが５０００～２００００の第１のポリオールＡ１と数平均分子量Ｍｎが３００～４９９９の第２のポリオールＡ２を含むことにより、本発明の効果をより発現し得る。 The polyol A contains a first polyol A1 having a number average molecular weight Mn of 5000 to 20000 and a second polyol A2 having a number average molecular weight Mn of 300 to 4999. The effect of the present invention can be further exhibited by the polyol A containing the first polyol A1 having a number average molecular weight Mn of 5000 to 20000 and the second polyol A2 having a number average molecular weight Mn of 300 to 4999.
　第１のポリオールＡ１は、１種のみであってもよいし、２種以上であってもよい。 The first polyol A1 may be only one kind or two or more kinds.
　第２のポリオールＡ２は、１種のみであってもよいし、２種以上であってもよい。 The second polyol A2 may be only one kind or two or more kinds.
　ポリオールＡ中の第１のポリオールＡ１と第２のポリオールＡ２の合計量の含有割合は、本発明の効果をより発現させ得る点で、好ましくは８０重量％～１００重量％であり、より好ましくは９０重量％～１００重量％であり、さらに好ましくは９５重量％～１００重量％であり、特に好ましくは９８重量％～１００重量％であり、最も好ましくは実質的に１００重量％である。 The content ratio of the total amount of the first polyol A1 and the second polyol A2 in the polyol A is preferably 80% by weight to 100% by weight, more preferably, in that the effect of the present invention can be more exhibited. It is 90% by weight to 100% by weight, more preferably 95% by weight to 100% by weight, particularly preferably 98% by weight to 100% by weight, and most preferably substantially 100% by weight.
　第１のポリオールＡ１の数平均分子量Ｍｎは、５０００～２００００であり、好ましくは６０００～１８０００であり、より好ましくは７０００～１６０００であり、さらに好ましくは８０００～１５０００であり、特に好ましくは９０００～１４０００である。第１のポリオールＡ１の数平均分子量Ｍｎが上記範囲内にあれば、本発明の効果をより発現し得る。 The number average molecular weight Mn of the first polyol A1 is 5000 to 20000, preferably 6000 to 18000, more preferably 7000 to 16000, still more preferably 8000 to 15000, and particularly preferably 9000 to 14000. Is. When the number average molecular weight Mn of the first polyol A1 is within the above range, the effect of the present invention can be more exhibited.
　第２のポリオールＡ２の数平均分子量Ｍｎは、３００～４９９９であり、好ましくは３５０～４５００であり、より好ましくは４００～４０００であり、さらに好ましくは５００～３８００であり、特に好ましくは７００～３５００である。第２のポリオールＡ２の数平均分子量Ｍｎが上記範囲内にあれば、本発明の効果をより発現し得る。 The number average molecular weight Mn of the second polyol A2 is 300 to 4999, preferably 350 to 4500, more preferably 400 to 4000, still more preferably 500 to 3800, and particularly preferably 700 to 3500. Is. When the number average molecular weight Mn of the second polyol A2 is within the above range, the effect of the present invention can be more exhibited.
　第１のポリオールＡ１と第２のポリオールＡ２との重量比率は、好ましくは１．０≦（Ａ１／Ａ２）≦３．５であり、より好ましくは１．０≦（Ａ１／Ａ２）≦３．０であり、さらに好ましくは１．０≦（Ａ１／Ａ２）≦２．５であり、特に好ましくは１．０≦（Ａ１／Ａ２）≦２．０である。第１のポリオールＡ１と第２のポリオールＡ２との重量比率が上記範囲内にあれば、本発明の効果をより発現し得る。 The weight ratio of the first polyol A1 to the second polyol A2 is preferably 1.0 ≦ (A1 / A2) ≦ 3.5, more preferably 1.0 ≦ (A1 / A2) ≦ 3. It is 0, more preferably 1.0 ≦ (A1 / A2) ≦ 2.5, and particularly preferably 1.0 ≦ (A1 / A2) ≦ 2.0. If the weight ratio of the first polyol A1 and the second polyol A2 is within the above range, the effect of the present invention can be more exhibited.
　第１のポリオールＡ１は、本発明の効果をより発現させ得る点で、それが有するＯＨ基の数が、好ましくは３個～６個であり、より好ましくは３個～５個であり、さらに好ましくは３個～４個であり、特に好ましくは３個である。 The first polyol A1 has preferably 3 to 6 OH groups, more preferably 3 to 5 groups, and further, in that the effect of the present invention can be more exhibited. The number is preferably 3 to 4, and particularly preferably 3.
　第１のポリオールＡ１は、本発明の効果をより発現させ得る点で、ＯＨ基の数が３個であるトリオールを、好ましくは５０重量％～１００重量％含み、より好ましくは７０重量％～１００重量％含み、さらに好ましくは９０重量％～１００重量％含み、特に好ましくは９５重量％～１００重量％含み、最も好ましくは実質的に１００重量％である。 The first polyol A1 contains triol having 3 OH groups, preferably 50% by weight to 100% by weight, and more preferably 70% by weight to 100% by weight, in that the effect of the present invention can be more exhibited. It contains% by weight, more preferably 90% by weight to 100% by weight, particularly preferably 95% by weight to 100% by weight, and most preferably substantially 100% by weight.
　第２のポリオールＡ２は、本発明の効果をより発現させ得る点で、それが有するＯＨ基の数が、好ましくは３個～６個であり、より好ましくは３個～５個であり、さらに好ましくは３個～４個であり、特に好ましくは３個である。 The second polyol A2 has preferably 3 to 6 OH groups, more preferably 3 to 5 groups, and further, in that the effect of the present invention can be more exhibited. The number is preferably 3 to 4, and particularly preferably 3.
　第２のポリオールＡ２は、本発明の効果をより発現させ得る点で、ＯＨ基の数が３個であるトリオールを、好ましくは５０重量％～１００重量％含み、より好ましくは７０重量％～１００重量％含み、さらに好ましくは９０重量％～１００重量％含み、特に好ましくは９５重量％～１００重量％含み、最も好ましくは実質的に１００重量％である。 The second polyol A2 contains triol having 3 OH groups in an amount of preferably 50% by weight to 100% by weight, more preferably 70% by weight to 100% by weight, in that the effect of the present invention can be more exhibited. It contains% by weight, more preferably 90% by weight to 100% by weight, particularly preferably 95% by weight to 100% by weight, and most preferably substantially 100% by weight.
＜１－１－３．多官能イソシアネート化合物Ｂ＞ <1-1-3. Polyfunctional isocyanate compound B>
　多官能イソシアネート化合物Ｂは、１種のみであってもよいし、２種以上であってもよい。 The polyfunctional isocyanate compound B may be only one kind or two or more kinds.
　多官能イソシアネート化合物Ｂとしては、ウレタン化反応に用い得る任意の適切な多官能イソシアネート化合物を採用し得る。このような多官能イソシアネート化合物Ｂとしては、例えば、多官能脂肪族系イソシアネート化合物、多官能脂環族系イソシアネート、多官能芳香族系イソシアネート化合物が挙げられる。 As the polyfunctional isocyanate compound B, any suitable polyfunctional isocyanate compound that can be used for the urethanization reaction can be adopted. Examples of such a polyfunctional isocyanate compound B include a polyfunctional aliphatic isocyanate compound, a polyfunctional alicyclic isocyanate, and a polyfunctional aromatic isocyanate compound.
　多官能脂肪族系イソシアネート化合物としては、例えば、トリメチレンジイソシアネート、テトラメチレンジイソシアネート、ヘキサメチレンジイソシアネート、ペンタメチレンジイソシアネート、１，２－プロピレンジイソシアネート、１，３－ブチレンジイソシアネート、ドデカメチレンジイソシアネート、２，４，４－トリメチルヘキサメチレンジイソシアネートが挙げられる。 Examples of the polyfunctional aliphatic isocyanate compound include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,3-butylenediocyanate, dodecamethylene diisocyanate, 2,4. Examples thereof include 4-trimethylhexamethylene diisocyanate.
　多官能脂環族系イソシアネート化合物としては、例えば、１，３－シクロペンテンジイソシアネート、１，３－シクロへキサンジイソシアネート、１，４－シクロヘキサンジイソシアネート、イソホロンジイソシアネート、水素添加ジフェニルメタンジイソシアネート、水素添加キシリレンジイソシアネート、水素添加トリレンジイソシアネート、水素添加テトラメチルキシリレンジイソシアネートが挙げられる。 Examples of the polyfunctional alicyclic isocyanate compound include 1,3-cyclopentene diisocyanate, 1,3-cyclohexanediisocyanate, 1,4-cyclohexanediisocyanate, isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, and hydrogenated xylylene diisocyanate. Examples thereof include hydrogenated tolylene diisocyanate and hydrogenated tetramethylxylylene diisocyanate.
　多官能芳香族系ジイソシアネート化合物としては、例えば、フェニレンジイソシアネート、２，４－トリレンジイソソアネート、２，６－トリレンジイソシアネート、２，２’一ジフェニルメタンジイソシアネート、４，４’－ジフェニルメタンジイソシアネート、４，４’－トルイジンジイソシアネート、４，４’－ジフェニルエーテルジイソシアネート、４，４’－ジフェニルジイソシアネート、１，５－ナフタレンジイソシアネート、キシリレンジイソシアネートが挙げられる。 Examples of the polyfunctional aromatic diisocyanate compound include phenylenediocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 2,2'-diphenylmethane diisocyanate, and 4,4'-diphenylmethane diisocyanate, 4 , 4'-toluene diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalenediocyanate, xylylene diisocyanate.
　多官能イソシアネート化合物Ｂとしては、上記のような各種多官能イソシアネート化合物のトリメチロールプロパンアダクト体、水と反応したビュウレット体、イソシアヌレート環を有する３量体も挙げられる。また、これらを併用しても良い。 Examples of the polyfunctional isocyanate compound B include a trimethylolpropane adduct body of various polyfunctional isocyanate compounds as described above, a biuret body reacted with water, and a trimer having an isocyanurate ring. Moreover, you may use these together.
＜１－１－４．他の成分＞
　ウレタン系粘着剤組成物は、ウレタンプレポリマーＰとポリオールＡと多官能イソシアネート化合物Ｂ以外に、本発明の効果を損なわない範囲で、任意の適切な他の成分を含み得る。このような他の成分としては、例えば、ウレタンプレポリマーＰとポリオールＡ以外の樹脂成分、多官能イソシアネート化合物Ｂ以外の架橋剤、架橋遅延剤、イオン性化合物、フッ素系添加剤、シリコーン系添加剤、脂肪酸エステル、粘着付与剤、無機充填剤、有機充填剤、金属粉、顔料、箔状物、軟化剤、老化防止剤、導電剤、紫外線吸収剤、酸化防止剤、光安定剤、表面潤滑剤、レベリング剤、腐食防止剤、耐熱安定剤、重合禁止剤、滑剤、溶剤、触媒が挙げられる。 <1-1-4. Other ingredients>
In addition to the urethane prepolymer P, the polyol A, and the polyfunctional isocyanate compound B, the urethane-based pressure-sensitive adhesive composition may contain any suitable other components as long as the effects of the present invention are not impaired. Examples of such other components include resin components other than urethane prepolymer P and polyol A, cross-linking agents other than polyfunctional isocyanate compound B, cross-linking retarders, ionic compounds, fluorine-based additives, and silicone-based additives. , Fatty ester, tackifier, inorganic filler, organic filler, metal powder, pigment, foil, softener, anti-aging agent, conductive agent, UV absorber, antioxidant, light stabilizer, surface lubricant , Leveling agents, corrosion inhibitors, heat stabilizers, polymerization inhibitors, lubricants, solvents, catalysts and the like.
〔イオン性化合物〕
　他の成分として、イオン性化合物を含むと、本発明の実施形態による表面保護フィルムの帯電防止性能が向上することが可能となる。 [Ionic compound]
When an ionic compound is contained as another component, the antistatic performance of the surface protective film according to the embodiment of the present invention can be improved.
　イオン性化合物の含有割合としては、本発明の効果を損なわない範囲で、任意の適切な含有割合を採用し得る。本発明の表面保護フィルムの帯電防止性能をより向上させ得る点で、ウレタンプレポリマーＰとポリオールＡの合計量に対するイオン性化合物の含有割合は、好ましくは０．０５重量％以上であり、より好ましくは０．１０重量％～５０重量％であり、さらに好ましくは０．２０重量％～３０重量％であり、特に好ましくは０．３０重量％～１０重量％であり、最も好ましくは０．５０重量％～１重量％である。ウレタンプレポリマーＰとポリオールＡの合計量に対するイオン性化合物の含有割合が上記範囲内にあれば、本発明の表面保護フィルムの帯電防止性能をより向上させ得る。ウレタンプレポリマーＰとポリオールＡの合計量に対するイオン性化合物の含有割合が上記範囲を外れて少なすぎると、本発明の表面保護フィルムに十分な帯電防止性能を付与できないおそれがある。ウレタンプレポリマーＰとポリオールＡの合計量に対するイオン性化合物の含有割合が上記範囲を外れて多すぎると、被着体への汚染が増加するおそれがある。 As the content ratio of the ionic compound, any appropriate content ratio can be adopted as long as the effect of the present invention is not impaired. The content ratio of the ionic compound to the total amount of the urethane prepolymer P and the polyol A is preferably 0.05% by weight or more, more preferably, in terms of further improving the antistatic performance of the surface protective film of the present invention. Is 0.10% by weight to 50% by weight, more preferably 0.20% by weight to 30% by weight, particularly preferably 0.30% by weight to 10% by weight, and most preferably 0.50% by weight. % To 1% by weight. When the content ratio of the ionic compound to the total amount of the urethane prepolymer P and the polyol A is within the above range, the antistatic performance of the surface protective film of the present invention can be further improved. If the content ratio of the ionic compound to the total amount of the urethane prepolymer P and the polyol A is too small outside the above range, it may not be possible to impart sufficient antistatic performance to the surface protective film of the present invention. If the content ratio of the ionic compound to the total amount of the urethane prepolymer P and the polyol A is too large outside the above range, contamination of the adherend may increase.
　イオン性化合物としては、本発明の効果を損なわない範囲で、任意の適切なイオン性化合物を採用し得る。イオン性化合物は、１種のみであってもよいし、２種以上であってもよい。 As the ionic compound, any appropriate ionic compound can be adopted as long as the effect of the present invention is not impaired. The ionic compound may be only one kind or two or more kinds.
　イオン性化合物としては、本発明の効果をより発現させ得る点で、好ましくは、オニウムカチオンおよび金属カチオンから選ばれる少なくとも１種とフルオロ有機アニオンを含むイオン性化合物、イオン性基含有シリコーンオリゴマーであり、粘着剤層の外観をより優れたものとし得る点で、より好ましくは、オニウムカチオンおよび金属カチオンから選ばれる少なくとも１種とフルオロ有機アニオンを含むイオン性化合物である。 The ionic compound is preferably an ionic compound containing at least one selected from an onium cation and a metal cation and a fluoroorganic anion, and an ionic group-containing silicone oligomer, in that the effects of the present invention can be further exhibited. An ionic compound containing at least one selected from an onium cation and a metal cation and a fluoroorganic anion is more preferable in that the appearance of the pressure-sensitive adhesive layer can be improved.
　イオン性化合物は、イオン性液体であってもよい。イオン性液体とは、２５℃で液状を呈する溶融塩（イオン性化合物）を意味する。 The ionic compound may be an ionic liquid. The ionic liquid means a molten salt (ionic compound) that exhibits a liquid at 25 ° C.
　イオン性基含有シリコーンオリゴマーとしては、本発明の効果を損なわない範囲で、任意の適切なイオン性基含有シリコーンオリゴマーを採用し得る。イオン性基含有シリコーンオリゴマーとして、例えば、信越化学工業社製の商品名「Ｘ－４０－２４５０」が挙げられる。 As the ionic group-containing silicone oligomer, any appropriate ionic group-containing silicone oligomer can be adopted as long as the effect of the present invention is not impaired. Examples of the ionic group-containing silicone oligomer include the trade name “X-40-2450” manufactured by Shin-Etsu Chemical Co., Ltd.
　オニウムカチオンとしては、本発明の効果を損なわない範囲で、任意の適切なオニウムカチオンを採用し得る。本発明の効果をより発現させ得る点で、このようなオニウムカチオンとしては、好ましくは、アンモニウムカチオン（窒素含有オニウムカチオン）、スルホニウムカチオン（硫黄含有オニウムカチオン）、リン含有オニウムカチオン（ホスホニウムカチオン）から選ばれる少なくとも１種であり、より好ましくは、アンモニウムカチオンである。 As the onium cation, any appropriate onium cation can be adopted as long as the effect of the present invention is not impaired. Such onium cations are preferably selected from ammonium cations (nitrogen-containing onium cations), sulfonium cations (sulfur-containing onium cations), and phosphorus-containing onium cations (phosphonium cations) in that the effects of the present invention can be further exhibited. At least one selected, more preferably an ammonium cation.
　金属カチオンとしては、本発明の効果を損なわない範囲で、任意の適切な金属カチオンを採用し得る。本発明の効果をより発現させ得る点で、このような金属カチオンとしては、好ましくは、Ｌｉカチオン、Ｎａカチオン、Ｋカチオン等のアルカリ金属カチオンである。 As the metal cation, any suitable metal cation can be adopted as long as the effect of the present invention is not impaired. Such metal cations are preferably alkali metal cations such as Li cations, Na cations and K cations in that the effects of the present invention can be further exhibited.
　フルオロ有機アニオンとしては、本発明の効果を損なわない範囲で、任意の適切なフルオロ有機アニオンを採用し得る。フルオロ有機アニオンは、完全にフッ素化（パーフルオロ化）されていてもよいし、部分的にフッ素化されていてもよい。 As the fluoroorganic anion, any suitable fluoroorganic anion can be adopted as long as the effect of the present invention is not impaired. The fluoroorganic anion may be completely fluorinated (perfluoro) or partially fluorinated.
　このようなフルオロ有機アニオンとしては、例えば、フッ素化されたアリールスルホネート、パーフルオロアルカンスルホネート、ビス（フルオロスルホニル）イミド、ビス（パーフルオロアルカンスルホニル）イミド、シアノパーフルオロアルカンスルホニルアミド、ビス（シアノ）パーフルオロアルカンスルホニルメチド、シアノ－ビス－（パーフルオロアルカンスルホニル）メチド、トリス（パーフルオロアルカンスルホニル）メチド、トリフルオロアセテート、パーフルオロアルキレート、トリス（パーフルオロアルカンスルホニル）メチド、（パーフルオロアルカンスルホニル）トリフルオロアセトアミドなどが挙げられる。 Examples of such fluoroorganic anions include fluorinated arylsulfonates, perfluoroalkanesulfonates, bis (fluorosulfonyl) imides, bis (perfluoroalkanesulfonyl) imides, cyanoperfluoroalkanesulfonylamides, and bis (cyano). Perfluoroalkanesulfonyl methide, cyano-bis- (perfluoroalkanesulfonyl) methide, tris (perfluoroalkanesulfonyl) methide, trifluoroacetate, perfluoroalkanelate, tris (perfluoroalkanesulfonyl) methide, (perfluoroalkane sulfonyl) Sulfonyl) Trifluoroacetamide and the like can be mentioned.
　これらのフルオロ有機アニオンの中でも、本発明の効果をより発現させ得る点で、好ましくは、パーフルオロアルキルスルホネート、ビス（フルオロスルホニル）イミド、ビス（パーフルオロアルカンスルホニル）イミドであり、より具体的には、例えば、トリフルオロメタンスルホネート、ペンタフルオロエタンスルホネート、ヘプタフルオロプロパンスルホネート、ノナフルオロブタンスルホネート、ビス（フルオロスルホニル）イミド、ビス（トリフルオロメタンスルホニル）イミドであり、好ましくは、ビス（フルオロスルホニル）イミド、ビス（トリフルオロメタンスルホニル）イミドである。 Among these fluoroorganic anions, perfluoroalkylsulfonate, bis (fluorosulfonyl) imide, and bis (perfluoroalkanesulfonyl) imide are preferable in that the effects of the present invention can be more exhibited, and more specifically. Is, for example, trifluoromethanesulfonate, pentafluoroethanesulfonate, heptafluoropropanesulfonate, nonafluorobutanesulfonate, bis (fluorosulfonyl) imide, bis (trifluoromethanesulfonyl) imide, preferably bis (fluorosulfonyl) imide, It is a bis (trifluoromethanesulfonyl) imide.
　イオン性化合物としては、本発明の効果をより発現させ得る点で、より好ましくは、オニウムカチオンとフルオロ有機アニオンとから構成されるイオン性化合物である。 The ionic compound is more preferably an ionic compound composed of an onium cation and a fluoroorganic anion in that the effects of the present invention can be more exhibited.
　オニウムカチオンとしては、好ましくは、一般式（１）～（４）で表される構造から選ばれる少なくとも１種を有する。
Figure JPOXMLDOC01-appb-C000001
 The onium cation preferably has at least one selected from the structures represented by the general formulas (1) to (4).
Figure JPOXMLDOC01-appb-C000001
　一般式（１）において、Ｒ
ａは、炭素数４から２０の炭化水素基を表し、ヘテロ原子を含んでいてもよく、ＲｂおよびＲｃは、同一または異なって、水素または炭素数１から１６の炭化水素基を表し、ヘテロ原子を含んでいてもよい。ただし、窒素原子が２重結合を含む場合、Ｒｃはない。 In the general formula (1), R
a represents a hydrocarbon group having 4 to 20 carbon atoms and may contain a heteroatom, and Rb and Rc represent hydrogen or a hydrocarbon group having 1 to 16 carbon atoms, which are the same or different, and are heteroatoms. May include. However, when the nitrogen atom contains a double bond, there is no Rc.
　一般式（２）において、Ｒｄは、炭素数２から２０の炭化水素基を表し、ヘテロ原子を含んでいてもよく、Ｒｅ、Ｒｆ、およびＲｇは、同一または異なって、水素または炭素数１から１６の炭化水素基を表し、ヘテロ原子を含んでいてもよい。 In the general formula (2), Rd represents a hydrocarbon group having 2 to 20 carbon atoms and may contain a heteroatom, and Re, Rf, and Rg are the same or different from hydrogen or 1 carbon atom. It represents 16 hydrocarbon groups and may contain heteroatoms.
　一般式（３）において、Ｒｈは、炭素数２から２０の炭化水素基を表し、ヘテロ原子を含んでいてもよく、Ｒｉ、Ｒｊ、およびＲｋは、同一または異なって、水素または炭素数１から１６の炭化水素基を表し、ヘテロ原子を含んでいてもよい。 In the general formula (3), Rh represents a hydrocarbon group having 2 to 20 carbon atoms and may contain a heteroatom, and Ri, Rj, and Rk are the same or different from hydrogen or 1 carbon atom. It represents 16 hydrocarbon groups and may contain heteroatoms.
　一般式（４）において、Ｚは、窒素原子、硫黄原子、またはリン原子を表し、Ｒｌ、Ｒｍ、Ｒｎ、およびＲｏは、同一または異なって、炭素数１から２０の炭化水素基を表し、ヘテロ原子を含んでいてもよい。ただしＺが硫黄原子の場合、Ｒｏはない。 In the general formula (4), Z represents a nitrogen atom, a sulfur atom, or a phosphorus atom, and Rl, Rm, Rn, and Ro represent a hydrocarbon group having 1 to 20 carbon atoms, which is the same or different, and is hetero. It may contain atoms. However, when Z is a sulfur atom, there is no Ro.
　一般式（１）で表されるカチオン構造としては、例えば、ピリジニウムカチオン構造、ピロリジニウムカチオン構造、ピペリジニウムカチオン構造、ピロリン骨格を有するカチオン構造、ピロール骨格を有するカチオン構造などが挙げられる。 Examples of the cation structure represented by the general formula (1) include a pyridinium cation structure, a pyrrolidinium cation structure, a piperidinium cation structure, a cation structure having a pyrroline skeleton, and a cation structure having a pyrrole skeleton.
　一般式（１）で表されるカチオンの具体例としては、例えば、１－エチルピリジニウムカチオン、１－ブチルピリジニウムカチオン、１－へキシルピリジニウムカチオン、１－エチル－３－メチルピリジニウムカチオン、１－ブチル－３－メチルピリジニウムカチオン、１－へキシル－３－メチルピリジニウムカチオン、１－ブチル－４－メチルピリジニウムカチオン、１－オクチル－４－メチルピリジニウムカチオン、１－ブチル－３，４－ジメチルピリジニウムカチオン、１，１－ジメチルピロリジニウムカチオン等のピリジニウムカチオン；１－エチル－１－メチルピロリジニウムカチオン、１－メチル－１－プロピルピロリジニウムカチオン、１－メチル－１－ブチルピロリジニウムカチオン、１－メチル－１－ペンチルピロリジニウムカチオン、１－メチル－１－へキシルピロリジニウムカチオン、１－メチル－１－ヘプチルピロリジニウムカチオン、１－エチル－１－プロピルピロリジニウムカチオン、１－エチル－１－ブチルピロリジニウムカチオン、１－エチル－１－ペンチルピロリジニウムカチオン、１－エチル－１－へキシルピロリジニウムカチオン、１－エチル－１－へプチルピロリジニウムカチオン、１，１－ジプロピルピロリジニウムカチオン、１－プロピル－１－ブチルピロリジニウムカチオン、１，１－ジブチルピロリジニウムカチオン等のピロリジニウムカチオン；１－プロピルピペリジニウムカチオン、１－ペンチルピペリジニウムカチオン、１－メチル－１－エチルピペリジニウムカチオン、１－メチル－１－プロピルピペリジニウムカチオン、１－メチル－１－ブチルピペリジニウムカチオン、１－メチル－１－ペンチルピペリジニウムカチオン、１－メチル－１－ヘキシルピペリジニウムカチオン、１－メチル－１－へプチルピペリジニウムカチオン、１－エチル－１－プロピルピペリジニウムカチオン、１－エチル－１－ブチルピペリジニウムカチオン、１－エチル－１－ペンチルピペリジニウムカチオン、１－エチル－１－ヘキシルピペリジニウムカチオン、１－エチル－１－へプチルピペリジニウムカチオン、１－プロピル－１－ブチルピペリジニウムカチオン、１，１－ジメチルピペリジニウムカチオン、１，１－ジプロピルピペリジニウムカチオン、１，１－ジブチルピペリジニウムカチオン等のピペリジニウムカチオン；２－メチル－１－ピロリンカチオン；１－エチル－２－フェニルインドールカチオン；１，２－ジメチルインドールカチオン；１－エチルカルバゾールカチオン；これらのカチオンがさらにビニル基（ＣＨ２＝ＣＨ－基）およびアリル基（ＣＨ２＝ＣＨ－ＣＨ２－基）から選ばれる少なくとも１種を有するカチオン；などが挙げられる。 Specific examples of the cation represented by the general formula (1) include, for example, 1-ethylpyridinium cation, 1-butylpyridinium cation, 1-hexylpyridinium cation, 1-ethyl-3-methylpyridinium cation, 1-butyl. -3-Methylpyridinium cation, 1-hexyl-3-methylpyridinium cation, 1-butyl-4-methylpyridinium cation, 1-octyl-4-methylpyridinium cation, 1-butyl-3,4-dimethylpyridinium cation, Pyridinium cations such as 1,1-dimethylpyrrolidinium cations; 1-ethyl-1-methylpyrrolidinium cations, 1-methyl-1-propylpyrrolidinium cations, 1-methyl-1-butylpyrrolidinium cations, 1-Methyl-1-pentylpyrrolidinium cation, 1-methyl-1-hexylpyrrolidinium cation, 1-methyl-1-heptylpyrrolidinium cation, 1-ethyl-1-propylpyrrolidinium cation, 1 -Ethyl-1-butylpyrridinium cation, 1-ethyl-1-pentylpyrrolidinium cation, 1-ethyl-1-hexylpyrrolidinium cation, 1-ethyl-1-heptylpyrrolidinium cation, 1 , 1-Dipropylpyrridinium cation, 1-propyl-1-butylpyrridinium cation, 1,1-dibutylpyrridinium cation and other pyrrolidinium cations; 1-propylpiperidinium cation, 1-pentylpi Pyridinium cation, 1-methyl-1-ethylpiperidinium cation, 1-methyl-1-propylpiperidinium cation, 1-methyl-1-butylpiperidinium cation, 1-methyl-1-pentylpiperidinium Cations, 1-methyl-1-hexylpiperidinium cations, 1-methyl-1-heptylpiperidinium cations, 1-ethyl-1-propylpiperidinium cations, 1-ethyl-1-butylpiperidinium cations , 1-Ethyl-1-pentylpiperidinium cation, 1-ethyl-1-hexylpiperidinium cation, 1-ethyl-1-heptylpiperidinium cation, 1-propyl-1-butylpiperidinium cation, Piperidinium cations such as 1,1-dimethylpiperidinium cation, 1,1-dipropylpiperidinium cation, 1,1-dibutylpiperidinium cation; 2-methyl-1-pyrrolinate cation; 1-d Chill-2-phenylindole cation; 1,2-dimethylindole cation; 1-ethylcarbazole cation; these cations are further vinyl group (CH 2 = CH- group) and allyl group (CH 2 = CH-CH 2- group). ), A cation having at least one selected from the above; and the like.
　これらの中でも、本発明の効果がより一層発現し得る点で、好ましくは、１－エチルピリジニウムカチオン、１－ブチルピリジニウムカチオン、１－へキシルピリジニウムカチオン、１－エチル－３－メチルピリジニウムカチオン、１－ブチル－３－メチルピリジニウムカチオン、１－へキシル－３－メチルピリジニウムカチオン、１－ブチル－４－メチルピリジニウムカチオン、１－オクチル－４－メチルピリジニウムカチオン等のピリジニウムカチオン；１－エチル－１－メチルピロリジニウムカチオン、１－メチル－１－プロピルピロリジニウムカチオン、１－メチル－１－ブチルピロリジニウムカチオン、１－メチル－１－ペンチルピロリジニウムカチオン、１－メチル－１－へキシルピロリジニウムカチオン、１－メチル－１－ヘプチルピロリジニウムカチオン、１－エチル－１－プロピルピロリジニウムカチオン、１－エチル－１－ブチルピロリジニウムカチオン、１－エチル－１－ペンチルピロリジニウムカチオン、１－エチル－１－へキシルピロリジニウムカチオン、１－エチル－１－へプチルピロリジニウムカチオン等のピロリジニウムカチオン；１－メチル－１－エチルピペリジニウムカチオン、１－メチル－１－プロピルピペリジニウムカチオン、１－メチル－１－ブチルピペリジニウムカチオン、１－メチル－１－ペンチルピペリジニウムカチオン、１－メチル－１－ヘキシルピペリジニウムカチオン、１－メチル－１－へプチルピペリジニウムカチオン、１－エチル－１－プロピルピペリジニウムカチオン、１－エチル－１－ブチルピペリジニウムカチオン、１－エチル－１－ペンチルピペリジニウムカチオン、１－エチル－１－ヘキシルピペリジニウムカチオン、１－エチル－１－へプチルピペリジニウムカチオン、１－プロピル－１－ブチルピペリジニウムカチオン等のピペリジニウムカチオン；これらのカチオンがさらにビニル基（ＣＨ２＝ＣＨ－基）およびアリル基（ＣＨ２＝ＣＨ－ＣＨ２－基）から選ばれる少なくとも１種を有するカチオン；などが挙げられ、より好ましくは、１－へキシルピリジニウムカチオン、１－エチル－３－メチルピリジニウムカチオン、１－ブチル－３－メチルピリジニウムカチオン、１－オクチル－４－メチルピリジニウムカチオン、１－メチル－１－プロピルピロリジニウムカチオン、１－メチル－１－プロピルピペリジニウムカチオン、これらのカチオンがさらにビニル基（ＣＨ２＝ＣＨ－基）およびアリル基（ＣＨ２＝ＣＨ－ＣＨ２－基）から選ばれる少なくとも１種を有するカチオンである。 Among these, 1-ethylpyridinium cation, 1-butylpyridinium cation, 1-hexylpyridinium cation, 1-ethyl-3-methylpyridinium cation, 1-ethylpyridinium cation are preferable in that the effect of the present invention can be further exhibited. -Pyridinium cations such as butyl-3-methylpyridinium cation, 1-hexyl-3-methylpyridinium cation, 1-butyl-4-methylpyridinium cation, 1-octyl-4-methylpyridinium cation; 1-ethyl-1- Methylpyrridinium cation, 1-methyl-1-propylpyrrolidinium cation, 1-methyl-1-butylpyrrolidinium cation, 1-methyl-1-pentylpyrrolidinium cation, 1-methyl-1-hexyl Pyridinium cation, 1-methyl-1-heptylpyrrolidinium cation, 1-ethyl-1-propylpyrrolidinium cation, 1-ethyl-1-butylpyrrolidinium cation, 1-ethyl-1-pentylpyrrolidinium Pyridinium cations such as nium cations, 1-ethyl-1-hexylpyrrolidinium cations, 1-ethyl-1-heptylpyrrolidinium cations; 1-methyl-1-ethylpiperidinium cations, 1-methyl -1-propylpiperidinium cation, 1-methyl-1-butylpiperidinium cation, 1-methyl-1-pentylpiperidinium cation, 1-methyl-1-hexylpiperidinium cation, 1-methyl-1 -Heptylpiperidinium cation, 1-ethyl-1-propylpiperidinium cation, 1-ethyl-1-butylpiperidinium cation, 1-ethyl-1-pentylpiperidinium cation, 1-ethyl-1- Piperidinium cations such as hexylpiperidinium cations, 1-ethyl-1-heptylpyridinium cations, 1-propyl-1-butylpiperidinium cations; these cations are further vinyl groups (CH 2 = CH- Groups) and cations having at least one selected from allyl groups (CH 2 = CH-CH 2 -group); and the like, more preferably 1-hexylpyridinium cations, 1-ethyl-3-methylpyridinium. Cationic, 1-butyl-3-methylpyridinium cation, 1-octyl-4-methylpyridinium cation, 1-methyl-1-propylpyrrolidinium cation, 1-methyl-1-propylpyridinium cation , These cations are cations having at least one selected from a vinyl group (CH 2 = CH- group) and an allyl group (CH 2 = CH-CH 2- group).
　一般式（２）で表されるカチオン構造としては、例えば、イミダゾリウムカチオン構造、テトラヒドロピリミジニウムカチオン構造、ジヒドロピリミジニウムカチオン構造などが挙げられる。 Examples of the cation structure represented by the general formula (2) include an imidazolium cation structure, a tetrahydropyrimidinium cation structure, and a dihydropyrimidinium cation structure.
　一般式（２）で表されるカチオンの具体例としては、例えば、１，３－ジメチルイミダゾリウムカチオン、１，３－ジエチルイミダゾリウムカチオン、１－エチル－３－メチルイミダゾリウムカチオン、１－ブチル－３－メチルイミダゾリウムカチオン、１－へキシル－３－メチルイミダゾリウムカチオン、１－オクチル－３－メチルイミダゾリウムカチオン、１－デシル－３－メチルイミダゾリウムカチオン、１－ドデシル－３－メチルイミダゾリウムカチオン、１－テトラデシル－３－メチルイミダゾリウムカチオン、１，２－ジメチル－３－プロピルイミダゾリウムカチオン、１－エチル－２，３－ジメチルイミダゾリウムカチオン、１－ブチル－２，３－ジメチルイミダゾリウムカチオン、１－へキシル－２，３－ジメチルイミダゾリウムカチオン等のイミダゾリウムカチオン；１，３－ジメチル－１，４，５，６－テトラヒドロピリミジニウムカチオン、１，２，３－トリメチル－１，４，５，６－テトラヒドロピリミジニウムカチオン、１，２，３，４－テトラメチル－１，４，５，６－テトラヒドロピリミジニウムカチオン、１，２，３，５－テトラメチル－１，４，５，６－テトラヒドロピリミジニウムカチオン等のテトラヒドロピリミジニウムカチオン；１，３－ジメチル－１，４－ジヒドロピリミジニウムカチオン、１，３－ジメチル－１，６－ジヒドロピリミジニウムカチオン、１，２，３－トリメチル－１，４－ジヒドロピリミジニウムカチオン、１，２，３－トリメチル－１，６－ジヒドロピリミジニウムカチオン、１，２，３，４－テトラメチル－１，４－ジヒドロピリミジニウムカチオン、１，２，３，４－テトラメチル－１，６－ジヒドロピリミジニウムカチオンなどのジヒドロピリミジニウムカチオン；これらのカチオンがさらにビニル基（ＣＨ２＝ＣＨ－基）およびアリル基（ＣＨ２＝ＣＨ－ＣＨ２－基）から選ばれる少なくとも１種を有するカチオン；などが挙げられる。 Specific examples of the cation represented by the general formula (2) include, for example, 1,3-dimethylimidazolium cation, 1,3-diethylimidazolium cation, 1-ethyl-3-methylimidazolium cation, and 1-butyl. -3-Methylimidazolium cation, 1-hexyl-3-methylimidazolium cation, 1-octyl-3-methylimidazolium cation, 1-decyl-3-methylimidazolium cation, 1-dodecyl-3-methylimidazolium cation Rium cation, 1-tetradecyl-3-methylimidazolium cation, 1,2-dimethyl-3-propylimidazolium cation, 1-ethyl-2,3-dimethylimidazolium cation, 1-butyl-2,3-dimethylimidazolium cation Imidazolium cations such as lithium cations, 1-hexyl-2,3-dimethylimidazolium cations; 1,3-dimethyl-1,4,5,6-tetrahydropyrimidinium cations, 1,2,3-trimethyl- 1,4,5,6-Tetrahydropyrimidinium cation, 1,2,3,4-tetramethyl-1,4,5,6-tetrahydropyrimidinium cation, 1,2,3,5-tetramethyl- Tetrahydropyrimidinium cations such as 1,4,5,6-tetrahydropyrimidinium cations; 1,3-dimethyl-1,4-dihydropyrimidinium cations, 1,3-dimethyl-1,6-dihydropyrimidi Nium cation, 1,2,3-trimethyl-1,4-dihydropyrimidinium cation, 1,2,3-trimethyl-1,6-dihydropyrimidinium cation, 1,2,3,4-tetramethyl- Dihydropyrimidinium cations such as 1,4-dihydropyrimidinium cations, 1,2,3,4-tetramethyl-1,6-dihydropyrimidinium cations; these cations are further vinyl groups (CH 2 = CH). -Groups) and cations having at least one selected from allyl groups (CH 2 = CH-CH 2 -groups); and the like.
　これらの中でも、本発明の効果がより一層発現し得る点で、好ましくは、１，３－ジメチルイミダゾリウムカチオン、１，３－ジエチルイミダゾリウムカチオン、１－エチル－３－メチルイミダゾリウムカチオン、１－ブチル－３－メチルイミダゾリウムカチオン、１－へキシル－３－メチルイミダゾリウムカチオン、１－オクチル－３－メチルイミダゾリウムカチオン、１－デシル－３－メチルイミダゾリウムカチオン、１－ドデシル－３－メチルイミダゾリウムカチオン、１－テトラデシル－３－メチルイミダゾリウムカチオン、これらのカチオンがさらにビニル基（ＣＨ２＝ＣＨ－基）およびアリル基（ＣＨ２＝ＣＨ－ＣＨ２－基）から選ばれる少なくとも１種を有するカチオン等のイミダゾリウムカチオンであり、より好ましくは、１－エチル－３－メチルイミダゾリウムカチオン、１－へキシル－３－メチルイミダゾリウムカチオン、これらのカチオンがさらにビニル基（ＣＨ２＝ＣＨ－基）およびアリル基（ＣＨ２＝ＣＨ－ＣＨ２－基）から選ばれる少なくとも１種を有するカチオンである。 Among these, 1,3-dimethylimidazolium cation, 1,3-diethylimidazolium cation, 1-ethyl-3-methylimidazolium cation, 1 are preferable in that the effect of the present invention can be further exhibited. -Butyl-3-methylimidazolium cation, 1-hexyl-3-methylimidazolium cation, 1-octyl-3-methylimidazolium cation, 1-decyl-3-methylimidazolium cation, 1-dodecyl-3- Methyl imidazolium cations, 1-tetradecyl-3-methyl imidazolium cations, at least one of which is further selected from a vinyl group (CH 2 = CH- group) and an allyl group (CH 2 = CH-CH 2 -group). It is an imidazolium cation such as a cation having a species, more preferably 1-ethyl-3-methylimidazolium cation, 1-hexyl-3-methylimidazolium cation, and these cations are further vinyl groups (CH 2 =). A cation having at least one selected from a CH-group) and an allyl group ( CH2 = CH- CH2 -group).
　一般式（３）で表されるカチオン構造としては、例えば、ピラゾリウムカチオン構造、ピラゾリニウムカチオン構造などが挙げられる。 Examples of the cation structure represented by the general formula (3) include a pyrazolium cation structure and a pyrazolinium cation structure.
　一般式（３）で表されるカチオンの具体例としては、例えば、１－メチルピラゾリウムカチオン、３－メチルピラゾリウムカチオン、１－エチル－２－メチルピラゾリニウムカチオン、１－エチル－２，３，５－トリメチルピラゾリウムカチオン、１－プロピル－２，３，５－トリメチルピラゾリウムカチオン、１－ブチル－２，３，５－トリメチルピラゾリウムカチオン等のピラゾリウムカチオン；１－エチル－２，３，５－トリメチルピラゾリニウムカチオン、１－プロピル－２，３，５－トリメチルピラゾリニウムカチオン、１－ブチル－２，３，５－トリメチルピラゾリニウムカチオン等のピラゾリニウムカチオン；これらのカチオンがさらにビニル基（ＣＨ２＝ＣＨ－基）およびアリル基（ＣＨ２＝ＣＨ－ＣＨ２－基）から選ばれる少なくとも１種を有するカチオン；などが挙げられる。 Specific examples of the cation represented by the general formula (3) include, for example, 1-methylpyrazolium cation, 3-methylpyrazolium cation, 1-ethyl-2-methylpyrazolinium cation, 1-ethyl-. Pyrazolium cations such as 2,3,5-trimethylpyrazolium cation, 1-propyl-2,3,5-trimethylpyrazolium cation, 1-butyl-2,3,5-trimethylpyrazolium cation; Pila such as 1-ethyl-2,3,5-trimethylpyrazolinium cation, 1-propyl-2,3,5-trimethylpyrazolinium cation, 1-butyl-2,3,5-trimethylpyrazolinium cation Zolinium cations; cations in which these cations have at least one selected from a vinyl group (CH 2 = CH-group) and an allyl group (CH 2 = CH-CH 2 -group); and the like.
　一般式（４）で表されるカチオン構造としては、例えば、テトラアルキルアンモニウムカチオン構造、トリアルキルスルホニウムカチオン構造、テトラアルキルホスホニウムカチオン構造や、上記アルキル基の一部がアルケニル基やアルコキシル基やエポキシ基に置換されたものなどが挙げられる。 Examples of the cation structure represented by the general formula (4) include a tetraalkylammonium cation structure, a trialkylsulfonium cation structure, a tetraalkylphosphonium cation structure, and a part of the above alkyl groups is an alkenyl group, an alkoxyl group, or an epoxy group. Examples include those replaced with.
　一般式（４）で表されるカチオンの具体例としては、例えば、テトラメチルアンモニウムカチオン、テトラエチルアンモニウムカチオン、テトラブチルアンモニウムカチオン、テトラペンチルアンモニウムカチオン、テトラヘキシルアンモニウムカチオン、テトラヘプチルアンモニウムカチオン、トリエチルメチルアンモニウムカチオン、トリブチルエチルアンモニウムカチオン、トリメチルプロピルアンモニウムカチオン、トリメチルデシルアンモニウムカチオン、Ｎ，Ｎ－ジエチル－Ｎ－メチル－Ｎ－（２－メトキシエチル）アンモニウムカチオン、グリシジルトリメチルアンモニウムカチオン、ジアリルジメチルアンモニウムカチオン、Ｎ，Ｎ－ジメチル－Ｎ－エチル－Ｎ－プロピルアンモニウムカチオン、Ｎ，Ｎ－ジメチル－Ｎ－エチル－Ｎ－ブチルアンモニウムカチオン、Ｎ，Ｎ－ジメチル－Ｎ－エチル－Ｎ－ペンチルアンモニウムカチオン、Ｎ，Ｎ－ジメチル－Ｎ－エチル－Ｎ－ヘキシルアンモニウムカチオン、Ｎ，Ｎ－ジメチル－Ｎ－エチル－Ｎ－ヘプチルアンモニウムカチオン、Ｎ，Ｎ－ジメチル－Ｎ－エチル－Ｎ－ノニルアンモニウムカチオン、Ｎ，Ｎ－ジメチル－Ｎ，Ｎ－ジプロピルアンモニウムカチオン、Ｎ，Ｎ－ジエチル－Ｎ－プロピル－Ｎ－ブチルアンモニウムカチオン、Ｎ，Ｎ－ジメチル－Ｎ－プロピル－Ｎ－ペンチルアンモニウムカチオン、Ｎ，Ｎ－ジメチル－Ｎ－プロピル－Ｎ－ヘキシルアンモニウムカチオン、Ｎ，Ｎ－ジメチル－Ｎ－プロピル－Ｎ－ヘプチルアンモニウムカチオン、Ｎ，Ｎ－ジメチル－Ｎ－ブチル－Ｎ－ヘキシルアンモニウムカチオン、Ｎ，Ｎ－ジエチル－Ｎ－ブチル－Ｎ－ヘプチルアンモニウムカチオン、Ｎ，Ｎ－ジメチル－Ｎ－ペンチル－Ｎ－ヘキシルアンモニウムカチオン、Ｎ，Ｎ－ジメチル－Ｎ，Ｎ－ジヘキシルアンモニウムカチオン、トリメチルヘプチルアンモニウムカチオン、Ｎ，Ｎ－ジエチル－Ｎ－メチル－Ｎ－プロピルアンモニウムカチオン、Ｎ，Ｎ－ジエチル－Ｎ－メチル－Ｎ－ペンチルアンモニウムカチオン、Ｎ，Ｎ－ジエチル－Ｎ－メチル－Ｎ－ヘプチルアンモニウムカチオン、Ｎ，Ｎ－ジエチル－Ｎ－プロピル－Ｎ－ペンチルアンモニウムカチオン、トリエチルプロピルアンモニウムカチオン、トリエチルペンチルアンモニウムカチオン、トリエチルヘプチルアンモニウムカチオン、Ｎ，Ｎ－ジプロピル－Ｎ－メチル－Ｎ－エチルアンモニウムカチオン、Ｎ，Ｎ－ジプロピル－Ｎ－メチル－Ｎ－ペンチルアンモニウムカチオン、Ｎ，Ｎ－ジプロピル－Ｎ－ブチル－Ｎ－ヘキシルアンモニウムカチオン、Ｎ，Ｎ－ジプロピル－Ｎ，Ｎ－ジヘキシルアンモニウムカチオン、Ｎ，Ｎ－ジブチル－Ｎ－メチル－Ｎ－ペンチルアンモニウムカチオン、Ｎ，Ｎ－ジブチル－Ｎ－メチル－Ｎ－ヘキシルアンモニウムカチオン、トリオクチルメチルアンモニウムカチオン、Ｎ－メチル－Ｎ－エチル－Ｎ－プロピル－Ｎ－ペンチルアンモニウムカチオン等のテトラアルキルアンモニウムカチオン；トリメチルスルホニウムカチオン、トリエチルスルホニウムカチオン、トリブチルスルホニウムカチオン、トリヘキシルスルホニウムカチオン、ジエチルメチルスルホニウムカチオン、ジブチルエチルスルホニウムカチオン、ジメチルデシルスルホニウムカチオン等のトリアルキルスルホニウムカチオン；テトラメチルホスホニウムカチオン、テトラエチルホスホニウムカチオン、テトラブチルホスホニウムカチオン、テトラヘキシルホスホニウムカチオン、テトラオクチルホスホニウムカチオン、トリエチルメチルホスホニウムカチオン、トリブチルエチルホスホニウムカチオン、トリメチルデシルホスホニウムカチオン等のテトラアルキルホスホニウムカチオン；これらのカチオンがさらにビニル基（ＣＨ２＝ＣＨ－基）およびアリル基（ＣＨ２＝ＣＨ－ＣＨ２－基）から選ばれる少なくとも１種を有するカチオン；などが挙げられる。 Specific examples of the cation represented by the general formula (4) include, for example, tetramethylammonium cation, tetraethylammonium cation, tetrabutylammonium cation, tetrapentylammonium cation, tetrahexylammonium cation, tetraheptylammonium cation, and triethylmethylammonium. Cationic, Tributylethylammonium cation, trimethylpropylammonium cation, trimethyldecylammonium cation, N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium cation, glycidyltrimethylammonium cation, diallyldimethylammonium cation, N, N-dimethyl-N-ethyl-N-propylammonium cation, N, N-dimethyl-N-ethyl-N-butylammonium cation, N, N-dimethyl-N-ethyl-N-pentylammonium cation, N, N- Dimethyl-N-ethyl-N-hexylammonium cation, N, N-dimethyl-N-ethyl-N-heptylammonium cation, N, N-dimethyl-N-ethyl-N-nonylammonium cation, N, N-dimethyl- N, N-dipropylammonium cation, N, N-diethyl-N-propyl-N-butylammonium cation, N, N-dimethyl-N-propyl-N-pentylammonium cation, N, N-dimethyl-N-propyl -N-hexylammonium cation, N, N-dimethyl-N-propyl-N-heptylammonium cation, N, N-dimethyl-N-butyl-N-hexylammonium cation, N, N-diethyl-N-butyl-N -Heptylammonium cation, N, N-dimethyl-N-pentyl-N-hexylammonium cation, N, N-dimethyl-N, N-dihexylammonium cation, trimethylheptylammonium cation, N, N-diethyl-N-methyl- N-propylammonium cation, N, N-diethyl-N-methyl-N-pentylammonium cation, N, N-diethyl-N-methyl-N-heptylammonium cation, N, N-diethyl-N-propyl-N- Pentylammonium cation, triethylpropylammonium cation, triethylpentylammonium cation, triethylheptylammonium cation, N, N-dipropyl-N-methyl-N-ethylammoniu Mucation, N, N-dipropyl-N-methyl-N-pentylammonium cation, N, N-dipropyl-N-butyl-N-hexylammonium cation, N, N-dipropyl-N, N-dihexylammonium cation, N, N-dibutyl-N-methyl-N-pentylammonium cation, N, N-dibutyl-N-methyl-N-hexylammonium cation, trioctylmethylammonium cation, N-methyl-N-ethyl-N-propyl-N- Tetraalkylammonium cations such as pentylammonium cations; trialkylsulfonium cations such as trimethylsulfonium cations, triethylsulfonium cations, tributylsulfonium cations, trihexylsulfonium cations, diethylmethylsulfonium cations, dibutylethylsulfonium cations, dimethyldecylsulfonium cations; tetramethyl Tetraalkylphosphonium cations such as phosphonium cations, tetraethylphosphonium cations, tetrabutylphosphonium cations, tetrahexylphosphonium cations, tetraoctylphosphonium cations, triethylmethylphosphonium cations, tributylethylphosphonium cations, trimethyldecylphosphonium cations; these cations are further vinyl groups. Examples thereof include a cation having at least one selected from (CH 2 = CH- group) and an allyl group (CH 2 = CH-CH 2- group); and the like.
　イオン性化合物としては、好ましくは、上記のオニウムカチオンおよび上記の金属カチオンから選ばれる少なくとも１種と上記のフルオロ有機アニオンを含むイオン性化合物、イオン性基含有シリコーンオリゴマーであり、より好ましくは、上記のオニウムカチオンおよび上記の金属カチオンから選ばれる少なくとも１種と上記のフルオロ有機アニオンを含むイオン性化合物であり、さらに好ましくは、上記のオニウムカチオンと上記のフルオロ有機アニオンを含むイオン性化合物である。 The ionic compound is preferably an ionic compound containing at least one selected from the above onium cation and the above metal cation and the above fluoroorganic anion, and an ionic group-containing silicone oligomer, and more preferably the above. It is an ionic compound containing at least one selected from the above-mentioned onium cation and the above-mentioned metal cation and the above-mentioned fluoroorganic anion, and more preferably, it is an ionic compound containing the above-mentioned onium cation and the above-mentioned fluoroorganic anion.
　本発明の効果をより発現させ得る点で、イオン性化合物としては、好ましくは、具体的には、１－ヘキシルピリジニウムビス（フルオロスルホニル）イミド、１－エチル－３－メチルピリジニウムトリフルオロメタンスルホネート、１－エチル－３－メチルピリジニウムペンタフルオロエタンスルホネート、１－エチル－３－メチルピリジニウムヘプタフルオロプロパンスルホネート、１－エチル－３－メチルピリジニウムノナフルオロブタンスルホネート、１－ブチル－３－メチルピリジニウムトリフルオロメタンスルホネート、１－ブチル－３－メチルピリジニウムビス（トリフルオロメタンスルホニル）イミド、１－オクチル－４－メチルピリジニウムビス（フルオロスルホニル）イミド、１－メチル－１－プロピルピロリジニウムビス（トリフルオロメタンスルホニル）イミド、１－メチル－１－プロピルピロリジニウムビス（フルオロスルホニル）イミド、１－メチル－１－プロピルピペリジニウムビス（トリフルオロメタンスルホニル）イミド、１－メチル－１－プロピルピペリジニウムビス（フルオロスルホニル）イミド、１－エチル－３－メチルイミダゾリウムトリフルオロメタンスルホネート、１－エチル－３－メチルイミダゾリウムヘプタフルオロプロパンスルホネート、１－エチル－３－メチルイミダゾリウムビス（トリフルオロメタンスルホニル）イミド、１－エチル－３－メチルイミダゾリウムビス（フルオロスルホニル）イミド、１－ヘキシル－３－メチルイミダゾリウムビス（フルオロスルホニル）イミド、１－アリル－３－メチル－イミダゾリウムトリフルオロメタンスルホネート、１－アリル－３－メチル－イミダゾリウムヘプタフルオロプロパンスルホネート、１－アリル－３－メチル－イミダゾリウムビス（トリフルオロメタンスルホニル）イミド、１－アリル－３－メチル－イミダゾリウムビス（フルオロスルホニル）イミド、メチルトリオクチルアンモニウムビス（トリフルオロメタンスルホニル）イミド、トリメチルプロピルアンモニウムビス（トリフルオロメタンスルホニル）イミド、リチウムビス（トリフルオロメタンスルホニル）イミド、リチウムビス（フルオロスルホニル）イミドであり、さらに好ましくは、１－ブチル－３－メチルピリジニウムビス（トリフルオロメタンスルホニル）イミド、１－エチル－３－メチルイミダゾリウムビス（フルオロスルホニル）イミド、１－アリル－３－メチル－イミダゾリウムビス（トリフルオロメタンスルホニル）イミド、メチルトリオクチルアンモニウムビス（トリフルオロメタンスルホニル）イミド、トリメチルプロピルアンモニウムビス（トリフルオロメタンスルホニル）イミド、リチウムビス（トリフルオロメタンスルホニル）イミドであり、特に好ましくは、１－ブチル－３－メチルピリジニウムビス（トリフルオロメタンスルホニル）イミド、１－エチル－３－メチルイミダゾリウムビス（フルオロスルホニル）イミド、１－アリル－３－メチル－イミダゾリウムビス（トリフルオロメタンスルホニル）イミド、メチルトリオクチルアンモニウムビス（トリフルオロメタンスルホニル）イミド、トリメチルプロピルアンモニウムビス（トリフルオロメタンスルホニル）イミドである。 In terms of further exhibiting the effects of the present invention, the ionic compound is preferably preferably 1-hexylpyridinium bis (fluorosulfonyl) imide, 1-ethyl-3-methylpyridinium trifluoromethanesulfonate, 1 -Ethyl-3-methylpyridinium pentafluoroethanesulfonate, 1-ethyl-3-methylpyridinium heptafluoropropanesulfonate, 1-ethyl-3-methylpyridinium nonafluorobutane sulfonate, 1-butyl-3-methylpyridinium trifluoromethanesulfonate, 1-butyl-3-methylpyridinium bis (trifluoromethanesulfonyl) imide, 1-octyl-4-methylpyridinium bis (fluorosulfonyl) imide, 1-methyl-1-propylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1 -Methyl-1-propylpyrrolidinium bis (fluorosulfonyl) imide, 1-methyl-1-propylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-propylpiperidinium bis (fluorosulfonyl) imide , 1-ethyl-3-methylimidazolium trifluoromethanesulfonate, 1-ethyl-3-methylimidazolium heptafluoropropanesulfonate, 1-ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide, 1-ethyl-3 -Methylimidazolium bis (fluorosulfonyl) imide, 1-hexyl-3-methylimidazolium bis (fluorosulfonyl) imide, 1-allyl-3-methyl-imidazolium trifluoromethanesulfonate, 1-allyl-3-methyl-imidazole Riumheptafluoropropanesulfonate, 1-allyl-3-methyl-imidazolium bis (trifluoromethanesulfonyl) imide, 1-allyl-3-methyl-imidazolium bis (fluorosulfonyl) imide, methyltrioctylammonium bis (trifluoromethanesulfonyl) ) Imide, trimethylpropylammonium bis (trifluoromethanesulfonyl) imide, lithium bis (trifluoromethanesulfonyl) imide, lithium bis (fluorosulfonyl) imide, more preferably 1-butyl-3-methylpyridinium bis (trifluoromethanesulfonyl). ) Imide, 1-ethyl-3-methylimidazolium bis (fluorosulfonyl) ) Imide, 1-allyl-3-methyl-imidazolium bis (trifluoromethanesulfonyl) imide, methyltrioctylammonium bis (trifluoromethanesulfonyl) imide, trimethylpropylammonium bis (trifluoromethanesulfonyl) imide, lithium bis (trifluoromethanesulfonyl) ) Imide, particularly preferably 1-butyl-3-methylpyridinium bis (trifluoromethanesulfonyl) imide, 1-ethyl-3-methylimidazolium bis (fluorosulfonyl) imide, 1-allyl-3-methyl-imidazole. Riumbis (trifluoromethanesulfonyl) imide, methyltrioctylammonium bis (trifluoromethanesulfonyl) imide, and trimethylpropylammonium bis (trifluoromethanesulfonyl) imide.
　イオン性化合物は、市販のものを使用してもよいし、任意の適切な方法によって合成したものを使用してもよい。例えば、イオン液体は、「イオン性液体－開発の最前線と未来－」（シーエムシー出版発行）に記載されているような、ハロゲン化物法、水酸化物法、酸エステル法、錯形成法、および中和法などによって合成してもよい。 As the ionic compound, a commercially available compound may be used, or a compound synthesized by any appropriate method may be used. For example, ionic liquids include halide methods, hydroxide methods, acid ester methods, complex formation methods, as described in "Ionic Liquids-Forefront and Future of Development-" (published by CMC Publishing). And may be synthesized by a neutralization method or the like.
〔フッ素系添加剤〕
　他の成分として、フッ素系添加剤を含むと、本発明の実施形態による表面保護フィルムの軽剥離性や帯電防止性能をより向上させることが可能となる。 [Fluorine-based additives]
When a fluorine-based additive is contained as another component, it is possible to further improve the light peelability and antistatic performance of the surface protective film according to the embodiment of the present invention.
　フッ素系添加剤としては、本発明の効果を損なわない範囲で、任意の適切なフッ素系添加剤を採用し得る。 As the fluorine-based additive, any appropriate fluorine-based additive can be adopted as long as the effect of the present invention is not impaired.
　フッ素系添加剤は、１種のみであってもよいし、２種以上であってもよい。 The fluorine-based additive may be only one kind or two or more kinds.
　ウレタンプレポリマーＰとポリオールＡの合計量に対するフッ素系添加剤の含有割合は、好ましくは０．０１重量％以上であり、より好ましくは０．０３重量％～３０重量部であり、さらに好ましくは０．０５重量部～１０重量部であり、特に好ましくは０．０５重量部～１重量部である。ウレタンプレポリマーＰとポリオールＡの合計量に対するフッ素系添加剤の含有割合が上記範囲内にあれば、本発明の実施形態による表面保護フィルムの軽剥離性や帯電防止性能をより向上させることが可能となる。 The content ratio of the fluorine-based additive to the total amount of the urethane prepolymer P and the polyol A is preferably 0.01% by weight or more, more preferably 0.03% by weight to 30 parts by weight, and further preferably 0. It is 0.05 parts by weight to 10 parts by weight, and particularly preferably 0.05 parts by weight to 1 part by weight. When the content ratio of the fluorine-based additive to the total amount of the urethane prepolymer P and the polyol A is within the above range, it is possible to further improve the light peelability and antistatic performance of the surface protective film according to the embodiment of the present invention. Will be.
　本発明の効果をより発現させ得る点で、ウレタンプレポリマーＰとポリオールＡの合計量に対するフッ素系添加剤および後述するシリコーン系添加剤の合計量の含有割合は、０．０１重量％以上であり、より好ましくは０．０３重量％～３０重量部であり、さらに好ましくは０．０５重量部～１０重量部であり、特に好ましくは０．０５重量部～１重量部である。 In terms of further exhibiting the effects of the present invention, the content ratio of the total amount of the fluorine-based additive and the silicone-based additive described later to the total amount of the urethane prepolymer P and the polyol A is 0.01% by weight or more. , More preferably 0.03% by weight to 30 parts by weight, still more preferably 0.05 parts by weight to 10 parts by weight, and particularly preferably 0.05 parts by weight to 1 part by weight.
　フッ素系添加剤としては、例えば、フッ素含有化合物、水酸基含有フッ素系化合物、架橋性官能基含有フッ素系化合物から選ばれる少なくとも１種が挙げられる。 Examples of the fluorine-based additive include at least one selected from a fluorine-containing compound, a hydroxyl group-containing fluorine-based compound, and a crosslinkable functional group-containing fluorine-based compound.
　フッ素含有化合物としては、例えば、フルオロ脂肪族炭化水素骨格を有する化合物、有機化合物とフッ素系化合物を共重合したフッ素含有有機化合物、有機化合物を含むフッ素含有化合物が挙げられる。フルオロ脂肪族炭化水素骨格としては、例えば、フルオロメタン、フルオロエタン、フルオロプロパン、フルオロイソプロパン、フルオロブタン、フルオロイソブタン、フルオロｔ－ブタン、フルオロペンタン、フルオロヘキサンなどのフルオロＣ１～Ｃ１０アルカンが挙げられる。ここで、「Ｃ１～Ｃ１０」の標記は、炭素数が１～１０を意味する。 Examples of the fluorine-containing compound include a compound having a fluoroaliphatic hydrocarbon skeleton, a fluorine-containing organic compound obtained by copolymerizing an organic compound and a fluorine-based compound, and a fluorine-containing compound containing an organic compound. Examples of the fluoroaliphatic hydrocarbon skeleton include fluoroC1 to C10 alkanes such as fluoromethane, fluoroethane, fluoropropane, fluoroisopropane, fluorobutane, fluoroisobutane, fluorot-butane, fluoropentane, and fluorohexane. .. Here, the notation of "C1 to C10" means that the number of carbon atoms is 1 to 10.
　フッ素含有化合物の好ましい実施形態は、含フッ素基と、親水性基および／または親油性基とを有するオリゴマー（「特定フッ素系化合物」）である。このような「特定フッ素系化合物」を採用することにより、本発明の実施形態による表面保護フィルムの軽剥離性や帯電防止性能を向上させることが可能となる。特に、このような「特定フッ素系化合物」を、イオン性化合物と併用することにより、本発明の実施形態による表面保護フィルムの軽剥離性や帯電防止性能をより向上させることが可能となる。これは、特定フッ素系化合物によって、イオン性化合物がウレタン系粘着剤層の表面側（被着体と貼り合わされる側）に偏在するようになるためと推察される。含フッ素基としては、代表的には、フッ素含有アルキル基（例えば、ＣＦ３－など）および／またはフッ素含有アルキレン基（例えば、－ＣＦ２－ＣＦ２－など）が挙げられる。親水性基とは、親水性を有する基であり、親水性とは、英語で「ｈｙｄｒｏｐｈｉｌｉｃ」と訳され、「水と親和性がある」なる意として当業者に一般に知られている特性である（例えば、マグローヒル科学技術用語大辞典（改訂第３版、日刊工業新聞社）など参照）。親油性基とは、親油性を有する基であり、親油性とは、英語で「ｌｉｐｏｐｈｉｌｉｃ」と訳され、「油と親和性がある」なる意として当業者に一般に知られている特性である（例えば、マグローヒル科学技術用語大辞典（改訂第３版、日刊工業新聞社）など参照）。 A preferred embodiment of the fluorine-containing compound is an oligomer having a fluorine-containing group and a hydrophilic group and / or a lipophilic group (“specific fluorine-based compound”). By adopting such a "specific fluorine-based compound", it is possible to improve the light peelability and antistatic performance of the surface protective film according to the embodiment of the present invention. In particular, by using such a "specific fluorine-based compound" in combination with an ionic compound, it is possible to further improve the light peelability and antistatic performance of the surface protective film according to the embodiment of the present invention. It is presumed that this is because the specific fluorine-based compound causes the ionic compound to be unevenly distributed on the surface side (the side to be bonded to the adherend) of the urethane-based pressure-sensitive adhesive layer. Typical examples of the fluorine-containing group include a fluorine-containing alkyl group (for example, CF 3- , etc.) and / or a fluorine-containing alkylene group (for example, -CF 2 -CF 2- , etc.). The hydrophilic group is a group having hydrophilicity, and hydrophilicity is a property generally known to those skilled in the art as having "hydrophilic" in English and having "affinity with water". (For example, see McGraw-Hill Science and Technology Glossary (Revised 3rd Edition, Nikkan Kogyo Shimbun)). A lipophilic group is a group having lipophilicity, and lipophilicity is a characteristic generally known to those skilled in the art as having "lipophilic" in English and "affinity with oil". (For example, see McGraw-Hill Science and Technology Glossary (Revised 3rd Edition, Nikkan Kogyo Shimbun)).
　フッ素含有化合物としては、本発明の実施形態による表面保護フィルムの軽剥離性をより向上させ得る観点からは、０．１％トルエン溶液とした場合の表面張力が、好ましくは１９．０ｍＮ／ｍ～２６．０ｍＮ／ｍである（トルエンの表面張力は２７．９ｍＮ／ｍ）。このように、フッ素含有化合物の、０．１％トルエン溶液とした場合の表面張力が１９．０ｍＮ／ｍ～２６．０ｍＮ／ｍという狭い特定範囲内にあれば、本発明の実施形態による表面保護フィルムの軽剥離性をより向上させ得る。 As the fluorine-containing compound, the surface tension in the case of a 0.1% toluene solution is preferably 19.0 mN / m or more from the viewpoint of further improving the light peelability of the surface protective film according to the embodiment of the present invention. It is 26.0 mN / m (the surface tension of toluene is 27.9 mN / m). As described above, if the surface tension of the fluorine-containing compound in the case of a 0.1% toluene solution is within a narrow specific range of 19.0 mN / m to 26.0 mN / m, the surface protection according to the embodiment of the present invention. The light peelability of the film can be further improved.
　フッ素含有化合物としては、本発明の実施形態による表面保護フィルムの帯電防止性能をより向上させ得る観点からは、０．１％トルエン溶液とした場合の表面張力が、好ましくは２６．０ｍＮ／ｍ～２８．０ｍＮ／ｍである（トルエンの表面張力は２７．９ｍＮ／ｍ）。このように、フッ素含有化合物の、０．１％トルエン溶液とした場合の表面張力が２６．０ｍＮ／ｍ～２８．０ｍＮ／ｍという狭い特定範囲内にあれば、本発明の実施形態による表面保護フィルムの帯電防止性能をより向上させ得る。 As the fluorine-containing compound, the surface tension in the case of a 0.1% toluene solution is preferably 26.0 mN / m or more from the viewpoint of further improving the antistatic performance of the surface protective film according to the embodiment of the present invention. It is 28.0 mN / m (the surface tension of toluene is 27.9 mN / m). As described above, if the surface tension of the fluorine-containing compound in the case of a 0.1% toluene solution is within a narrow specific range of 26.0 mN / m to 28.0 mN / m, the surface protection according to the embodiment of the present invention. The antistatic performance of the film can be further improved.
　フッ素含有化合物としては、市販品としては、例えば、下記のようなものが挙げられる。 Examples of commercially available fluorine-containing compounds include the following.
　ＤＩＣ（株）製のメガファックシリーズ：
　代表的には、「メガファックＦ－１１４」、「メガファックＦ－２５１」、「メガファックＦ－２５３」、「メガファックＦ－２８１」、「メガファックＦ－４１０」、「メガファックＦ－４３０」、「メガファックＦ－４４４」、「メガファックＦ－４７７」、「メガファックＦ－５１０」、「メガファックＦ－５５１－Ａ」、「メガファックＦ－５５３」、「メガファックＦ－５５４」、「メガファックＦ－５５５－Ａ」、「メガファックＦ－５５６」、「メガファックＦ－５５７」、「メガファックＦ－５５８」、「メガファックＦ－５５９」、「メガファックＦ－５６０」、「メガファックＦ－５６１」、「メガファックＦ－５６２」、「メガファックＦ－５６３」、「メガファックＦ－５６５」、「メガファックＦ－５６８」、「メガファックＦ－５６９」、「メガファックＦ－５７０」、「メガファックＦ－５７６」、「メガファックＲ－０１」、「メガファックＲ－４０」、「メガファックＲ－４０－ＬＭ」、「メガファックＲ－４１」、「メガファックＲ－４１－ＬＭ」、「メガファックＲ－９４」、「メガファックＲＳ－５６」、「メガファックＲＳ－７２－Ｋ」、「メガファックＲＳ－７５－Ａ」、「メガファックＲＳ－７５－ＮＳ」、「メガファックＲＳ－７８」、「メガファックＲＳ－９０」など。 Mega Fuck Series manufactured by DIC Corporation:
Representatively, "Mega Fuck F-114", "Mega Fuck F-251", "Mega Fuck F-253", "Mega Fuck F-281", "Mega Fuck F-410", "Mega Fuck F-" 430 "," Mega Fuck F-444 "," Mega Fuck F-477 "," Mega Fuck F-510 "," Mega Fuck F-551-A "," Mega Fuck F-553 "," Mega Fuck F- 554 "," Mega Fuck F-555-A "," Mega Fuck F-556 "," Mega Fuck F-557 "," Mega Fuck F-558 "," Mega Fuck F-559 "," Mega Fuck F- 560 ”,“ Mega Fuck F-561 ”,“ Mega Fuck F-562 ”,“ Mega Fuck F-563 ”,“ Mega Fuck F-565 ”,“ Mega Fuck F-568 ”,“ Mega Fuck F-569 ” , "Mega Fuck F-570", "Mega Fuck F-576", "Mega Fuck R-01", "Mega Fuck R-40", "Mega Fuck R-40-LM", "Mega Fuck R-41" , "Mega Fuck R-41-LM", "Mega Fuck R-94", "Mega Fuck RS-56", "Mega Fuck RS-72-K", "Mega Fuck RS-75-A", "Mega Fuck""RS-75-NS","Mega Fuck RS-78", "Mega Fuck RS-90", etc.
　ＡＧＣセイミケミカル（株）製のサーフロンシリーズ：
　代表的には、「Ｓ－２４２」、「Ｓ－２４３」、「Ｓ－３８６」など。 Surflon series manufactured by AGC Seimi Chemical Co., Ltd .:
Representatively, "S-242", "S-243", "S-386" and the like.
　住友スリーエム（株）製のＦＣシリーズ：
　代表的には、「ＦＣ－４４３０」、「ＦＣ－４４３２」など。 FC series manufactured by Sumitomo 3M Ltd .:
Representatively, "FC-4430", "FC-4432" and the like.
　（株）ネオス製のフタージェントシリーズ：
　代表的には、「フタージェント１００」、「フタージェント１００Ｃ」、「フタージェント１１０」、「フタージェント１５０」、「フタージェント１５０ＣＨ」、「フタージェント２５０」、「フタージェント４００ＳＷ」など。 Footergent series made by Neos Co., Ltd .:
Representatively, "Futagent 100", "Futagent 100C", "Futagent 110", "Futagent 150", "Futagent 150CH", "Futagent 250", "Futagent 400SW", etc.
　北村化学産業（株）製のＰＦシリーズ：
　代表的には、「ＰＦ－１３６Ａ」、「ＰＦ－１５６Ａ」、「ＰＦ－１５１Ｎ」、「ＰＦ－６３６」、「ＰＦ－６３２０」、「ＰＦ－６５６」、「ＰＦ－６５２０」、「ＰＦ－６５１」、「ＰＦ－６５２」、「ＰＦ－３３２０」など。 PF series manufactured by Kitamura Chemical Industry Co., Ltd .:
Representatively, "PF-136A", "PF-156A", "PF-151N", "PF-636", "PF-6320", "PF-656", "PF-6520", "PF-" 651 ”,“ PF-652 ”,“ PF-3320 ”, etc.
　水酸基含有フッ素系化合物としては、例えば、従来公知の樹脂が使用でき、例えば、国際公開第９４／０６８７０号パンフレット、特開平８－１２９２１号公報、特開平１０－７２５６９号公報、特開平４－２７５３７９号公報、国際公開第９７／１１１３０号パンフレット、国際公開第９６／２６２５４号パンフレットなどに記載された水酸基含有フッ素樹脂が挙げられる。その他の水酸基含有フッ素樹脂としては、例えば、特開平８－２３１９１９号公報、特開平１０－２６５７３１号公報、特開平１０－２０４３７４号公報、特開平８－１２９２２号公報などに記載されたフルオロオレフィン共重合体などが挙げられる。その他、水酸基含有化合物にフッ素化されたアルキル基を有する化合物の共重合体、水酸基含有化合物にフッ素含有化合物を共重合したフッ素含有有機化合物、水酸基含有有機化合物を含むフッ素含有化合物などが挙げられる。このような水酸基含有フッ素系化合物としては、市販品としては、例えば、商品名「ルミフロン」（旭硝子（株）製）、商品名「セフラルコート」（セントラル硝子（株）製）、商品名「ザフロン」（東亜合成（株）製）、商品名「ゼッフル」（ダイキン工業（株）製）などが挙げられる。 As the hydroxyl group-containing fluoropolymer, for example, a conventionally known resin can be used. For example, International Publication No. 94/06870 Pamphlet, JP-A-8-12921, JP-A-10-72569, JP-A-4-275379 Examples thereof include the hydroxyl group-containing fluororesins described in Japanese Patent Publication No. 97/11130 Pamphlet, International Publication No. 96/26254 Pamphlet and the like. Examples of other hydroxyl group-containing fluororesins include fluoroolefins described in JP-A-8-231919, JP-A-10-265731, JP-A-10-204374, JP-A-8-12922, and the like. Examples include polymers. In addition, a copolymer of a compound having a fluorinated alkyl group in a hydroxyl group-containing compound, a fluorine-containing organic compound obtained by copolymerizing a fluorine-containing compound with a hydroxyl group-containing compound, a fluorine-containing compound containing a hydroxyl group-containing organic compound, and the like can be mentioned. Examples of commercially available products such as the hydroxyl group-containing fluorine-based compound include the trade name "Lumiflon" (manufactured by Asahi Glass Co., Ltd.), the trade name "Cefral Coat" (manufactured by Central Glass Co., Ltd.), and the trade name "Zaflon". (Manufactured by Toagosei Co., Ltd.), trade name "Zeffle" (manufactured by Daikin Industries, Ltd.), etc. can be mentioned.
　架橋性官能基含有フッ素系化合物としては、例えば、ペルフルオロオクタン酸などのようなフッ素化されたアルキル基を有するカルボン酸化合物、架橋性官能基含有化合物にフッ素化されたアルキル基を有する化合物の共重合体、架橋性官能基含有化合物にフッ素含有化合物を共重合したフッ素含有有機化合物、架橋性官能基含有化合物を含むフッ素含有化合物などが挙げられる。このような架橋性官能基含有フッ素系化合物としては、市販品としては、例えば、商品名「メガファック　Ｆ－５７０」、「メガファックＲＳ－５５」、「メガファックＲＳ－５６」、「メガファックＲＳ－７２－Ｋ」、「メガファックＲＳ－７５」、「メガファックＲＳ－７６－Ｅ」、「メガファックＲＳ－７６－ＮＳ」、「メガファックＲＳ－７８」、「メガファックＲＳ－９０」（ＤＩＣ（株）製）などが挙げられる。 Examples of the fluorinated compound containing a crosslinkable functional group include a carboxylic acid compound having a fluorinated alkyl group such as perfluorooctanoic acid and a compound having a fluorinated alkyl group in the crosslinkable functional group-containing compound. Examples thereof include a polymer, a fluorine-containing organic compound obtained by copolymerizing a fluorine-containing compound with a crosslinkable functional group-containing compound, and a fluorine-containing compound containing a crosslinkable functional group-containing compound. Examples of commercially available products such as crosslinkable functional group-containing fluorine-based compounds include trade names "Megafuck F-570", "Megafuck RS-55", "Megafuck RS-56", and "Megafuck". RS-72-K ”,“ Mega Fuck RS-75 ”,“ Mega Fuck RS-76-E ”,“ Mega Fuck RS-76-NS ”,“ Mega Fuck RS-78 ”,“ Mega Fuck RS-90 ” (Manufactured by DIC Co., Ltd.) and the like.
　市販品として入手可能なフッ素含有化合物の中でも、前述の「含フッ素基と、親水性基および／または親油性基とを有するオリゴマー」に該当するものとしては、代表的には、ＤＩＣ（株）製の、
「メガファックＦ－４７７」（含フッ素基・親水性基・親油性基含有オリゴマー、０．１％トルエン溶液とした場合の表面張力＝２６．４ｍＮ／ｍ）、
「メガファックＦ－５５１－Ａ」（含フッ素基・親油性基含有オリゴマー、０．１％トルエン溶液とした場合の表面張力＝２５．６ｍＮ／ｍ）、
「メガファックＦ－５５３」（含フッ素基・親水性基・親油性基含有オリゴマー、０．１％トルエン溶液とした場合の表面張力＝２６．４ｍＮ／ｍ）、
「メガファックＦ－５５４」（含フッ素基・親油性基含有オリゴマー、０．１％トルエン溶液とした場合の表面張力＝２５．０ｍＮ／ｍ）、
「メガファックＦ－５５５－Ａ」（含フッ素基・親水性基・親油性基含有オリゴマー、０．１％トルエン溶液とした場合の表面張力＝２０．４ｍＮ／ｍ）、
「メガファックＦ－５５７」（含フッ素基・親水性基・親油性基含有オリゴマー、０．１％トルエン溶液とした場合の表面張力＝２６．３ｍＮ／ｍ）、
「メガファックＦ－５５９」（含フッ素基・親水性基・親油性基含有オリゴマー、０．１％トルエン溶液とした場合の表面張力＝２６．１ｍＮ／ｍ）、
「メガファックＦ－５６３」（含フッ素基・親油性基含有オリゴマー、０．１％トルエン溶液とした場合の表面張力＝２０．２ｍＮ／ｍ）、
「メガファックＦ－５６９」（含フッ素基・親水性基含有オリゴマー、０．１％トルエン溶液とした場合の表面張力＝１９．７ｍＮ／ｍ）、
などが挙げられる。 Among the fluorine-containing compounds available as commercially available products, those corresponding to the above-mentioned "oligomers having a fluorine-containing group and a hydrophilic group and / or a lipophilic group" are typically DIC Co., Ltd. Made of
"Megafuck F-477" (fluorine-containing group / hydrophilic group / lipophilic group-containing oligomer, surface tension in the case of 0.1% toluene solution = 26.4 mN / m),
"Megafuck F-551-A" (fluorine-containing group / lipophilic group-containing oligomer, surface tension in the case of 0.1% toluene solution = 25.6 mN / m),
"Megafuck F-553" (fluorine-containing group / hydrophilic group / lipophilic group-containing oligomer, surface tension in the case of 0.1% toluene solution = 26.4 mN / m),
"Megafuck F-554" (fluorine-containing group / lipophilic group-containing oligomer, surface tension in the case of 0.1% toluene solution = 25.0 mN / m),
"Megafuck F-555-A" (fluorine-containing group / hydrophilic group / lipophilic group-containing oligomer, surface tension in the case of 0.1% toluene solution = 20.4 mN / m),
"Megafuck F-557" (fluorine-containing group / hydrophilic group / lipophilic group-containing oligomer, surface tension in the case of 0.1% toluene solution = 26.3 mN / m),
"Megafuck F-559" (fluorine-containing group / hydrophilic group / lipophilic group-containing oligomer, surface tension in the case of 0.1% toluene solution = 26.1 mN / m),
"Megafuck F-563" (fluorine-containing group / lipophilic group-containing oligomer, surface tension in the case of 0.1% toluene solution = 20.2 mN / m),
"Megafuck F-569" (fluorine-containing group / hydrophilic group-containing oligomer, surface tension in the case of 0.1% toluene solution = 19.7 mN / m),
And so on.
〔シリコーン系添加剤〕
　他の成分として、シリコーン系添加剤を含むと、本発明の実施形態による表面保護フィルムの軽剥離性をより向上させることが可能となる。 [Silicone-based additives]
When a silicone-based additive is included as another component, it is possible to further improve the light peelability of the surface protective film according to the embodiment of the present invention.
　シリコーン系添加剤としては、本発明の効果を損なわない範囲で、任意の適切なシリコーン系添加剤を採用し得る。 As the silicone-based additive, any suitable silicone-based additive can be adopted as long as the effect of the present invention is not impaired.
　シリコーン系添加剤は、１種のみであってもよいし、２種以上であってもよい。 The silicone-based additive may be only one kind or two or more kinds.
　ウレタンプレポリマーＰとポリオールＡの合計量に対するシリコーン系添加剤の含有割合は、好ましくは０．０１重量％以上であり、より好ましくは０．０１５重量％～３０重量部であり、さらに好ましくは０．０２重量部～１０重量部であり、特に好ましくは０．０２５重量部～１重量部である。ウレタンプレポリマーＰとポリオールＡの合計量に対するシリコーン系添加剤の含有割合が上記範囲内にあれば、本発明の実施形態による表面保護フィルムの軽剥離性をより向上させることが可能となる。 The content ratio of the silicone-based additive to the total amount of the urethane prepolymer P and the polyol A is preferably 0.01% by weight or more, more preferably 0.015% by weight to 30 parts by weight, and further preferably 0. It is 0.02 parts by weight to 10 parts by weight, and particularly preferably 0.025 parts by weight to 1 part by weight. When the content ratio of the silicone-based additive to the total amount of the urethane prepolymer P and the polyol A is within the above range, it is possible to further improve the light peelability of the surface protective film according to the embodiment of the present invention.
　本発明の効果をより発現させ得る点で、ウレタンプレポリマーＰとポリオールＡの合計量に対する前述のフッ素系添加剤およびシリコーン系添加剤の合計量の含有割合は、０．０１重量％以上であり、より好ましくは０．０３重量％～３０重量部であり、さらに好ましくは０．０５重量部～１０重量部であり、特に好ましくは０．０５重量部～１重量部である。 In terms of further exhibiting the effects of the present invention, the content ratio of the total amount of the above-mentioned fluorine-based additive and silicone-based additive to the total amount of the urethane prepolymer P and the polyol A is 0.01% by weight or more. , More preferably 0.03% by weight to 30 parts by weight, still more preferably 0.05 parts by weight to 10 parts by weight, and particularly preferably 0.05 parts by weight to 1 part by weight.
　シリコーン系添加剤は、本発明の効果を損なわない範囲で、任意の適切なシリコーン系添加剤を採用し得る。このようなシリコーン系添加剤としては、例えば、反応性シリコーンオイル、非反応性シリコーンオイルが挙げられる。 As the silicone-based additive, any suitable silicone-based additive can be adopted as long as the effect of the present invention is not impaired. Examples of such silicone-based additives include reactive silicone oil and non-reactive silicone oil.
　反応性シリコーンオイルとしては、例えば、シロキサン結合に供するＳｉ原子に側鎖として有機基が結合した側鎖型反応性シリコーンオイル、構造の両末端に位置するＳｉ原子に有機基が結合した両末端型反応性シリコーンオイル、構造の両末端に位置するＳｉ原子の一方のみに有機基が結合した片末端型反応性シリコーンオイル、シロキサン結合に供するＳｉ原子に側鎖として有機基が結合し且つ構造の両末端に位置するＳｉ原子に有機基が結合した側鎖両末端型反応性シリコーンオイルが挙げられる。 Examples of the reactive silicone oil include a side chain type reactive silicone oil in which an organic group is bonded as a side chain to a Si atom used for a siloxane bond, and a double-ended type in which an organic group is bonded to Si atoms located at both ends of the structure. Reactive silicone oil, one-ended reactive silicone oil in which an organic group is bonded to only one of the Si atoms located at both ends of the structure, and organic groups bonded to the Si atom used for the siloxane bond as a side chain and both in the structure. Examples thereof include side chain double-ended reactive silicone oil in which an organic group is bonded to a Si atom located at the terminal.
　側鎖型反応性シリコーンオイルとしては、例えば、アミノ変性タイプの側鎖型反応性シリコーンオイル、エポキシ変性タイプの側鎖型反応性シリコーンオイル、カルビノール変性タイプの側鎖型反応性シリコーンオイル、メルカプト変性タイプの側鎖型反応性シリコーンオイル、カルボキシル変性タイプの側鎖型反応性シリコーンオイル、メチルハイドロジェンシリコーンオイルタイプの側鎖型反応性シリコーンオイルが挙げられる。これらの市販品としては、例えば、信越化学工業社製の側鎖型反応性シリコーンオイルとして市販されている各種シリコーンオイルが挙げられる。 Examples of the side chain reactive silicone oil include amino-modified type side-chain reactive silicone oil, epoxy-modified type side-chain reactive silicone oil, carbinol-modified type side-chain reactive silicone oil, and mercapto. Examples thereof include a modified type side chain reactive silicone oil, a carboxyl modified type side chain reactive silicone oil, and a methylhydrogen silicone oil type side chain reactive silicone oil. Examples of these commercially available products include various silicone oils commercially available as side chain reactive silicone oils manufactured by Shin-Etsu Chemical Co., Ltd.
　両末端型反応性シリコーンオイルとしては、例えば、アミノ変性タイプの両末端型反応性シリコーンオイル、エポキシ変性タイプの両末端型反応性シリコーンオイル、カルビノール変性タイプの両末端型反応性シリコーンオイル、メタクリル変性タイプの両末端型反応性シリコーンオイル、ポリエーテル変性タイプの両末端型反応性シリコーンオイル、メルカプト変性タイプの両末端型反応性シリコーンオイル、カルボキシル変性タイプの両末端型反応性シリコーンオイル、フェノール変性タイプの両末端型反応性シリコーンオイル、シラノール末端タイプの両末端型反応性シリコーンオイル、アクリル変性タイプの両末端型反応性シリコーンオイル、カルボン酸無水物変性タイプの両末端型反応性シリコーンオイルが挙げられる。これらの市販品としては、例えば、信越化学工業社製の両末端型反応性シリコーンオイルとして市販されている各種シリコーンオイルが挙げられる。特に、信越化学工業社製の「ＫＦ－６０００」、「ＫＦ－６００１」、「ＫＦ－６００２」、「ＫＦ－６００３」、「ＫＦ－６０２８」などの、カルビノール変性タイプの両末端型反応性シリコーンオイルが好ましく採用できる。 Examples of the two-ended reactive silicone oil include an amino-modified type two-ended reactive silicone oil, an epoxy-modified type two-ended reactive silicone oil, a carbinol-modified type two-ended reactive silicone oil, and methacryl. Modified type two-ended reactive silicone oil, polyether modified type two-ended reactive silicone oil, Mercapto modified type two-ended reactive silicone oil, carboxyl-modified type two-ended reactive silicone oil, phenol-modified Type two-ended reactive silicone oil, silanol-terminated type two-ended reactive silicone oil, acrylic modified type two-ended reactive silicone oil, carboxylic acid anhydride-modified type two-ended reactive silicone oil. Be done. Examples of these commercially available products include various silicone oils commercially available as double-ended reactive silicone oils manufactured by Shin-Etsu Chemical Co., Ltd. In particular, both-terminal reactivity of carbinol-modified type such as "KF-6000", "KF-6001", "KF-6002", "KF-6003", "KF-6028" manufactured by Shin-Etsu Chemical Co., Ltd. Silicone oil can be preferably used.
　片末端型反応性シリコーンオイルとしては、例えば、片末端反応性変性タイプの片末端型反応性シリコーンオイル、平均的片末端カルボキシル変性タイプの片末端型反応性シリコーンオイルが挙げられる。これらの市販品としては、例えば、信越化学工業社製の片末端型反応性シリコーンオイルとして市販されている各種シリコーンオイルが挙げられる。特に、信越化学工業社製の「Ｘ－２２－１７０ＢＸ」、「Ｘ－２２－１７０ＤＸ」、「Ｘ－２２－４０１５」などの、カルビノール変性タイプの片末端型反応性シリコーンオイルが好ましく採用できる。 Examples of the one-ended reactive silicone oil include one-ended reactive silicone oil of one-ended reactive modified type and one-ended reactive silicone oil of average one-ended carboxyl modified type. Examples of these commercially available products include various silicone oils commercially available as one-ended reactive silicone oils manufactured by Shin-Etsu Chemical Co., Ltd. In particular, carbinol-modified type one-ended reactive silicone oils such as "X-22-170BX", "X-22-170DX", and "X-22-4015" manufactured by Shin-Etsu Chemical Co., Ltd. can be preferably adopted. ..
　側鎖両末端型反応性シリコーンオイルとしては、例えば、側鎖アミノ・両末端メトキシ変性タイプの側鎖両末端型反応性シリコーンオイル、エポキシ変性タイプの側鎖両末端型反応性シリコーンオイルが挙げられる。これらの市販品としては、例えば、信越化学工業社製の側鎖両末端型反応性シリコーンオイルとして市販されている各種シリコーンオイルが挙げられる。 Examples of the side chain double-ended reactive silicone oil include side chain amino / double-ended methoxy-modified type side-chain double-ended reactive silicone oil and epoxy-modified type side-chain double-ended reactive silicone oil. .. Examples of these commercially available products include various silicone oils commercially available as side chain double-ended reactive silicone oils manufactured by Shin-Etsu Chemical Co., Ltd.
　非反応性シリコーンオイルとしては、例えば、シロキサン結合に供するＳｉ原子に側鎖として有機基が結合した側鎖型非反応性シリコーンオイル、構造の両末端に位置するＳｉ原子に有機基が結合した両末端型非反応性シリコーンオイルが挙げられる。 Examples of the non-reactive silicone oil include a side chain type non-reactive silicone oil in which an organic group is bonded as a side chain to a Si atom used for a siloxane bond, and a side chain type non-reactive silicone oil in which an organic group is bonded to Si atoms located at both ends of the structure. Examples include terminal non-reactive silicone oils.
　側鎖型非反応性シリコーンオイルとしては、例えば、ポリエーテル変性タイプの側鎖型非反応性シリコーンオイル、アラルキル変性タイプの側鎖型非反応性シリコーンオイル、フルオロアルキル変性タイプの側鎖型非反応性シリコーンオイル、長鎖アルキル変性タイプの側鎖型非反応性シリコーンオイル、高級脂肪酸エステル変性タイプの側鎖型非反応性シリコーンオイル、高級脂肪酸含有タイプの側鎖型非反応性シリコーンオイル、フェニル変性タイプの側鎖型非反応性シリコーンオイルが挙げられる。これらの市販品としては、例えば、信越化学工業社製の側鎖型非反応性シリコーンオイルとして市販されている各種シリコーンオイルが挙げられる。特に、信越化学工業社製の「ＫＦ－３５１Ａ」、「ＫＦ－３５２Ａ」、「ＫＦ－３５３」、「ＫＦ－３５４Ｌ」、「ＫＦ－３５５Ａ」、「ＫＦ－６１５Ａ」、「ＫＦ－９４５」、「ＫＦ－６４０」、「ＫＦ－６４２」、「ＫＦ－６４３」、「ＫＦ－６４４」、「ＫＦ－６０２０」、「ＫＦ－６２０４」、「Ｘ－２２－４５１５」などの、ポリエーテル変性タイプの側鎖型非反応性シリコーンオイルが好ましく採用できる。 Examples of the side chain non-reactive silicone oil include a polyether-modified type side-chain non-reactive silicone oil, an aralkyl-modified type side-chain non-reactive silicone oil, and a fluoroalkyl-modified type side chain non-reactive. Sexual silicone oil, long-chain alkyl-modified type side-chain non-reactive silicone oil, higher fatty acid ester-modified type side-chain non-reactive silicone oil, higher fatty acid-containing type side-chain non-reactive silicone oil, phenyl-modified Examples include side chain non-reactive silicone oils of the type. Examples of these commercially available products include various silicone oils commercially available as side chain type non-reactive silicone oils manufactured by Shin-Etsu Chemical Co., Ltd. In particular, "KF-351A", "KF-352A", "KF-353", "KF-354L", "KF-355A", "KF-615A", "KF-945", manufactured by Shin-Etsu Chemical Co., Ltd., Polyether modified types such as "KF-640", "KF-642", "KF-643", "KF-644", "KF-6020", "KF-6204", "X-22-4515" Side chain non-reactive silicone oil can be preferably used.
　これらのポリエーテル変性タイプの側鎖型非反応性シリコーンオイルの中でも、糊残り性をより低減し得る点で、ＨＬＢ値が、好ましくは８以上、より好ましくは９以上、さらに好ましくは１０以上のポリエーテル変性タイプの側鎖型非反応性シリコーンオイルが好ましい。このようなポリエーテル変性タイプの側鎖型非反応性シリコーンオイルとしては、例えば、「ＫＦ－３５１Ａ」（ＨＬＢ＝１２）、「ＫＦ－３５３」（ＨＬＢ＝１０）、「ＫＦ－３５４Ｌ」（ＨＬＢ＝１６）、「ＫＦ－３５５Ａ」（ＨＬＢ＝１２）、「ＫＦ－６１５Ａ」（ＨＬＢ＝１０）、「ＫＦ－６４０」（ＨＬＢ＝１４）、「ＫＦ－６４２」（ＨＬＢ＝１２）、「ＫＦ－６４３」（ＨＬＢ＝１４）、「ＫＦ－６４４」（ＨＬＢ＝１１）、「ＫＦ－６２０４」（ＨＬＢ＝１０）が挙げられる。 Among these polyether-modified type side chain non-reactive silicone oils, the HLB value is preferably 8 or more, more preferably 9 or more, still more preferably 10 or more in that the adhesive residue can be further reduced. A polyether-modified type side chain non-reactive silicone oil is preferable. Examples of such polyether-modified type side chain non-reactive silicone oils include "KF-351A" (HLB = 12), "KF-353" (HLB = 10), and "KF-354L" (HLB). = 16), "KF-355A" (HLB = 12), "KF-615A" (HLB = 10), "KF-640" (HLB = 14), "KF-642" (HLB = 12), "KF" -643 "(HLB = 14)," KF-644 "(HLB = 11)," KF-6204 "(HLB = 10).
　両末端型非反応性シリコーンオイルとしては、例えば、ポリエーテル変性タイプの両末端型非反応性シリコーンオイルが挙げられる。これらの市販品としては、例えば、信越化学工業社製の両末端型非反応性シリコーンオイルとして市販されている各種シリコーンオイルが挙げられる。特に、信越化学工業社製の「ＫＦ－６００４」などの、ポリエーテル変性タイプの両末端型非反応性シリコーンオイルが好ましく採用できる。 Examples of the double-ended non-reactive silicone oil include a polyether-modified type double-ended non-reactive silicone oil. Examples of these commercially available products include various silicone oils commercially available as double-ended non-reactive silicone oils manufactured by Shin-Etsu Chemical Co., Ltd. In particular, a polyether-modified type double-ended non-reactive silicone oil such as "KF-6004" manufactured by Shin-Etsu Chemical Co., Ltd. can be preferably adopted.
　シリコーン系添加剤としては、上記の他にも、従来公知の、任意の適切なシリコーン系添加剤を採用し得る。このようなシリコーン系添加剤としては、例えば、上記したもの以外のシロキサン結合含有ポリマー、上記したもの以外の水酸基含有シリコーン系化合物、上記したもの以外の架橋性官能基含有シリコーン系化合物が挙げられる。 As the silicone-based additive, in addition to the above, any conventionally known and suitable silicone-based additive can be adopted. Examples of such silicone-based additives include siloxane bond-containing polymers other than those described above, hydroxyl group-containing silicone compounds other than those described above, and crosslinkable functional group-containing silicone compounds other than those described above.
　上記したもの以外のシロキサン結合含有ポリマーの市販品としては、例えば、商品名「ＬＥ－３０２」（共栄社化学株式会社製）、ビックケミー・ジャパン（株）製のＢＹＫシリーズのレベリング剤（「ＢＹＫ－３００」、「ＢＹＫ－３０１／３０２」、「ＢＹＫ－３０６」、「ＢＹＫ－３０７」、「ＢＹＫ－３１０」、「ＢＹＫ－３１５」、「ＢＹＫ－３１３」、「ＢＹＫ－３２０」、「ＢＹＫ－３２２」、「ＢＹＫ－３２３」、「ＢＹＫ－３２５」、「ＢＹＫ－３３０」、「ＢＹＫ－３３１」、「ＢＹＫ－３３３」、「ＢＹＫ－３３７」、「ＢＹＫ－３４１」、「ＢＹＫ－３４４」、「ＢＹＫ－３４５／３４６」、「ＢＹＫ－３４７」、「ＢＹＫ－３４８」、「ＢＹＫ－３４９」、「ＢＹＫ－３７０」、「ＢＹＫ－３７５」、「ＢＹＫ－３７７」、「ＢＹＫ－３７８」、「ＢＹＫ－ＵＶ３５００」、「ＢＹＫ－ＵＶ３５１０」、「ＢＹＫ－ＵＶ３５７０」、「ＢＹＫ－３５５０」、「ＢＹＫ－ＳＩＬＣＬＥＡＮ３７００」、「ＢＹＫ－ＳＩＬＣＬＥＡＮ３７２０」など）、Ａｌｇｉｎ　Ｃｈｅｍｉｅ社製のＡＣシリーズのレベリング剤（「ＡＣ　ＦＳ１８０」、「ＡＣ　ＦＳ３６０」、「ＡＣ　Ｓ２０」など）、共栄社化学（株）製のポリフローシリーズのレベリング剤（「ポリフローＫＬ－４００Ｘ」、「ポリフローＫＬ－４００ＨＦ」、「ポリフローＫＬ－４０１」、「ポリフローＫＬ－４０２」、「ポリフローＫＬ－４０３」、「ポリフローＫＬ－４０４」など）、信越化学工業（株）製のＫＰシリーズのレベリング剤（「ＫＰ－３２３」、「ＫＰ－３２６」、「ＫＰ－３４１」、「ＫＰ－１０４」、「ＫＰ－１１０」、「ＫＰ－１１２」など）、東レ・ダウコーニング（株）製のレベリング剤（「ＬＰ－７００１」、「ＬＰ－７００２」、「８０３２ＡＤＤＩＴＩＶＥ」、「５７ＡＤＤＩＴＩＶＥ」、「Ｌ－７６０４」、「ＦＺ－２１１０」、「ＦＺ－２１０５」、「６７ＡＤＤＩＴＩＶＥ」、「８６１８ＡＤＤＩＴＩＶＥ」、「３ＡＤＤＩＴＩＶＥ」、「５６ＡＤＤＩＴＩＶＥ」など）が挙げられる。 Commercially available products of siloxane bond-containing polymers other than those described above include, for example, the brand name "LE-302" (manufactured by Kyoeisha Chemical Co., Ltd.) and the BYK series leveling agent manufactured by Big Chemie Japan Co., Ltd. ("BYK-300"). , "BYK-301 / 302", "BYK-306", "BYK-307", "BYK-310", "BYK-315", "BYK-313", "BYK-320", "BYK-322" , "BYK-323", "BYK-325", "BYK-330", "BYK-331", "BYK-333", "BYK-337", "BYK-341", "BYK-344", "BYK-345 / 346", "BYK-347", "BYK-348", "BYK-349", "BYK-370", "BYK-375", "BYK-377", "BYK-378", "BYK-UV3500", "BYK-UV3510", "BYK-UV3570", "BYK-3550", "BYK-SILCLEAN3700", "BYK-SILCLEAN3720", etc.), AC series leveling agent manufactured by Algin Chemie ("" AC FS180, AC FS360, AC S20, etc.), Polyflow series leveling agents manufactured by Kyoeisha Chemical Co., Ltd. ("Polyflow KL-400X", "Polyflow KL-400HF", "Polyflow KL-401" , "Polyflow KL-402", "Polyflow KL-403", "Polyflow KL-404", etc.), KP series leveling agents manufactured by Shin-Etsu Chemical Industry Co., Ltd. ("KP-323", "KP-326", "KP-341", "KP-104", "KP-110", "KP-112", etc.), Leveling agent manufactured by Toray Dow Corning Co., Ltd. ("LP-7001", "LP-7002", Examples thereof include "8032ADDITION", "57ADDITION", "L-7604", "FZ-2110", "FZ-2105", "67ADDITIVE", "8618ADDITION", "3ADDITIVE", "56ADDITIVE").
　上記したもの以外の水酸基含有シリコーンの市販品としては、例えば、ビックケミー・ジャパン（株）製の「ＢＹＫ－３７０」、「ＢＹＫ－ＳＩＬＣＬＥＡＮ３７００」、「ＢＹＫ－ＳＩＬＣＬＥＡＮ３７２０」が挙げられる。 Examples of commercially available products of hydroxyl group-containing silicones other than those described above include "BYK-370", "BYK-SILCLEAN3700", and "BYK-SILCLEAN3720" manufactured by Big Chemie Japan Co., Ltd.
　上記したもの以外の架橋性官能基含有シリコーン系化合物の市販品としては、例えば、東レ・ダウコーニング（株）製の「ＢＹ１６－８５５」、「ＳＦ８４１３」、「ＢＹ１６－８３９」、「ＳＦ８４２１」、「ＢＹ１６－７５０」、「ＢＹ１６－８８０」、「ＢＹ１６－１５２Ｃ」が挙げられる。 Commercially available products of crosslinkable functional group-containing silicone compounds other than those described above include, for example, "BY16-855", "SF8413", "BY16-839", "SF8421" manufactured by Toray Dow Corning Co., Ltd. Examples thereof include "BY16-750", "BY16-880", and "BY16-152C".
〔酸化防止剤〕
　ウレタン系粘着剤組成物は、ウレタン系粘着剤層の劣化抑制等の点から、他の成分として、酸化防止剤を含んでいてもよい。酸化防止剤は、１種のみであってもよいし、２種以上であってもよい。 〔Antioxidant〕
The urethane-based pressure-sensitive adhesive composition may contain an antioxidant as another component from the viewpoint of suppressing deterioration of the urethane-based pressure-sensitive adhesive layer. The antioxidant may be only one kind or two or more kinds.
　ウレタン系粘着剤組成物中の酸化防止剤の含有割合は、本発明の効果を損なわない範囲で、任意の適切な含有割合を採用し得る。このような含有割合は、ウレタンプレポリマーＰとポリオールＡの合計量に対する酸化防止剤の含有割合として、好ましくは０．０１重量％～１０重量％以上であり、より好ましくは０．０５重量％～５重量％であり、さらに好ましくは０．１重量％～３重量％であり、特に好ましくは０．２重量％～１重量％である。 As the content ratio of the antioxidant in the urethane-based pressure-sensitive adhesive composition, any appropriate content ratio can be adopted as long as the effect of the present invention is not impaired. Such a content ratio is preferably 0.01% by weight to 10% by weight or more, more preferably 0.05% by weight or more, as the content ratio of the antioxidant with respect to the total amount of the urethane prepolymer P and the polyol A. It is 5% by weight, more preferably 0.1% by weight to 3% by weight, and particularly preferably 0.2% by weight to 1% by weight.
　酸化防止剤としては、例えば、ラジカル連鎖禁止剤、過酸化物分解剤などが挙げられる。 Examples of the antioxidant include a radical chain inhibitor, a peroxide decomposing agent, and the like.
　ラジカル連鎖禁止剤としては、例えば、フェノール系酸化防止剤、アミン系酸化防止剤などが挙げられる。 Examples of the radical chain inhibitor include phenol-based antioxidants and amine-based antioxidants.
　過酸化物分解剤としては、例えば、硫黄系酸化防止剤、リン系酸化防止剤が挙げられる。 Examples of the peroxide decomposing agent include sulfur-based antioxidants and phosphorus-based antioxidants.
　フェノール系酸化防止剤としては、例えば、モノフェノール系酸化防止剤、ビスフェノール系酸化防止剤、高分子型フェノール系酸化防止剤が挙げられる。 Examples of the phenol-based antioxidant include monophenol-based antioxidants, bisphenol-based antioxidants, and polymer-type phenol-based antioxidants.
　モノフェノール系酸化防止剤としては、例えば、２，６－ジ－ｔ－ブチル－ｐ－クレゾール、ブチル化ヒドロキシアニソール、２，６－ジ－ｔ－ブチル－４－エチルフェノール、ステアリン－β－（３，５－ジ－ｔ－ブチル－４－ヒドロキシフェニル）プロピオネートが挙げられる。 Examples of the monophenolic antioxidant include 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-4-ethylphenol, and stearin-β- ( 3,5-Di-t-butyl-4-hydroxyphenyl) propionate can be mentioned.
　ビスフェノール系酸化防止剤としては、例えば、２，２’－メチレンビス（４－メチル－６－ｔ－ブチルフェノール）、２，２’－メチレンビス（４－エチル－６－ｔ－ブチルフェノール）、４，４’－チオビス（３－メチル－６－ｔ－ブチルフェノール）、４，４’－ブチリデンビス（３－メチル－６－ｔ－ブチルフェノール）、３，９－ビス［１，１－ジメチル－２－［β－（３－ｔ－ブチル－４－ヒドロキシ－５－メチルフェニル）プロピオニルオキシ］エチル］２，４，８，１０－テトラオキサスピロ［５，５］ウンデカンが挙げられる。 Examples of the bisphenol-based antioxidant include 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2,2'-methylenebis (4-ethyl-6-t-butylphenol), and 4,4'. -Thiobis (3-methyl-6-t-butylphenol), 4,4'-butylidenebis (3-methyl-6-t-butylphenol), 3,9-bis [1,1-dimethyl-2- [β- (β- ( 3-t-Butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl] 2,4,8,10-tetraoxaspiro [5,5] undecane can be mentioned.
　高分子型フェノール系酸化防止剤としては、例えば、１，１，３－トリス（２－メチル－４－ヒドロキシ－５－ｔ－ブチルフェニル）ブタン、１，３，５－トリメチル－２，４，６－トリス（３，５－ジ－ｔ－ブチル－４－ヒドロキシベンジル）ベンゼン、テトラキス－［メチレン－３－（３’，５’－ジ－ｔ－ブチル－４’－ヒドロキシフェニル）プロピオネート］メタン、ビス［３，３’－ビス－（４’－ヒドロキシ－３’－ｔ－ブチルフェニル）ブチリックアシッド］グリコールエステル、１，３，５－トリス（３’，５’－ジ－ｔ－ブチル－４’－ヒドロキシベンジル）－Ｓ－トリアジン－２，４，６－（１Ｈ、３Ｈ、５Ｈ）トリオン、トコフェノールが挙げられる。 Examples of the high molecular weight phenolic antioxidant include 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 1,3,5-trimethyl-2,4. 6-Tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, tetrakis- [methylene-3- (3', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane , Bis [3,3'-bis- (4'-hydroxy-3'-t-butylphenyl) butyric acid] glycol ester, 1,3,5-tris (3', 5'-di-t-butyl) -4'-Hydroxybenzyl) -S-triazine-2,4,6- (1H, 3H, 5H) trione, tocophenol can be mentioned.
　硫黄系酸化防止剤としては、例えば、ジラウリル３，３’－チオジプロピオネート、ジミリスチル３，３’－チオジプロピオネート、ジステアリル３，３’－チオジプロピオネートが挙げられる。 Examples of the sulfur-based antioxidant include dilauryl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate, and disstearyl 3,3'-thiodipropionate.
　リン系酸化防止剤としては、例えば、トリフェニルホスファイト、ジフェニルイソデシルホスファイト、フェニルジイソデシルホスファイトが挙げられる。 Examples of the phosphorus-based antioxidant include triphenylphosphine, diphenylisodecylphosphite, and phenyldiisodecylphosphite.
〔紫外線吸収剤〕
　ウレタン系粘着剤組成物は、ウレタン系粘着剤層の劣化抑制等の点から、他の成分として、紫外線吸収剤を含んでいてもよい。紫外線吸収剤は、１種のみであってもよいし、２種以上であってもよい。 [UV absorber]
The urethane-based pressure-sensitive adhesive composition may contain an ultraviolet absorber as another component from the viewpoint of suppressing deterioration of the urethane-based pressure-sensitive adhesive layer. The ultraviolet absorber may be only one kind or two or more kinds.
　ウレタン系粘着剤組成物中の紫外線吸収剤の含有割合は、本発明の効果を損なわない範囲で、任意の適切な含有割合を採用し得る。このような含有割合は、ウレタンプレポリマーＰとポリオールＡの合計量に対する紫外線吸収剤の含有割合として、好ましくは０．０１重量％～１０重量％以上であり、より好ましくは０．０５重量％～５重量％であり、さらに好ましくは０．１重量％～３重量％であり、特に好ましくは０．２重量％～１重量％である。 As the content ratio of the ultraviolet absorber in the urethane-based pressure-sensitive adhesive composition, any appropriate content ratio can be adopted as long as the effect of the present invention is not impaired. Such a content ratio is preferably 0.01% by weight to 10% by weight or more, more preferably 0.05% by weight or more, as the content ratio of the ultraviolet absorber with respect to the total amount of the urethane prepolymer P and the polyol A. It is 5% by weight, more preferably 0.1% by weight to 3% by weight, and particularly preferably 0.2% by weight to 1% by weight.
　紫外線吸収剤としては、例えば、ベンゾフェノン系紫外線吸収剤、ベンゾトリアゾール系紫外線吸収剤、サリチル酸系紫外線吸収剤、シュウ酸アニリド系紫外線吸収剤、シアノアクリレート系紫外線吸収剤、トリアジン系紫外線吸収剤が挙げられる。 Examples of the ultraviolet absorber include benzophenone-based ultraviolet absorbers, benzotriazole-based ultraviolet absorbers, salicylic acid-based ultraviolet absorbers, oxalic acid anilide-based ultraviolet absorbers, cyanoacrylate-based ultraviolet absorbers, and triazine-based ultraviolet absorbers. ..
　ベンゾフェノン系紫外線吸収剤としては、例えば、２，４－ジヒドロキシベンゾフェノン、２－ヒドロキシ－４－メトキシベンゾフェノン、２－ヒドロキシ－４－オクトキシベンゾフェノン、２－ヒドロキシ－４－ドデシルオキシベンゾフェノン、２，２’－ジヒドロキシ－４－ジメトキシベンゾフェノン、２，２’－ジヒドロキシ－４，４’－ジメトキシベンゾフェノン、２－ヒドロキシ－４－メトキシ－５－スルホベンゾフェノン、ビス（２－メトキシ－４－ヒドロキシ－５－ベンゾイルフェニル）メタンが挙げられる。 Examples of the benzophenone-based ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, and 2,2'. -Dihydroxy-4-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone, bis (2-methoxy-4-hydroxy-5-benzoylphenyl) ) Methane is mentioned.
　ベンゾトリアゾール系紫外線吸収剤としては、例えば、２－（２’－ヒドロキシ－５’－メチルフェニル）ベンゾトリアゾール、２－（２’－ヒドロキシ－５’－ｔｅｒｔ－ブチルフェニル）ベンゾトリアゾール、２－（２’－ヒドロキシ－３’，５’－ジ－ｔｅｒｔ－ブチルフェニル）ベンゾトリアゾール、２－（２’－ヒドロキシ－３’－ｔｅｒｔ－ブチル－５’－メチルフェニル）－５－クロロベンゾトリアゾール、２－（２’－ヒドロキシ－３’，５’－ジ－ｔｅｒｔ－ブチルフェニル）５－クロロベンゾトリアゾール、２－（２’－ヒドロキシ－３’，５’－ジ－ｔｅｒｔ－アミルフェニル）ベンゾトリアゾール、２－（２’－ヒドロキシ－４’－オクトキシフェニル）ベンゾトリアゾール、２－［２’－ヒドロキシ－３’－（３’’，４’’，５’’，６’’，－テトラヒドロフタルイミドメチル）－５’－メチルフェニル］ベンゾトリアゾール、２，２’メチレンビス［４－（１，１，３，３－テトラメチルブチル）－６－（２Ｈ－ベンゾトリアゾール－２－イル）フェノール］、［２（２’－ヒドロキシ－５’－メタアクリロキシフェニル）－２Ｈ－ベンゾトリアゾールが挙げられる。 Examples of the benzotriazole-based ultraviolet absorber include 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-5'-tert-butylphenyl) benzotriazole, 2-( 2'-Hydroxy-3', 5'-di-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2 -(2'-Hydroxy-3', 5'-di-tert-butylphenyl) 5-chlorobenzotriazole, 2- (2'-hydroxy-3', 5'-di-tert-amylphenyl) benzotriazole, 2- (2'-Hydroxy-4'-octoxyphenyl) benzotriazole, 2- [2'-hydroxy-3'-(3'', 4'', 5'', 6'', -tetrahydrophthalimidemethyl ) -5'-Methylphenyl] benzotriazole, 2,2'methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazole-2-yl) phenol], [2 (2'-Hydroxy-5'-metaacryloxyphenyl) -2H-benzotriazole can be mentioned.
　サリチル酸系紫外線吸収剤としては、例えば、フェニルサリシレート、ｐ－ｔｅｒｔ－ブチルフェニルサリシレート、ｐ－オクチルフェニルサリシレートが挙げられる。 Examples of the salicylic acid-based ultraviolet absorber include phenylsalicylate, p-tert-butylphenylsalicylate, and p-octylphenylsalicylate.
　シアノアクリレート系紫外線吸収剤としては、例えば、２－エチルヘキシル－２－シアノ－３，３’－ジフェニルアクリレート、エチル－２－シアノ－３，３’－ジフェニルアクリレートが挙げられる。 Examples of the cyanoacrylate-based ultraviolet absorber include 2-ethylhexyl-2-cyano-3,3'-diphenylacrylate and ethyl-2-cyano-3,3'-diphenylacrylate.
〔光安定剤〕
　ウレタン系粘着剤組成物は、ウレタン系粘着剤層の劣化抑制等の点から、他の成分として、光安定剤を含んでいてもよい。光安定剤は、１種のみであってもよいし、２種以上であってもよい。 [Light stabilizer]
The urethane-based pressure-sensitive adhesive composition may contain a light stabilizer as another component from the viewpoint of suppressing deterioration of the urethane-based pressure-sensitive adhesive layer. The light stabilizer may be only one kind or two or more kinds.
　ウレタン系粘着剤組成物中の光安定剤の含有割合は、本発明の効果を損なわない範囲で、任意の適切な含有割合を採用し得る。このような含有割合は、ウレタンプレポリマーＰとポリオールＡの合計量に対する光安定剤の含有割合として、好ましくは０．０１重量％～１０重量％以上であり、より好ましくは０．０５重量％～５重量％であり、さらに好ましくは０．１重量％～３重量％であり、特に好ましくは０．２重量％～１重量％である。 As the content ratio of the light stabilizer in the urethane-based pressure-sensitive adhesive composition, any appropriate content ratio can be adopted as long as the effect of the present invention is not impaired. Such a content ratio is preferably 0.01% by weight to 10% by weight or more, more preferably 0.05% by weight or more, as the content ratio of the light stabilizer with respect to the total amount of the urethane prepolymer P and the polyol A. It is 5% by weight, more preferably 0.1% by weight to 3% by weight, and particularly preferably 0.2% by weight to 1% by weight.
　光安定剤としては、例えば、ヒンダードアミン系光安定剤、紫外線安定剤が挙げられる。 Examples of the light stabilizer include a hindered amine-based light stabilizer and an ultraviolet stabilizer.
　ヒンダードアミン系光安定剤としては、例えば、［ビス（２，２，６，６－テトラメチル－４－ピペリジル）セバケート］、ビス（１，２，２，６，６－ペンタメチル－４－ピペリジル）セバケート、メチル１，２，２，６，６－ペンタメチル－４－ピペリジルセバケートが挙げられる。 Examples of the hindered amine-based light stabilizer include [bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate] and bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate. , Methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacate.
　紫外線安定剤としては、例えば、ニッケルビス（オクチルフェニル）サルファイド、［２，２’－チオビス（４－ｔｅｒｔ－オクチルフェノラート）］－ｎ－ブチルアミンニッケル、ニッケルコンプレックス－３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシベンジル－リン酸モノエチレート、ニッケル－ジブチルジチオカーバメート、ベンゾエートタイプのクエンチャー、ニッケル－ジブチルジチオカーバメートが挙げられる。 Examples of the ultraviolet stabilizer include nickel bis (octylphenyl) sulfide, [2,2'-thiobis (4-tert-octylphenolate)] -n-butylamine nickel, nickel complex-3,5-di-tert-. Examples thereof include butyl-4-hydroxybenzyl-phosphate monoethylate, nickel-dibutyldithiocarbamate, benzoate type quencher, and nickel-dibutyldithiocarbamate.
〔脂肪酸エステル〕
　ウレタン系粘着剤組成物は、ウレタン系粘着剤層の濡れ性向上等の点から、他の成分として、脂肪酸エステルを含んでいてもよい。脂肪酸エステルは、１種のみであってもよいし、２種以上であってもよい。 [Fatty acid ester]
The urethane-based pressure-sensitive adhesive composition may contain a fatty acid ester as another component from the viewpoint of improving the wettability of the urethane-based pressure-sensitive adhesive layer. The fatty acid ester may be only one kind or two or more kinds.
　脂肪酸エステルの数平均分子量Ｍｎは、好ましくは２００～４００であり、より好ましくは２１０～３９５であり、さらに好ましくは２３０～３８０であり、特に好ましくは２４０～３６０であり、最も好ましくは２５０～３５０である。脂肪酸エステルの数平均分子量Ｍｎを上記範囲内に調整することによって、濡れ速度がより向上し得る。脂肪酸エステルの数平均分子量Ｍｎが小さすぎると、添加部数が多くても濡れ速度が向上しないおそれがある。脂肪酸エステルの数平均分子量Ｍｎが大きすぎると、乾燥時の粘着剤の硬化性が悪化し、濡れ特性に留まらずその他粘着特性に悪影響を及ぼすおそれがある。 The number average molecular weight Mn of the fatty acid ester is preferably 200 to 400, more preferably 210 to 395, still more preferably 230 to 380, particularly preferably 240 to 360, and most preferably 250 to 350. Is. By adjusting the number average molecular weight Mn of the fatty acid ester within the above range, the wetting rate can be further improved. If the number average molecular weight Mn of the fatty acid ester is too small, the wetting rate may not be improved even if the number of added portions is large. If the number average molecular weight Mn of the fatty acid ester is too large, the curability of the adhesive during drying deteriorates, which may adversely affect not only the wettability but also other adhesive properties.
　脂肪酸エステルとしては、本発明の効果を損なわない範囲で、任意の適切な脂肪酸エステルを採用し得る。このような脂肪酸エステルとしては、例えば、ポリオキシエチレンビスフェノールＡラウリン酸エステル、ステアリン酸ブチル、パルミチン酸２－エチルヘキシル、ステアリン酸２－エチルヘキシル、べへニン酸モノグリセライド、２－エチルヘキサン酸セチル、ミリスチン酸イソプロピル、パルミチン酸イソプロピル、イソステアリン酸コレステリル、メタクリル酸ラウリル、ヤシ脂肪酸メチル、ラウリン酸メチル、オレイン酸メチル、ステアリン酸メチル、ミリスチン酸ミリスチル、ミリスチン酸オクチルドデシル、ペンタエリスリトールモノオレエート、ペンタエリスリトールモノステアレート、ペンタエリスリトールテトラパルミテート、ステアリン酸ステアリル、ステアリン酸イソトリデシル、２－エチルヘキサン酸トリグリセライド、ラウリン酸ブチル、オレイン酸オクチルが挙げられる。 As the fatty acid ester, any suitable fatty acid ester can be adopted as long as the effect of the present invention is not impaired. Examples of such fatty acid esters include polyoxyethylene bisphenol A lauric acid ester, butyl stearate, 2-ethylhexyl palmitate, 2-ethylhexyl stearate, monoglyceride behenic acid, cetyl 2-ethylhexanoate, and myristic acid. Isopropyl, isopropyl palmitate, cholesteryl isostearate, lauryl methacrylate, methyl palm fatty acid, methyl laurate, methyl oleate, methyl stearate, myristyl myristate, octyldodecyl myristate, pentaerythritol monooleate, pentaerythritol monostearate , Pentaerythritol tetrapalmitate, stearyl stearate, isotridecyl stearate, triglyceride 2-ethylhexanoate, butyl laurate, octyl oleate.
≪１－２．基材層≫
　基材層の厚みとしては、用途に応じて、任意の適切な厚みを採用し得る。基材層の厚みは、好ましくは５μｍ～３００μｍであり、より好ましくは１０μｍ～２５０μｍであり、さらに好ましくは１５μｍ～２００μｍであり、特に好ましくは２０μｍ～１５０μｍである。 ≪1-2. Base material layer ≫
As the thickness of the base material layer, any appropriate thickness may be adopted depending on the intended use. The thickness of the base material layer is preferably 5 μm to 300 μm, more preferably 10 μm to 250 μm, further preferably 15 μm to 200 μm, and particularly preferably 20 μm to 150 μm.
　基材層は、単層でもよいし、２層以上の積層体であってもよい。基材層は、延伸されたものであっても良い。 The base material layer may be a single layer or a laminated body having two or more layers. The base material layer may be a stretched one.
　基材層の材料としては、用途に応じて、任意の適切な材料を採用し得る。例えば、プラスチック、紙、金属フィルム、不織布などが挙げられる。好ましくは、プラスチックである。基材層は、１種の材料から構成されていてもよいし、２種以上の材料から構成されていてもよい。例えば、２種以上のプラスチックから構成されていてもよい。 As the material of the base material layer, any appropriate material can be adopted depending on the application. For example, plastic, paper, metal film, non-woven fabric and the like can be mentioned. It is preferably plastic. The base material layer may be composed of one kind of material, or may be made of two or more kinds of materials. For example, it may be composed of two or more kinds of plastics.
　上記プラスチックとしては、例えば、ポリエステル系樹脂、ポリアミド系樹脂、ポリオレフィン系樹脂が挙げられる。ポリエステル系樹脂としては、例えば、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナフタレートが挙げられる。ポリオレフィン系樹脂としては、例えば、オレフィンモノマーの単独重合体、オレフィンモノマーの共重合体が挙げられる。ポリオレフィン系樹脂としては、具体的には、例えば、ホモポリプロピレン；エチレン成分を共重合成分とするブロック系、ランダム系、グラフト系等のプロピレン系共重合体；リアクターＴＰＯ；低密度、高密度、リニア低密度、超低密度等のエチレン系重合体；エチレン・プロピレン共重合体、エチレン・酢酸ビニル共重合体、エチレン・アクリル酸メチル共重合体、エチレン・アクリル酸エチル共重合体、エチレン・アクリル酸ブチル共重合体、エチレン・メタクリル酸共重合体、エチレン・メタクリル酸メチル共重合体等のエチレン系共重合体；が挙げられる。 Examples of the plastic include polyester-based resin, polyamide-based resin, and polyolefin-based resin. Examples of the polyester resin include polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate. Examples of the polyolefin-based resin include homopolymers of olefin monomers and copolymers of olefin monomers. Specific examples of the polyolefin-based resin include homopolypoly; a block-based, random-based, and graft-based propylene-based copolymer having an ethylene component as a copolymer; reactor TPO; low density, high density, and linear. Low-density, ultra-low-density, etc. ethylene-based copolymers; ethylene / propylene copolymer, ethylene / vinyl acetate copolymer, ethylene / methyl acrylate copolymer, ethylene / ethyl acrylate copolymer, ethylene / acrylic acid Examples thereof include butyl copolymers, ethylene / methacrylic acid copolymers, and ethylene-based copolymers such as ethylene / methyl methacrylate copolymers.
　基材層は、必要に応じて、任意の適切な添加剤を含有し得る。基材層に含有され得る添加剤としては、例えば、酸化防止剤、紫外線吸収剤、光安定剤、帯電防止剤、充填剤、顔料が挙げられる。基材層に含有され得る添加剤の種類、数、量は、目的に応じて適切に設定され得る。特に、基材層の材料がプラスチックの場合は、劣化防止等を目的として、上記の添加剤のいくつかを含有することが好ましい。耐候性向上等の観点から、添加剤として特に好ましくは、酸化防止剤、紫外線吸収剤、光安定剤、充填剤が挙げられる。 The substrate layer may contain any suitable additive, if desired. Examples of additives that can be contained in the base material layer include antioxidants, ultraviolet absorbers, light stabilizers, antistatic agents, fillers, and pigments. The type, number, and amount of additives that can be contained in the base material layer can be appropriately set according to the purpose. In particular, when the material of the base material layer is plastic, it is preferable to contain some of the above additives for the purpose of preventing deterioration and the like. From the viewpoint of improving weather resistance and the like, particularly preferable additives include antioxidants, ultraviolet absorbers, light stabilizers and fillers.
　酸化防止剤としては、任意の適切な酸化防止剤を採用し得る。このような酸化防止剤としては、例えば、フェノール系酸化防止剤、リン系加工熱安定剤、ラクトン系加工熱安定剤、イオウ系耐熱安定剤、フェノール・リン系酸化防止剤などが挙げられる。酸化防止剤の含有割合は、基材層のベース樹脂（基材層がブレンド物の場合にはそのブレンド物がベース樹脂である）に対して、好ましくは１重量％以下であり、より好ましくは０．５重量％以下であり、さらに好ましくは０．０１重量％～０．２重量％である。 As the antioxidant, any suitable antioxidant can be adopted. Examples of such antioxidants include phenol-based antioxidants, phosphorus-based processing heat stabilizers, lactone-based processing heat stabilizers, sulfur-based heat-resistant stabilizers, phenol-phosphorus-based antioxidants, and the like. The content ratio of the antioxidant is preferably 1% by weight or less, more preferably 1% by weight or less, based on the base resin of the base material layer (when the base material layer is a blend product, the blend product is the base resin). It is 0.5% by weight or less, more preferably 0.01% by weight to 0.2% by weight.
　紫外線吸収剤としては、任意の適切な紫外線吸収剤を採用し得る。このような紫外線吸収剤としては、例えば、ベンゾトリアゾール系紫外線吸収剤、トリアジン系紫外線吸収剤、ベンゾフェノン系紫外線吸収剤などが挙げられる。紫外線吸収剤の含有割合は、基材層を形成するベース樹脂（基材層がブレンド物の場合にはそのブレンド物がベース樹脂である）に対して、好ましくは２重量％以下であり、より好ましくは１重量％以下であり、さらに好ましくは０．０１重量％～０．５重量％である。 As the ultraviolet absorber, any appropriate ultraviolet absorber can be adopted. Examples of such an ultraviolet absorber include a benzotriazole-based ultraviolet absorber, a triazine-based ultraviolet absorber, and a benzophenone-based ultraviolet absorber. The content ratio of the ultraviolet absorber is preferably 2% by weight or less with respect to the base resin forming the base material layer (when the base material layer is a blend product, the blend product is the base resin), and more. It is preferably 1% by weight or less, and more preferably 0.01% by weight to 0.5% by weight.
　光安定剤としては、任意の適切な光安定剤を採用し得る。このような光安定剤としては、例えば、ヒンダードアミン系光安定剤、ベンゾエート系光安定剤などが挙げられる。光安定剤の含有割合は、基材層を形成するベース樹脂（基材層がブレンド物の場合にはそのブレンド物がベース樹脂である）に対して、好ましくは２重量％以下であり、より好ましくは１重量％以下であり、さらに好ましくは０．０１重量％～０．５重量％である。 As the light stabilizer, any appropriate light stabilizer can be adopted. Examples of such a light stabilizer include a hindered amine-based light stabilizer and a benzoate-based light stabilizer. The content ratio of the light stabilizer is preferably 2% by weight or less with respect to the base resin forming the base material layer (when the base material layer is a blend product, the blend product is the base resin), and more. It is preferably 1% by weight or less, and more preferably 0.01% by weight to 0.5% by weight.
　充填剤としては、任意の適切な充填剤を採用し得る。このような充填剤としては、例えば、無機系充填剤などが挙げられる。無機系充填剤としては、具体的には、例えば、カーボンブラック、酸化チタン、酸化亜鉛などが挙げられる。充填剤の含有割合は、基材層を形成するベース樹脂（基材層がブレンド物の場合にはそのブレンド物がベース樹脂である）に対して、好ましくは２０重量％以下であり、より好ましくは１０重量％以下であり、さらに好ましくは０．０１重量％～１０重量％である。 As the filler, any suitable filler can be adopted. Examples of such a filler include an inorganic filler and the like. Specific examples of the inorganic filler include carbon black, titanium oxide, zinc oxide and the like. The content ratio of the filler is preferably 20% by weight or less, more preferably 20% by weight or less, based on the base resin forming the base material layer (when the base material layer is a blend product, the blend product is the base resin). Is 10% by weight or less, more preferably 0.01% by weight to 10% by weight.
　さらに、添加剤としては、帯電防止性付与を目的として、界面活性剤、無機塩、多価アルコール、金属化合物、カーボン等の無機系、低分子量系および高分子量系帯電防止剤も好ましく挙げられる。特に、汚染、粘着性維持の観点から、高分子量系帯電防止剤やカーボンが好ましい。 Further, as the additive, an inorganic type such as a surfactant, an inorganic salt, a polyhydric alcohol, a metal compound, and carbon, a low molecular weight type, and a high molecular weight type antistatic agent are also preferably mentioned for the purpose of imparting antistatic properties. In particular, from the viewpoint of contamination and maintenance of adhesiveness, high molecular weight antistatic agents and carbon are preferable.
≪≪２．表面保護フィルムの製造方法≫≫
　本発明の表面保護フィルムは、任意の適切な方法により製造することができる。このような製造方法としては、例えば、
（１）粘着剤層の形成材料の溶液や熱溶融液を基材層上に塗布する方法、
（２）それに準じ、セパレーター状に塗布、形成した粘着剤層を基材層上に移着する方法、
（３）粘着剤層の形成材料を基材層上に押出して形成塗布する方法、
（４）基材層と粘着剤層を二層または多層にて押出しする方法、
（５）基材層上に粘着剤層を単層ラミネートする方法またはラミネート層とともに粘着剤層を二層ラミネートする方法、
（６）粘着剤層とフィルムやラミネート層等の基材層形成材料とを二層または多層ラミネートする方法、
などの、任意の適切な製造方法に準じて行うことができる。 ≪≪2. Manufacturing method of surface protection film ≫≫
The surface protective film of the present invention can be produced by any suitable method. As such a manufacturing method, for example,
(1) A method of applying a solution of a material for forming an adhesive layer or a thermal melt solution onto a base material layer,
(2) A method of transferring the pressure-sensitive adhesive layer applied and formed in the form of a separator onto the base material layer according to the method.
(3) A method of extruding a material for forming an adhesive layer onto a base material layer to form and apply the adhesive layer.
(4) A method of extruding a base material layer and an adhesive layer in two or multiple layers,
(5) A method of laminating a single layer of an adhesive layer on a base material layer or a method of laminating two layers of an adhesive layer together with a laminating layer.
(6) A method of laminating a pressure-sensitive adhesive layer and a base material layer forming material such as a film or a laminate layer in two or multiple layers.
It can be carried out according to any suitable manufacturing method such as.
　塗布の方法としては、例えば、ロールコーター法、コンマコーター法、ダイコーター法、リバースコーター法、シルクスクリーン法、グラビアコーター法などが使用できる。 As the coating method, for example, a roll coater method, a comma coater method, a die coater method, a reverse coater method, a silk screen method, a gravure coater method, etc. can be used.
≪≪３．表面保護フィルムの用途≫≫
　本発明の実施形態による表面保護フィルムは、任意の適切な用途に用い得る。好ましくは、本発明の表面保護フィルムは、被着体への汚染が非常に少なく、好ましくは、濡れ性やリワーク性に優れるので、例えば、光学部材や電子部材の表面保護に好ましく用いられる。光学部材としては、例えば、ＬＣＤ、ＬＣＤなどを用いたタッチパネル、ＬＣＤに使用されるカラーフィルター、偏光板などが挙げられる。 ≪≪3. Uses of surface protective film ≫≫
The surface protective film according to the embodiment of the present invention can be used for any suitable application. Preferably, the surface protective film of the present invention is preferably used for surface protection of optical members and electronic members, for example, because it has very little contamination on the adherend and is preferably excellent in wettability and reworkability. Examples of the optical member include a touch panel using an LCD, an LCD, a color filter used for the LCD, a polarizing plate, and the like.
　本発明の実施形態による表面保護フィルムが貼着された部材、例えば、光学部材や電子部材は、貼着された表面保護フィルムを手作業で何度も貼り合わせ・剥離を行うことが可能である。 For a member to which the surface protective film according to the embodiment of the present invention is attached, for example, an optical member or an electronic member, the attached surface protective film can be manually attached and peeled off many times. ..
　すなわち、本発明の実施形態による光学部材は、本発明の表面保護フィルムが貼着されたものである。また、本発明の実施形態による電子部材は、本発明の表面保護フィルムが貼着されたものである。 That is, the optical member according to the embodiment of the present invention is the one to which the surface protective film of the present invention is attached. Further, the electronic member according to the embodiment of the present invention is the one to which the surface protective film of the present invention is attached.
　以下、実施例により本発明を具体的に説明するが、本発明はこれら実施例になんら限定されるものではない。なお、実施例等における、試験および評価方法は以下のとおりである。なお、「部」と記載されている場合は、特記事項がない限り「重量部」を意味し、「％」と記載されている場合は、特記事項がない限り「重量％」を意味する。 Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples. The tests and evaluation methods in the examples and the like are as follows. In addition, when it is described as "part", it means "part by weight" unless there is a special note, and when it is described as "%", it means "% by weight" unless there is a special note.
＜対ガラス粘着力＞
　セパレーターを剥がした表面保護フィルム（幅２５ｍｍ×長さ１４０ｍｍ）をガラス（ソーダライムガラス、松浪硝子工業株式会社製）に２ｋｇハンドローラー１往復にて貼着した。その後、２３℃の環境温度下で３０分間放置した。得られた評価用試料を、引っ張り試験機にて測定した。引っ張り試験機としては、島津製作所社製の商品名「オートグラフＡＧ－Ｘｐｌｕｓ　ＨＳ　６０００ｍｍ／ｍｉｎ高速モデル（ＡＧ－５０ＮＸ　ｐｌｕｓ）」を用いた。引っ張り試験機に評価用試料をセットした後、引っ張り試験を開始した。引っ張り試験の条件は、剥離角度＝１８０度、剥離速度（引っ張り速度）＝３００ｍｍ／分とした。ガラスから表面保護フィルムを剥離した時の荷重を測定し、その際の平均荷重を表面保護フィルムの対ガラス粘着力（剥離力）とした。 <Adhesive strength against glass>
A surface protective film (width 25 mm × length 140 mm) from which the separator had been peeled off was attached to glass (soda lime glass, manufactured by Matsunami Glass Ind. Co., Ltd.) with a 2 kg hand roller reciprocating once. Then, it was left for 30 minutes at an environmental temperature of 23 ° C. The obtained evaluation sample was measured with a tensile tester. As the tensile tester, a product name "Autograph AG-Xplus HS 6000 mm / min high-speed model (AG-50NX plus)" manufactured by Shimadzu Corporation was used. After setting the evaluation sample in the tensile tester, the tensile test was started. The conditions for the tensile test were a peeling angle = 180 degrees and a peeling speed (pulling speed) = 300 mm / min. The load when the surface protective film was peeled from the glass was measured, and the average load at that time was taken as the adhesive force (peeling force) of the surface protective film against the glass.
＜対ガラス残留接着率＞
　ガラス板（松浪硝子製、１．３５ｍｍ×１０ｃｍ×１０ｃｍ）に、表面保護フィルムをハンドローラーで全面に貼り合せ、温度２３℃、湿度５５％ＲＨの雰囲気下で、２４時間保管した後、剥離角度＝１８０度、０．３ｍ／ｍｉｎの速度で表面保護フィルムを剥離し、長さ１５０ｍｍに切断した１９ｍｍ幅のＮｏ．３１Ｂテープ（日東電工（株）製、基材厚：２５μｍ）を温度２３℃、湿度５５％ＲＨの雰囲気下で、２．０ｋｇローラー１往復により貼り付けた。温度２３℃、湿度５５％ＲＨの雰囲気下で、３０分間養生した後、引張試験機（島津製作所社製の商品名「オートグラフＡＧ－Ｘｐｌｕｓ　ＨＳ　６０００ｍｍ／ｍｉｎ高速モデル（ＡＧ－５０ＮＸ　ｐｌｕｓ）」）を用い、剥離角度＝１８０度、引っ張り速度＝３００ｍｍ／ｍｉｎで剥離し、粘着力を測定した。
　別途、上記のような処理を行っていないガラス板に対して、同様に、１９ｍｍ幅のＮｏ．３１Ｂテープの粘着力を測定し、下記の式で残留接着率を算出した。
　残留接着率（％）＝（表面保護フィルム剥離後のガラス板に対するＮｏ．３１Ｂ粘着力／ガラス板に対するＮｏ．３１Ｂ粘着力）×１００
　この残留接着率は、表面保護フィルムの粘着剤成分が被着体に対してどの程度表面に転写し汚染しているかの指標となる。残留接着率の値が高いほど、被着体を汚染せずより良い表面保護フィルムであり、残留接着率の値が低いほど、被着体の表面を粘着剤成分などで汚染していると言える。 <Residual adhesion to glass>
A surface protective film is attached to the entire surface of a glass plate (made by Matsunami Glass, 1.35 mm x 10 cm x 10 cm) with a hand roller, stored in an atmosphere of temperature 23 ° C and humidity 55% RH for 24 hours, and then the peeling angle. The surface protective film was peeled off at a speed of 180 degrees and 0.3 m / min, and the No. 19 mm wide No. was cut to a length of 150 mm. A 31B tape (manufactured by Nitto Denko Corporation, substrate thickness: 25 μm) was attached by one reciprocating 2.0 kg roller in an atmosphere of a temperature of 23 ° C. and a humidity of 55% RH. After curing for 30 minutes in an atmosphere with a temperature of 23 ° C and a humidity of 55% RH, a tensile tester (trade name "Autograph AG-Xplus HS 6000 mm / min high-speed model (AG-50NX plus)" manufactured by Shimadzu Corporation) Was peeled off at a peeling angle = 180 degrees and a tensile speed = 300 mm / min, and the adhesive strength was measured.
Separately, for a glass plate that has not been treated as described above, a 19 mm wide No. The adhesive strength of the 31B tape was measured, and the residual adhesive ratio was calculated by the following formula.
Residual Adhesive Rate (%) = (No. 31B Adhesive Strength on Glass Plate after Peeling of Surface Protective Film / No. 31B Adhesive Strength on Glass Plate) x 100
This residual adhesive ratio is an index of how much the pressure-sensitive adhesive component of the surface protective film is transferred to the surface of the adherend and contaminated. It can be said that the higher the residual adhesion ratio value, the better the surface protection film without contaminating the adherend, and the lower the residual adhesion ratio value, the more the surface of the adherend is contaminated with an adhesive component or the like. ..
＜耐ガラス剥離帯電圧＞
　セパレーターを剥がした表面保護フィルムを幅７０ｍｍ、長さ１００ｍｍのサイズにカットし、ガラス（ソーダライムガラス、松浪硝子工業株式会社製）の表面に、表面保護フィルムの片方の端部が該被着体の端から３０ｍｍはみ出すようにして、ハンドローラーにて圧着した。このサンプルを２３℃×５０％ＲＨの環境下に１日放置した後、高さ２０ｍｍのサンプル固定台の所定の位置にセットした。該被着体から３０ｍｍはみ出した表面保護フィルムの端部を自動巻取り機（図示せず）に固定し、剥離角度＝１５０°、剥離速度＝３０ｍ／ｍｉｎとなるように剥離した。このときに発生する被着体表面の電位を、被着体の中央から高さ３０ｍｍの位置に固定してある電位測定器（シシド静電気社製、型式「ＳＴＡＴＩＲＯＮ　ＤＺ－４」）にて、「剥離帯電圧」を測定した。測定は、２３℃、５０％ＲＨの環境下で行った。 <Glass-resistant band voltage>
The surface protective film from which the separator has been peeled off is cut into a size of 70 mm in width and 100 mm in length, and one end of the surface protective film is attached to the surface of glass (soda lime glass, manufactured by Matsunami Glass Ind.). It was crimped with a hand roller so as to protrude 30 mm from the end of the glass. This sample was left in an environment of 23 ° C. × 50% RH for 1 day, and then set in a predetermined position on a sample fixing table having a height of 20 mm. The end portion of the surface protective film protruding 30 mm from the adherend was fixed to an automatic winder (not shown) and peeled so that the peeling angle = 150 ° and the peeling speed = 30 m / min. The potential on the surface of the adherend generated at this time is fixed at a position 30 mm in height from the center of the adherend with a potential measuring instrument (manufactured by Sisid Electrostatic Co., Ltd., model "STATIRON DZ-4"). "Peeling band voltage" was measured. The measurement was performed in an environment of 23 ° C. and 50% RH.
＜ヘイズ＞
　ウレタン系粘着剤組成物を、片面をシリコーンで剥離処理した厚み７５μｍのポリエステルフィルム（商品名：ダイアホイルＭＲＦ７５、三菱ケミカル株式会社製）の剥離処理面に、実施例・比較例の条件にて塗工乾燥し、ウレタン系粘着剤層を作製した。次いで、ウレタン系粘着剤層の表面に、片面をシリコーンで剥離処理した厚み７５μｍのポリエステルフィルム（商品名：ダイアホイルＭＲＥ７５、三菱ケミカル株式会社製）を、そのポリエステルフィルムの剥離処理面がウレタン系粘着剤層側になるようにして被覆し、常温で５日間エージングを行った。
　５０ｍｍ×５０ｍｍの厚紙の中央に２０ｍｍ×２０ｍｍの穴をあけたものを２枚用意し、片方に試料単体をハンドローラー１往復にて貼着後、もう一方を貼着した。
　上記のようにして得られた評価用試料のヘイズを、村上色彩技術研究所社製の「ＨＭ－１５０Ｎ」で測定した。 <Haze>
The urethane adhesive composition is applied to the peeled surface of a polyester film (trade name: Diafoil MRF75, manufactured by Mitsubishi Chemical Corporation) having a thickness of 75 μm, one side of which is peeled with silicone, under the conditions of Examples and Comparative Examples. It was industrially dried to prepare a urethane-based pressure-sensitive adhesive layer. Next, a polyester film with a thickness of 75 μm (trade name: Diafoil MRE75, manufactured by Mitsubishi Chemical Corporation) whose one side was peeled off with silicone was applied to the surface of the urethane adhesive layer, and the peeled surface of the polyester film was urethane-based adhesive. The film was coated so as to be on the agent layer side, and aged at room temperature for 5 days.
Two sheets of 50 mm × 50 mm thick paper with a hole of 20 mm × 20 mm were prepared, and a single sample was attached to one of them with one reciprocating hand roller, and then the other was attached.
The haze of the evaluation sample obtained as described above was measured with "HM-150N" manufactured by Murakami Color Technology Research Institute.
＜粘着剤厚塗り可否＞
　実施例、比較例のそれぞれにおいて、ウレタン系粘着剤溶液を、ポリエステル樹脂からなる基材（商品名「Ｔ１００－７５Ｓ」、厚み７５μｍ、三菱ケミカル株式会社製）に塗布して乾燥して、乾燥後の厚みが７５μｍの粘着剤層が得られるか否かを観察した。
〇：乾燥後の厚みが７５μｍの粘着剤層を形成できた。
×：乾燥後の厚みが７５μｍの粘着剤層を形成できなかった。 <Availability of thick adhesive coating>
In each of Examples and Comparative Examples, a urethane-based pressure-sensitive adhesive solution was applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 μm, manufactured by Mitsubishi Chemical Co., Ltd.), dried, and then dried. It was observed whether or not a pressure-sensitive adhesive layer having a thickness of 75 μm could be obtained.
◯: An adhesive layer having a thickness of 75 μm after drying could be formed.
X: The pressure-sensitive adhesive layer having a thickness of 75 μm after drying could not be formed.
〔製造例１〕：ウレタンプレポリマーの製造
　１Ｌ丸底セパラブルフラスコ、セパラブルカバー、分液ロート、温度計、窒素導入管、リービッヒ冷却器、バキュームシール、攪拌棒、攪拌羽が装備された重合用実験装置に、ポリプロピレングリコール（製品名「サンニックスＰＰ－２０００」、三洋化成工業社製）を１５０ｇ、ポリエステルポリオール（製品名「クラレポリオールＰ－２０１０」、クラレ社製）を１５０ｇ、溶剤としてトルエン（東ソー社製）を１１０ｇ、触媒としてジラウリン酸ジブチルすず（ＩＶ）（和光純薬工業社製）を０．０４１ｇ、を投入し、撹拌しながら、常温で窒素置換を１時間実施した。その後、窒素流入下、攪拌しながら、ヘキサメチレンジイソシアネート（製品名「ＨＤＩ」、東ソー社製）を３３．５ｇ投入し、ウオーターバスにて実験装置内溶液温度が９０±２℃となるように制御しつつ、４時間保持した後、ポリプロピレングリコール（製品名「ＧＰ１０００」、三洋化成工業社製）を７４．９ｇ投入し、ウオーターバスにて実験装置内溶液温度が９０±２℃となるように制御しつつ、２時間保持した後、ヘキサメチレンジイソシアネート（製品名「ＨＤＩ」、東ソー社製）を２５．４ｇ投入し、ウオーターバスにて実験装置内溶液温度が９０±２℃となるように制御しつつ、２時間保持し、ウレタンプレポリマーの溶液を得た。なお、重合途中に、重合中の温度制御および粘度上昇による撹拌性低下防止のために、適宜トルエンを滴下した。滴下したトルエンの総量は３２０ｇであった。ウレタンプレポリマーの溶液の固形分濃度は５０重量％であった。このウレタンプレポリマーを実施例、比較例で用いた。 [Production Example 1]: Production of urethane prepolymer 1L round bottom separable flask, separable cover, liquid separation funnel, thermometer, nitrogen introduction tube, Leibich cooler, vacuum seal, stirring rod, polymerization equipped with stirring blades 150 g of polypropylene glycol (product name "Sannicks PP-2000", manufactured by Sanyo Kasei Kogyo Co., Ltd.), 150 g of polyester polyol (product name "Kurare polyol P-2010", manufactured by Kuraray Co., Ltd.), and toluene as a solvent in the experimental equipment for use. 110 g of (manufactured by Toso Co., Ltd.) and 0.041 g of dibutyl tin dilaurate (IV) (manufactured by Wako Pure Chemical Industries, Ltd.) were added as a catalyst, and nitrogen substitution was carried out at room temperature for 1 hour while stirring. After that, 33.5 g of hexamethylene diisocyanate (product name "HDI", manufactured by Tosoh Corporation) was added while stirring under the inflow of nitrogen, and the solution temperature in the experimental device was controlled to 90 ± 2 ° C. in a water bath. After holding for 4 hours, 74.9 g of polypropylene glycol (product name "GP1000", manufactured by Sanyo Kasei Kogyo Co., Ltd.) was added, and the solution temperature in the experimental device was controlled to 90 ± 2 ° C. in a water bath. After holding for 2 hours, 25.4 g of hexamethylene diisocyanate (product name "HDI", manufactured by Tosoh Corporation) was added, and the solution temperature in the experimental device was controlled to 90 ± 2 ° C. in a water bath. While holding for 2 hours, a solution of urethane prepolymer was obtained. In addition, during the polymerization, toluene was appropriately added dropwise in order to control the temperature during the polymerization and prevent the decrease in agitation due to the increase in viscosity. The total amount of toluene dropped was 320 g. The solid content concentration of the urethane prepolymer solution was 50% by weight. This urethane prepolymer was used in Examples and Comparative Examples.
〔実施例１〕
　ウレタンプレポリマー５０重量部、ポリオールとして、ヒドロキシル基を３個有するポリオールであるプレミノールＳ３０１１（旭硝子社製、Ｍｎ＝１００００）３０重量部、ヒドロキシル基を３個有するポリオールであるサンニックスＧＰ４０００（三洋化成社製、Ｍｎ＝４０００）２０重量部、架橋剤としてイソシアネート化合物（コロネートＨＸ：Ｃ／ＨＸ、日本ポリウレタン社製）８．６重量部、酸化防止剤として、Ｉｒｇａｎｏｘ１０１０（ＢＡＳＦ社製）０．５重量部、触媒として、ナーセム第２鉄（日本化学産業社製）０．０３重量部を、全体の固形分が５０重量％となるように酢酸エチルで希釈し、ウレタン系粘着剤溶液を得た。そして、ウレタン系粘着剤溶液を、ポリエステル樹脂からなる基材（商品名「Ｔ１００－７５Ｓ」、厚み７５μｍ、三菱ケミカル株式会社製）に乾燥後の厚みが７５μｍとなるよう塗布し、乾燥温度１３０℃、乾燥時間３分の条件でキュアーして乾燥し、粘着剤組成物（１）からなる粘着剤層を作製した。次いで、得られた粘着剤層の表面に、一方の面にシリコーン処理を施した厚さ２５μｍのポリエステル樹脂からなる剥離シート（商品名「ＭＲＦ２５」、厚み２５μｍ、三菱ケミカル株式会社製）のシリコーン処理面を貼合せて、表面保護フィルム（１）を得た。常温で５日間エージングを行い、評価を行った。剥離シートは評価の直前に剥離した。結果を表１に示した。 [Example 1]
50 parts by weight of urethane prepolymer, 30 parts by weight of Preminol S3011 (Mn = 10000, manufactured by Asahi Glass Co., Ltd.), which is a polyol having 3 hydroxyl groups, and Sanniks GP4000 (Sanyo Kasei Co., Ltd.), which is a polyol having 3 hydroxyl groups. , Mn = 4000) 20 parts by weight, isocyanate compound (Coronate HX: C / HX, manufactured by Nippon Polyurethane Co., Ltd.) 8.6 parts by weight as a cross-linking agent, Irganox1010 (manufactured by BASF) 0.5 parts by weight as an antioxidant. As a catalyst, 0.03 part by weight of Nasem ferrous iron (manufactured by Nippon Kagaku Sangyo Co., Ltd.) was diluted with ethyl acetate so that the total solid content was 50% by weight to obtain a urethane-based pressure-sensitive adhesive solution. Then, the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 μm, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 μm, and the drying temperature is 130 ° C. , Cure and dry under the condition of drying time of 3 minutes to prepare a pressure-sensitive adhesive layer composed of the pressure-sensitive adhesive composition (1). Next, the surface of the obtained pressure-sensitive adhesive layer was treated with a silicone-treated release sheet (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 μm, one of which was treated with silicone. The surfaces were bonded together to obtain a surface protective film (1). Aging was performed at room temperature for 5 days for evaluation. The release sheet was peeled off immediately before the evaluation. The results are shown in Table 1.
〔実施例２〕
　ウレタンプレポリマー５０重量部、ポリオールとして、ヒドロキシル基を３個有するポリオールであるプレミノールＳ３０１１（旭硝子社製、Ｍｎ＝１００００）３０重量部、ヒドロキシル基を３個有するポリオールであるサンニックスＧＰ３０００（三洋化成社製、Ｍｎ＝３０００）２０重量部、架橋剤としてイソシアネート化合物（コロネートＨＸ：Ｃ／ＨＸ、日本ポリウレタン社製）１０．１重量部、酸化防止剤として、Ｉｒｇａｎｏｘ１０１０（ＢＡＳＦ社製）０．５重量部、触媒として、ナーセム第２鉄（日本化学産業社製）０．０３重量部を、全体の固形分が５０重量％となるように酢酸エチルで希釈し、ウレタン系粘着剤溶液を得た。そして、ウレタン系粘着剤溶液を、ポリエステル樹脂からなる基材（商品名「Ｔ１００－７５Ｓ」、厚み７５μｍ、三菱ケミカル株式会社製）に乾燥後の厚みが７５μｍとなるよう塗布し、乾燥温度１３０℃、乾燥時間３分の条件でキュアーして乾燥し、粘着剤組成物（２）からなる粘着剤層を作製した。次いで、得られた粘着剤層の表面に、一方の面にシリコーン処理を施した厚さ２５μｍのポリエステル樹脂からなる剥離シート（商品名「ＭＲＦ２５」、厚み２５μｍ、三菱ケミカル株式会社製）のシリコーン処理面を貼合せて、表面保護フィルム（２）を得た。常温で５日間エージングを行い、評価を行った。剥離シートは評価の直前に剥離した。結果を表１に示した。 [Example 2]
Preminol S3011 (Mn = 10000, manufactured by Asahi Glass Co., Ltd.), which is a polyol having 3 hydroxyl groups, and Sanniks GP3000 (Sanyo Kasei Co., Ltd.), which is a polyol having 3 hydroxyl groups and 50 parts by weight of urethane prepolymer. , Mn = 3000) 20 parts by weight, isocyanate compound (Coronate HX: C / HX, manufactured by Nippon Polyurethane Co., Ltd.) 10.1 parts by weight as a cross-linking agent, Irganox 1010 (manufactured by BASF) 0.5 parts by weight as an antioxidant. As a catalyst, 0.03 part by weight of Nasem ferrous iron (manufactured by Nippon Kagaku Sangyo Co., Ltd.) was diluted with ethyl acetate so that the total solid content was 50% by weight to obtain a urethane-based pressure-sensitive adhesive solution. Then, the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 μm, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 μm, and the drying temperature is 130 ° C. , Cure and dry under the condition of drying time of 3 minutes to prepare a pressure-sensitive adhesive layer composed of the pressure-sensitive adhesive composition (2). Next, the surface of the obtained pressure-sensitive adhesive layer was treated with a silicone-treated release sheet (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 μm, one of which was treated with silicone. The surfaces were bonded together to obtain a surface protective film (2). Aging was performed at room temperature for 5 days for evaluation. The release sheet was peeled off immediately before the evaluation. The results are shown in Table 1.
〔実施例３〕
　ウレタンプレポリマー５０重量部、ポリオールとして、ヒドロキシル基を３個有するポリオールであるプレミノールＳ３０１１（旭硝子社製、Ｍｎ＝１００００）３０重量部、ヒドロキシル基を３個有するポリオールであるサンニックスＧＰ３０００（三洋化成社製、Ｍｎ＝３０００）１５重量部、ヒドロキシル基を３個有するポリオールであるサンニックスＧＰ１０００（三洋化成社製、Ｍｎ＝１０００）５重量部、架橋剤としてイソシアネート化合物（コロネートＨＸ：Ｃ／ＨＸ、日本ポリウレタン社製）１２．９重量部、酸化防止剤として、Ｉｒｇａｎｏｘ１０１０（ＢＡＳＦ社製）０．５重量部、触媒として、ナーセム第２鉄（日本化学産業社製）０．０３重量部を、全体の固形分が５０重量％となるように酢酸エチルで希釈し、ウレタン系粘着剤溶液を得た。そして、ウレタン系粘着剤溶液を、ポリエステル樹脂からなる基材（商品名「Ｔ１００－７５Ｓ」、厚み７５μｍ、三菱ケミカル株式会社製）に乾燥後の厚みが７５μｍとなるよう塗布し、乾燥温度１３０℃、乾燥時間３分の条件でキュアーして乾燥し、粘着剤組成物（３）からなる粘着剤層を作製した。次いで、得られた粘着剤層の表面に、一方の面にシリコーン処理を施した厚さ２５μｍのポリエステル樹脂からなる剥離シート（商品名「ＭＲＦ２５」、厚み２５μｍ、三菱ケミカル株式会社製）のシリコーン処理面を貼合せて、表面保護フィルム（３）を得た。常温で５日間エージングを行い、評価を行った。剥離シートは評価の直前に剥離した。結果を表１に示した。 [Example 3]
50 parts by weight of urethane prepolymer, 30 parts by weight of Preminol S3011 (Mn = 10000, manufactured by Asahi Glass Co., Ltd.), which is a polyol having 3 hydroxyl groups, and Sanniks GP3000 (Sanyo Kasei Co., Ltd.), which is a polyol having 3 hydroxyl groups. Mn = 3000) 15 parts by weight, Sanniks GP1000 (Mn = 1000, manufactured by Sanyo Kasei Co., Ltd.), which is a polyol having three hydroxyl groups, 5 parts by weight, isocyanate compound (Coronate HX: C / HX, Japan) as a cross-linking agent 12.9 parts by weight of polyurethane (manufactured by Polyurethane), 0.5 parts by weight of Irganox1010 (manufactured by BASF) as an antioxidant, and 0.03 parts by weight of Nasem ferrous iron (manufactured by Nippon Kagaku Sangyo) as a catalyst. It was diluted with ethyl acetate so that the solid content was 50% by weight to obtain a urethane-based pressure-sensitive adhesive solution. Then, the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 μm, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 μm, and the drying temperature is 130 ° C. , Cure and dry under the condition of drying time of 3 minutes to prepare a pressure-sensitive adhesive layer composed of the pressure-sensitive adhesive composition (3). Next, the surface of the obtained pressure-sensitive adhesive layer was treated with a silicone-treated release sheet (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 μm, one of which was treated with silicone. The surfaces were bonded together to obtain a surface protective film (3). Aging was performed at room temperature for 5 days for evaluation. The release sheet was peeled off immediately before the evaluation. The results are shown in Table 1.
〔実施例４〕
　ウレタンプレポリマー５０重量部、ポリオールとして、ヒドロキシル基を３個有するポリオールであるプレミノールＳ３０１１（旭硝子社製、Ｍｎ＝１００００）３０重量部、ヒドロキシル基を３個有するポリオールであるサンニックスＧＰ３０００（三洋化成社製、Ｍｎ＝３０００）１８重量部、ヒドロキシル基を３個有するポリオールであるサンニックスＧＰ６００（三洋化成社製、Ｍｎ＝６００）２重量部、架橋剤としてイソシアネート化合物（コロネートＨＸ：Ｃ／ＨＸ、日本ポリウレタン社製）１２．７重量部、酸化防止剤として、Ｉｒｇａｎｏｘ１０１０（ＢＡＳＦ社製）０．５重量部、触媒として、ナーセム第２鉄（日本化学産業社製）０．０３重量部を、全体の固形分が５０重量％となるように酢酸エチルで希釈し、ウレタン系粘着剤溶液を得た。そして、ウレタン系粘着剤溶液を、ポリエステル樹脂からなる基材（商品名「Ｔ１００－７５Ｓ」、厚み７５μｍ、三菱ケミカル株式会社製）に乾燥後の厚みが７５μｍとなるよう塗布し、乾燥温度１３０℃、乾燥時間３分の条件でキュアーして乾燥し、粘着剤組成物（４）からなる粘着剤層を作製した。次いで、得られた粘着剤層の表面に、一方の面にシリコーン処理を施した厚さ２５μｍのポリエステル樹脂からなる剥離シート（商品名「ＭＲＦ２５」、厚み２５μｍ、三菱ケミカル株式会社製）のシリコーン処理面を貼合せて、表面保護フィルム（４）を得た。常温で５日間エージングを行い、評価を行った。剥離シートは評価の直前に剥離した。結果を表１に示した。 [Example 4]
50 parts by weight of urethane prepolymer, 30 parts by weight of Preminol S3011 (Mn = 10000, manufactured by Asahi Glass Co., Ltd.), which is a polyol having 3 hydroxyl groups, and Sanniks GP3000 (Sanyo Kasei Co., Ltd.), which is a polyol having 3 hydroxyl groups. Mn = 3000) 18 parts by weight, Sanniks GP600 (Mn = 600, manufactured by Sanyo Kasei Co., Ltd.), which is a polyol having three hydroxyl groups, 2 parts by weight, isocyanate compound (Coronate HX: C / HX, Japan) as a cross-linking agent 12.7 parts by weight of polyurethane (manufactured by Polyurethane), 0.5 parts by weight of Irganox1010 (manufactured by BASF) as an antioxidant, and 0.03 parts by weight of Nasem ferrous iron (manufactured by Nippon Kagaku Sangyo) as a catalyst. It was diluted with ethyl acetate so that the solid content was 50% by weight to obtain a urethane-based pressure-sensitive adhesive solution. Then, the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 μm, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 μm, and the drying temperature is 130 ° C. , Cure and dry under the condition of drying time of 3 minutes to prepare a pressure-sensitive adhesive layer composed of the pressure-sensitive adhesive composition (4). Next, the surface of the obtained pressure-sensitive adhesive layer was treated with a silicone-treated release sheet (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 μm, one of which was treated with silicone. The surfaces were bonded together to obtain a surface protective film (4). Aging was performed at room temperature for 5 days for evaluation. The release sheet was peeled off immediately before the evaluation. The results are shown in Table 1.
〔実施例５〕
　ウレタンプレポリマー５０重量部、ポリオールとして、ヒドロキシル基を３個有するポリオールであるプレミノールＳ３０１１（旭硝子社製、Ｍｎ＝１００００）３０重量部、ヒドロキシル基を３個有するポリオールであるサンニックスＧＰ３０００（三洋化成社製、Ｍｎ＝３０００）１８重量部、ヒドロキシル基を３個有するポリオールであるサンニックスＧＰ４００（三洋化成社製、Ｍｎ＝４００）２重量部、架橋剤としてイソシアネート化合物（コロネートＨＸ：Ｃ／ＨＸ、日本ポリウレタン社製）１３．８重量部、酸化防止剤として、Ｉｒｇａｎｏｘ１０１０（ＢＡＳＦ社製）０．５重量部、触媒として、ナーセム第２鉄（日本化学産業社製）０．０３重量部を、全体の固形分が５０重量％となるように酢酸エチルで希釈し、ウレタン系粘着剤溶液を得た。そして、ウレタン系粘着剤溶液を、ポリエステル樹脂からなる基材（商品名「Ｔ１００－７５Ｓ」、厚み７５μｍ、三菱ケミカル株式会社製）に乾燥後の厚みが７５μｍとなるよう塗布し、乾燥温度１３０℃、乾燥時間３分の条件でキュアーして乾燥し、粘着剤組成物（５）からなる粘着剤層を作製した。次いで、得られた粘着剤層の表面に、一方の面にシリコーン処理を施した厚さ２５μｍのポリエステル樹脂からなる剥離シート（商品名「ＭＲＦ２５」、厚み２５μｍ、三菱ケミカル株式会社製）のシリコーン処理面を貼合せて、表面保護フィルム（５）を得た。常温で５日間エージングを行い、評価を行った。剥離シートは評価の直前に剥離した。結果を表１に示した。 [Example 5]
50 parts by weight of urethane prepolymer, 30 parts by weight of Preminol S3011 (Mn = 10000, manufactured by Asahi Glass Co., Ltd.), which is a polyol having 3 hydroxyl groups, and Sanniks GP3000 (Sanyo Kasei Co., Ltd.), which is a polyol having 3 hydroxyl groups. Mn = 3000) 18 parts by weight, Sanniks GP400 (Sanyo Kasei Co., Ltd., Mn = 400) 2 parts by weight, which is a polyol having three hydroxyl groups, isocyanate compound (Coronate HX: C / HX, Japan) as a cross-linking agent 13.8 parts by weight of polyurethane (manufactured by Polyurethane), 0.5 parts by weight of Irganox1010 (manufactured by BASF) as an antioxidant, and 0.03 parts by weight of Nasem ferrous iron (manufactured by Nippon Kagaku Sangyo) as a catalyst. It was diluted with ethyl acetate so that the solid content was 50% by weight to obtain a urethane-based pressure-sensitive adhesive solution. Then, the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 μm, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 μm, and the drying temperature is 130 ° C. , Cure and dry under the condition of drying time of 3 minutes to prepare a pressure-sensitive adhesive layer composed of the pressure-sensitive adhesive composition (5). Next, the surface of the obtained pressure-sensitive adhesive layer was treated with a silicone-treated release sheet (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 μm, one of which was treated with silicone. The surfaces were bonded together to obtain a surface protective film (5). Aging was performed at room temperature for 5 days for evaluation. The release sheet was peeled off immediately before the evaluation. The results are shown in Table 1.
〔実施例６〕
　ウレタンプレポリマー５０重量部、ポリオールとして、ヒドロキシル基を３個有するポリオールであるプレミノールＳ３０１１（旭硝子社製、Ｍｎ＝１００００）３５重量部、ヒドロキシル基を３個有するポリオールであるサンニックスＧＰ３０００（三洋化成社製、Ｍｎ＝３０００）１５重量部、架橋剤としてイソシアネート化合物（コロネートＨＸ：Ｃ／ＨＸ、日本ポリウレタン社製）９．１重量部、酸化防止剤として、Ｉｒｇａｎｏｘ１０１０（ＢＡＳＦ社製）０．５重量部、触媒として、ナーセム第２鉄（日本化学産業社製）０．０３重量部を、全体の固形分が５０重量％となるように酢酸エチルで希釈し、ウレタン系粘着剤溶液を得た。そして、ウレタン系粘着剤溶液を、ポリエステル樹脂からなる基材（商品名「Ｔ１００－７５Ｓ」、厚み７５μｍ、三菱ケミカル株式会社製）に乾燥後の厚みが７５μｍとなるよう塗布し、乾燥温度１３０℃、乾燥時間３分の条件でキュアーして乾燥し、粘着剤組成物（６）からなる粘着剤層を作製した。次いで、得られた粘着剤層の表面に、一方の面にシリコーン処理を施した厚さ２５μｍのポリエステル樹脂からなる剥離シート（商品名「ＭＲＦ２５」、厚み２５μｍ、三菱ケミカル株式会社製）のシリコーン処理面を貼合せて、表面保護フィルム（６）を得た。常温で５日間エージングを行い、評価を行った。剥離シートは評価の直前に剥離した。結果を表１に示した。 [Example 6]
50 parts by weight of urethane prepolymer, 35 parts by weight of Preminol S3011 (Mn = 10000, manufactured by Asahi Glass Co., Ltd.), which is a polyol having 3 hydroxyl groups, and Sanniks GP3000 (Sanyo Kasei Co., Ltd.), which is a polyol having 3 hydroxyl groups. , Mn = 3000) 15 parts by weight, isocyanate compound (Coronate HX: C / HX, manufactured by Nippon Polyurethane Co., Ltd.) 9.1 parts by weight as a cross-linking agent, Irganox 1010 (manufactured by BASF) 0.5 parts by weight as an antioxidant. As a catalyst, 0.03 part by weight of Nasem ferrous iron (manufactured by Nippon Kagaku Sangyo Co., Ltd.) was diluted with ethyl acetate so that the total solid content was 50% by weight to obtain a urethane-based pressure-sensitive adhesive solution. Then, the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 μm, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 μm, and the drying temperature is 130 ° C. , Cure and dry under the condition of drying time of 3 minutes to prepare a pressure-sensitive adhesive layer composed of the pressure-sensitive adhesive composition (6). Next, the surface of the obtained pressure-sensitive adhesive layer was treated with a silicone-treated release sheet (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 μm, one of which was treated with silicone. The surfaces were bonded together to obtain a surface protective film (6). Aging was performed at room temperature for 5 days for evaluation. The release sheet was peeled off immediately before the evaluation. The results are shown in Table 1.
〔実施例７〕
　ウレタンプレポリマー６０重量部、ポリオールとして、ヒドロキシル基を３個有するポリオールであるプレミノールＳ３０１１（旭硝子社製、Ｍｎ＝１００００）２５重量部、ヒドロキシル基を３個有するポリオールであるサンニックスＧＰ３０００（三洋化成社製、Ｍｎ＝３０００）１５重量部、架橋剤としてイソシアネート化合物（コロネートＨＸ：Ｃ／ＨＸ、日本ポリウレタン社製）８．５重量部、酸化防止剤として、Ｉｒｇａｎｏｘ１０１０（ＢＡＳＦ社製）０．５重量部、触媒として、ナーセム第２鉄（日本化学産業社製）０．０３重量部を、全体の固形分が５０重量％となるように酢酸エチルで希釈し、ウレタン系粘着剤溶液を得た。そして、ウレタン系粘着剤溶液を、ポリエステル樹脂からなる基材（商品名「Ｔ１００－７５Ｓ」、厚み７５μｍ、三菱ケミカル株式会社製）に乾燥後の厚みが７５μｍとなるよう塗布し、乾燥温度１３０℃、乾燥時間３分の条件でキュアーして乾燥し、粘着剤組成物（７）からなる粘着剤層を作製した。次いで、得られた粘着剤層の表面に、一方の面にシリコーン処理を施した厚さ２５μｍのポリエステル樹脂からなる剥離シート（商品名「ＭＲＦ２５」、厚み２５μｍ、三菱ケミカル株式会社製）のシリコーン処理面を貼合せて、表面保護フィルム（７）を得た。常温で５日間エージングを行い、評価を行った。剥離シートは評価の直前に剥離した。結果を表１に示した。 [Example 7]
60 parts by weight of urethane prepolymer, 25 parts by weight of Preminol S3011 (Mn = 10000, manufactured by Asahi Glass Co., Ltd.), which is a polyol having 3 hydroxyl groups, and Sanniks GP3000 (Sanyo Kasei Co., Ltd.), which is a polyol having 3 hydroxyl groups. , Mn = 3000) 15 parts by weight, isocyanate compound (Coronate HX: C / HX, manufactured by Nippon Polyurethane Co., Ltd.) 8.5 parts by weight as a cross-linking agent, Irganox1010 (manufactured by BASF) 0.5 parts by weight as an antioxidant. As a catalyst, 0.03 part by weight of Nasem ferrous iron (manufactured by Nippon Kagaku Sangyo Co., Ltd.) was diluted with ethyl acetate so that the total solid content was 50% by weight to obtain a urethane-based pressure-sensitive adhesive solution. Then, the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 μm, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 μm, and the drying temperature is 130 ° C. , Cure and dry under the condition of drying time of 3 minutes to prepare a pressure-sensitive adhesive layer composed of the pressure-sensitive adhesive composition (7). Next, the surface of the obtained pressure-sensitive adhesive layer was treated with a silicone-treated release sheet (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 μm, one of which was treated with silicone. The surfaces were bonded together to obtain a surface protective film (7). Aging was performed at room temperature for 5 days for evaluation. The release sheet was peeled off immediately before the evaluation. The results are shown in Table 1.
〔実施例８〕
　ウレタンプレポリマー６０重量部、ポリオールとして、ヒドロキシル基を３個有するポリオールであるプレミノールＳ３０１１（旭硝子社製、Ｍｎ＝１００００）２８重量部、ヒドロキシル基を３個有するポリオールであるサンニックスＧＰ３０００（三洋化成社製、Ｍｎ＝３０００）１２重量部、架橋剤としてイソシアネート化合物（コロネートＨＸ：Ｃ／ＨＸ、日本ポリウレタン社製）７．８重量部、酸化防止剤として、Ｉｒｇａｎｏｘ１０１０（ＢＡＳＦ社製）０．５重量部、触媒として、ナーセム第２鉄（日本化学産業社製）０．０３重量部を、全体の固形分が５０重量％となるように酢酸エチルで希釈し、ウレタン系粘着剤溶液を得た。そして、ウレタン系粘着剤溶液を、ポリエステル樹脂からなる基材（商品名「Ｔ１００－７５Ｓ」、厚み７５μｍ、三菱ケミカル株式会社製）に乾燥後の厚みが７５μｍとなるよう塗布し、乾燥温度１３０℃、乾燥時間３分の条件でキュアーして乾燥し、粘着剤組成物（８）からなる粘着剤層を作製した。次いで、得られた粘着剤層の表面に、一方の面にシリコーン処理を施した厚さ２５μｍのポリエステル樹脂からなる剥離シート（商品名「ＭＲＦ２５」、厚み２５μｍ、三菱ケミカル株式会社製）のシリコーン処理面を貼合せて、表面保護フィルム（８）を得た。常温で５日間エージングを行い、評価を行った。剥離シートは評価の直前に剥離した。結果を表１に示した。 [Example 8]
60 parts by weight of urethane prepolymer, 28 parts by weight of Preminol S3011 (Mn = 10000, manufactured by Asahi Glass Co., Ltd.), which is a polyol having 3 hydroxyl groups, and Sanniks GP3000 (Sanyo Kasei Co., Ltd.), which is a polyol having 3 hydroxyl groups. , Mn = 3000) 12 parts by weight, isocyanate compound (Coronate HX: C / HX, manufactured by Nippon Polyurethane Co., Ltd.) 7.8 parts by weight as a cross-linking agent, Irganox1010 (manufactured by BASF) 0.5 parts by weight as an antioxidant. As a catalyst, 0.03 part by weight of Nasem ferrous iron (manufactured by Nippon Kagaku Sangyo Co., Ltd.) was diluted with ethyl acetate so that the total solid content was 50% by weight to obtain a urethane-based pressure-sensitive adhesive solution. Then, the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 μm, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 μm, and the drying temperature is 130 ° C. , Cure and dry under the condition of drying time of 3 minutes to prepare a pressure-sensitive adhesive layer composed of the pressure-sensitive adhesive composition (8). Next, the surface of the obtained pressure-sensitive adhesive layer was treated with a silicone-treated release sheet (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 μm, one of which was treated with silicone. The surfaces were bonded together to obtain a surface protective film (8). Aging was performed at room temperature for 5 days for evaluation. The release sheet was peeled off immediately before the evaluation. The results are shown in Table 1.
〔実施例９〕
　ウレタンプレポリマー８０重量部、ポリオールとして、ヒドロキシル基を３個有するポリオールであるプレミノールＳ３０１１（旭硝子社製、Ｍｎ＝１００００）１２重量部、ヒドロキシル基を３個有するポリオールであるサンニックスＧＰ３０００（三洋化成社製、Ｍｎ＝３０００）８重量部、架橋剤としてイソシアネート化合物（コロネートＨＸ：Ｃ／ＨＸ、日本ポリウレタン社製）５．８重量部、酸化防止剤として、Ｉｒｇａｎｏｘ１０１０（ＢＡＳＦ社製）０．５重量部、触媒として、ナーセム第２鉄（日本化学産業社製）０．０３重量部を、全体の固形分が５０重量％となるように酢酸エチルで希釈し、ウレタン系粘着剤溶液を得た。そして、ウレタン系粘着剤溶液を、ポリエステル樹脂からなる基材（商品名「Ｔ１００－７５Ｓ」、厚み７５μｍ、三菱ケミカル株式会社製）に乾燥後の厚みが７５μｍとなるよう塗布し、乾燥温度１３０℃、乾燥時間３分の条件でキュアーして乾燥し、粘着剤組成物（９）からなる粘着剤層を作製した。次いで、得られた粘着剤層の表面に、一方の面にシリコーン処理を施した厚さ２５μｍのポリエステル樹脂からなる剥離シート（商品名「ＭＲＦ２５」、厚み２５μｍ、三菱ケミカル株式会社製）のシリコーン処理面を貼合せて、表面保護フィルム（９）を得た。常温で５日間エージングを行い、評価を行った。剥離シートは評価の直前に剥離した。結果を表１に示した。 [Example 9]
80 parts by weight of urethane prepolymer, 12 parts by weight of Preminol S3011 (Mn = 10000, manufactured by Asahi Glass Co., Ltd.), which is a polyol having 3 hydroxyl groups, and Sanniks GP3000 (Sanyo Kasei Co., Ltd.), which is a polyol having 3 hydroxyl groups. Mn = 3000) 8 parts by weight, isocyanate compound (Coronate HX: C / HX, manufactured by Nippon Polyurethane Co., Ltd.) 5.8 parts by weight as a cross-linking agent, Irganox1010 (manufactured by BASF) 0.5 parts by weight as an antioxidant. As a catalyst, 0.03 part by weight of Nasem ferrous iron (manufactured by Nippon Kagaku Sangyo Co., Ltd.) was diluted with ethyl acetate so that the total solid content was 50% by weight to obtain a urethane-based pressure-sensitive adhesive solution. Then, the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 μm, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 μm, and the drying temperature is 130 ° C. , Cure and dry under the condition of drying time of 3 minutes to prepare a pressure-sensitive adhesive layer composed of the pressure-sensitive adhesive composition (9). Next, the surface of the obtained pressure-sensitive adhesive layer was treated with a silicone-treated release sheet (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 μm, one of which was treated with silicone. The surfaces were bonded together to obtain a surface protective film (9). Aging was performed at room temperature for 5 days for evaluation. The release sheet was peeled off immediately before the evaluation. The results are shown in Table 1.
〔実施例１０〕
　ウレタンプレポリマー８０重量部、ポリオールとして、ヒドロキシル基を３個有するポリオールであるプレミノールＳ３０１１（旭硝子社製、Ｍｎ＝１００００）１５重量部、ヒドロキシル基を３個有するポリオールであるサンニックスＧＰ３０００（三洋化成社製、Ｍｎ＝３０００）５重量部、架橋剤としてイソシアネート化合物（コロネートＨＸ：Ｃ／ＨＸ、日本ポリウレタン社製）５．２重量部、酸化防止剤として、Ｉｒｇａｎｏｘ１０１０（ＢＡＳＦ社製）０．５重量部、触媒として、ナーセム第２鉄（日本化学産業社製）０．０３重量部を、全体の固形分が５０重量％となるように酢酸エチルで希釈し、ウレタン系粘着剤溶液を得た。そして、ウレタン系粘着剤溶液を、ポリエステル樹脂からなる基材（商品名「Ｔ１００－７５Ｓ」、厚み７５μｍ、三菱ケミカル株式会社製）に乾燥後の厚みが７５μｍとなるよう塗布し、乾燥温度１３０℃、乾燥時間３分の条件でキュアーして乾燥し、粘着剤組成物（１０）からなる粘着剤層を作製した。次いで、得られた粘着剤層の表面に、一方の面にシリコーン処理を施した厚さ２５μｍのポリエステル樹脂からなる剥離シート（商品名「ＭＲＦ２５」、厚み２５μｍ、三菱ケミカル株式会社製）のシリコーン処理面を貼合せて、表面保護フィルム（１０）を得た。常温で５日間エージングを行い、評価を行った。剥離シートは評価の直前に剥離した。結果を表１に示した。 [Example 10]
80 parts by weight of urethane prepolymer, 15 parts by weight of Preminol S3011 (Mn = 10000, manufactured by Asahi Glass Co., Ltd.), which is a polyol having 3 hydroxyl groups, and Sanniks GP3000 (Sanyo Kasei Co., Ltd.), which is a polyol having 3 hydroxyl groups. , Mn = 3000) 5 parts by weight, isocyanate compound (Coronate HX: C / HX, manufactured by Nippon Polyurethane Co., Ltd.) 5.2 parts by weight as a cross-linking agent, Irganox1010 (manufactured by BASF) 0.5 parts by weight as an antioxidant. As a catalyst, 0.03 part by weight of Nasem ferrous iron (manufactured by Nippon Kagaku Sangyo Co., Ltd.) was diluted with ethyl acetate so that the total solid content was 50% by weight to obtain a urethane-based pressure-sensitive adhesive solution. Then, the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 μm, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 μm, and the drying temperature is 130 ° C. , Cure and dry under the condition of drying time of 3 minutes to prepare a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition (10). Next, the surface of the obtained pressure-sensitive adhesive layer was treated with a silicone-treated release sheet (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 μm, one of which was treated with silicone. The surfaces were bonded together to obtain a surface protective film (10). Aging was performed at room temperature for 5 days for evaluation. The release sheet was peeled off immediately before the evaluation. The results are shown in Table 1.
〔実施例１１〕
　ウレタンプレポリマー９５重量部、ポリオールとして、ヒドロキシル基を３個有するポリオールであるプレミノールＳ３０１１（旭硝子社製、Ｍｎ＝１００００）３重量部、ヒドロキシル基を３個有するポリオールであるサンニックスＧＰ３０００（三洋化成社製、Ｍｎ＝３０００）２重量部、架橋剤としてイソシアネート化合物（コロネートＨＸ：Ｃ／ＨＸ、日本ポリウレタン社製）３．６重量部、酸化防止剤として、Ｉｒｇａｎｏｘ１０１０（ＢＡＳＦ社製）０．５重量部、触媒として、ナーセム第２鉄（日本化学産業社製）０．０３重量部を、全体の固形分が５０重量％となるように酢酸エチルで希釈し、ウレタン系粘着剤溶液を得た。そして、ウレタン系粘着剤溶液を、ポリエステル樹脂からなる基材（商品名「Ｔ１００－７５Ｓ」、厚み７５μｍ、三菱ケミカル株式会社製）に乾燥後の厚みが７５μｍとなるよう塗布し、乾燥温度１３０℃、乾燥時間３分の条件でキュアーして乾燥し、粘着剤組成物（１１）からなる粘着剤層を作製した。次いで、得られた粘着剤層の表面に、一方の面にシリコーン処理を施した厚さ２５μｍのポリエステル樹脂からなる剥離シート（商品名「ＭＲＦ２５」、厚み２５μｍ、三菱ケミカル株式会社製）のシリコーン処理面を貼合せて、表面保護フィルム（１１）を得た。常温で５日間エージングを行い、評価を行った。剥離シートは評価の直前に剥離した。結果を表１に示した。 [Example 11]
95 parts by weight of urethane prepolymer, 3 parts by weight of Preminol S3011 (Mn = 10000, manufactured by Asahi Glass Co., Ltd.), which is a polyol having 3 hydroxyl groups, and Sanniks GP3000 (Sanyo Kasei Co., Ltd.), which is a polyol having 3 hydroxyl groups. , Mn = 3000) 2 parts by weight, isocyanate compound (Coronate HX: C / HX, manufactured by Nippon Polyurethane Co., Ltd.) 3.6 parts by weight as a cross-linking agent, Irganox1010 (manufactured by BASF) 0.5 parts by weight as an antioxidant. As a catalyst, 0.03 part by weight of Nasem ferrous iron (manufactured by Nippon Kagaku Sangyo Co., Ltd.) was diluted with ethyl acetate so that the total solid content was 50% by weight to obtain a urethane-based pressure-sensitive adhesive solution. Then, the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 μm, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 μm, and the drying temperature is 130 ° C. , Cure and dry under the condition of drying time of 3 minutes to prepare a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition (11). Next, the surface of the obtained pressure-sensitive adhesive layer was treated with a silicone-treated release sheet (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 μm, one of which was treated with silicone. The surfaces were bonded together to obtain a surface protective film (11). Aging was performed at room temperature for 5 days for evaluation. The release sheet was peeled off immediately before the evaluation. The results are shown in Table 1.
〔実施例１２〕
　ウレタンプレポリマー９５重量部、ポリオールとして、ヒドロキシル基を３個有するポリオールであるプレミノールＳ３０１１（旭硝子社製、Ｍｎ＝１００００）３．５重量部、ヒドロキシル基を３個有するポリオールであるサンニックスＧＰ３０００（三洋化成社製、Ｍｎ＝３０００）１．５重量部、架橋剤としてイソシアネート化合物（コロネートＨＸ：Ｃ／ＨＸ、日本ポリウレタン社製）３．５重量部、酸化防止剤として、Ｉｒｇａｎｏｘ１０１０（ＢＡＳＦ社製）０．５重量部、触媒として、ナーセム第２鉄（日本化学産業社製）０．０３重量部を、全体の固形分が５０重量％となるように酢酸エチルで希釈し、ウレタン系粘着剤溶液を得た。そして、ウレタン系粘着剤溶液を、ポリエステル樹脂からなる基材（商品名「Ｔ１００－７５Ｓ」、厚み７５μｍ、三菱ケミカル株式会社製）に乾燥後の厚みが７５μｍとなるよう塗布し、乾燥温度１３０℃、乾燥時間３分の条件でキュアーして乾燥し、粘着剤組成物（１２）からなる粘着剤層を作製した。次いで、得られた粘着剤層の表面に、一方の面にシリコーン処理を施した厚さ２５μｍのポリエステル樹脂からなる剥離シート（商品名「ＭＲＦ２５」、厚み２５μｍ、三菱ケミカル株式会社製）のシリコーン処理面を貼合せて、表面保護フィルム（１２）を得た。常温で５日間エージングを行い、評価を行った。剥離シートは評価の直前に剥離した。結果を表１に示した。 [Example 12]
95 parts by weight of urethane prepolymer, 3.5 parts by weight of Preminol S3011 (Mn = 10000, manufactured by Asahi Glass Co., Ltd.), which is a polyol having 3 hydroxyl groups, and Sanniks GP3000 (Sanyo), which is a polyol having 3 hydroxyl groups. Chemical company, Mn = 3000) 1.5 parts by weight, isocyanate compound (Coronate HX: C / HX, manufactured by Nippon Polyurethane Co., Ltd.) 3.5 parts by weight as a cross-linking agent, Irganox1010 (manufactured by BASF) 0 as an antioxidant. .5 parts by weight, 0.03 parts by weight of Nasem ferrous iron (manufactured by Nippon Kagaku Sangyo Co., Ltd.) as a catalyst is diluted with ethyl acetate so that the total solid content is 50% by weight, and a urethane-based pressure-sensitive adhesive solution is prepared. Obtained. Then, the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 μm, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 μm, and the drying temperature is 130 ° C. , Cure and dry under the condition of drying time of 3 minutes to prepare a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition (12). Next, the surface of the obtained pressure-sensitive adhesive layer was treated with a silicone-treated release sheet (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 μm, one of which was treated with silicone. The surfaces were bonded together to obtain a surface protective film (12). Aging was performed at room temperature for 5 days for evaluation. The release sheet was peeled off immediately before the evaluation. The results are shown in Table 1.
〔実施例１３〕
　ウレタンプレポリマー５０重量部、ポリオールとして、ヒドロキシル基を３個有するポリオールであるプレミノールＳ３０１５（旭硝子社製、Ｍｎ＝１５０００）３０重量部、ヒドロキシル基を３個有するポリオールであるサンニックスＧＰ３０００（三洋化成社製、Ｍｎ＝３０００）２０重量部、架橋剤としてイソシアネート化合物（コロネートＨＸ：Ｃ／ＨＸ、日本ポリウレタン社製）９．２重量部、酸化防止剤として、Ｉｒｇａｎｏｘ１０１０（ＢＡＳＦ社製）０．５重量部、触媒として、ナーセム第２鉄（日本化学産業社製）０．０３重量部を、全体の固形分が５０重量％となるように酢酸エチルで希釈し、ウレタン系粘着剤溶液を得た。そして、ウレタン系粘着剤溶液を、ポリエステル樹脂からなる基材（商品名「Ｔ１００－７５Ｓ」、厚み７５μｍ、三菱ケミカル株式会社製）に乾燥後の厚みが７５μｍとなるよう塗布し、乾燥温度１３０℃、乾燥時間３分の条件でキュアーして乾燥し、粘着剤組成物（１３）からなる粘着剤層を作製した。次いで、得られた粘着剤層の表面に、一方の面にシリコーン処理を施した厚さ２５μｍのポリエステル樹脂からなる剥離シート（商品名「ＭＲＦ２５」、厚み２５μｍ、三菱ケミカル株式会社製）のシリコーン処理面を貼合せて、表面保護フィルム（１３）を得た。常温で５日間エージングを行い、評価を行った。剥離シートは評価の直前に剥離した。結果を表１に示した。 [Example 13]
Preminol S3015 (Mn = 15000, manufactured by Asahi Glass Co., Ltd.), which is a polyol having 3 hydroxyl groups, and Sanniks GP3000 (Sanyo Kasei Co., Ltd.), which is a polyol having 3 hydroxyl groups and 50 parts by weight of urethane prepolymer. , Mn = 3000) 20 parts by weight, isocyanate compound (Coronate HX: C / HX, manufactured by Nippon Polyurethane Co., Ltd.) 9.2 parts by weight as a cross-linking agent, Irganox1010 (manufactured by BASF) 0.5 parts by weight as an antioxidant. As a catalyst, 0.03 part by weight of Nasem ferrous iron (manufactured by Nippon Kagaku Sangyo Co., Ltd.) was diluted with ethyl acetate so that the total solid content was 50% by weight to obtain a urethane-based pressure-sensitive adhesive solution. Then, the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 μm, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 μm, and the drying temperature is 130 ° C. , Cure and dry under the condition of drying time of 3 minutes to prepare a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition (13). Next, the surface of the obtained pressure-sensitive adhesive layer was treated with a silicone-treated release sheet (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 μm, one of which was treated with silicone. The surfaces were bonded together to obtain a surface protective film (13). Aging was performed at room temperature for 5 days for evaluation. The release sheet was peeled off immediately before the evaluation. The results are shown in Table 1.
〔実施例１４〕
　ウレタンプレポリマー５０重量部、ポリオールとして、ヒドロキシル基を３個有するポリオールであるプレミノールＳ３００８（旭硝子社製、Ｍｎ＝８０００）３０重量部、ヒドロキシル基を３個有するポリオールであるサンニックスＧＰ３０００（三洋化成社製、Ｍｎ＝３０００）２０重量部、架橋剤としてイソシアネート化合物（コロネートＨＸ：Ｃ／ＨＸ、日本ポリウレタン社製）１０．８重量部、酸化防止剤として、Ｉｒｇａｎｏｘ１０１０（ＢＡＳＦ社製）０．５重量部、触媒として、ナーセム第２鉄（日本化学産業社製）０．０３重量部を、全体の固形分が５０重量％となるように酢酸エチルで希釈し、ウレタン系粘着剤溶液を得た。そして、ウレタン系粘着剤溶液を、ポリエステル樹脂からなる基材（商品名「Ｔ１００－７５Ｓ」、厚み７５μｍ、三菱ケミカル株式会社製）に乾燥後の厚みが７５μｍとなるよう塗布し、乾燥温度１３０℃、乾燥時間３分の条件でキュアーして乾燥し、粘着剤組成物（１４）からなる粘着剤層を作製した。次いで、得られた粘着剤層の表面に、一方の面にシリコーン処理を施した厚さ２５μｍのポリエステル樹脂からなる剥離シート（商品名「ＭＲＦ２５」、厚み２５μｍ、三菱ケミカル株式会社製）のシリコーン処理面を貼合せて、表面保護フィルム（１４）を得た。常温で５日間エージングを行い、評価を行った。剥離シートは評価の直前に剥離した。結果を表１に示した。 [Example 14]
50 parts by weight of urethane prepolymer, 30 parts by weight of Preminol S3008 (Mn = 8000, manufactured by Asahi Glass Co., Ltd.), which is a polyol having three hydroxyl groups, and Sanniks GP3000 (Sanyo Kasei Co., Ltd.), which is a polyol having three hydroxyl groups. , Mn = 3000) 20 parts by weight, isocyanate compound (Coronate HX: C / HX, manufactured by Nippon Polyurethane Co., Ltd.) 10.8 parts by weight as a cross-linking agent, Irganox 1010 (manufactured by BASF) 0.5 parts by weight as an antioxidant. As a catalyst, 0.03 part by weight of Nasem ferrous iron (manufactured by Nippon Kagaku Sangyo Co., Ltd.) was diluted with ethyl acetate so that the total solid content was 50% by weight to obtain a urethane-based pressure-sensitive adhesive solution. Then, the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 μm, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 μm, and the drying temperature is 130 ° C. , Cure and dry under the condition of drying time of 3 minutes to prepare a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition (14). Next, the surface of the obtained pressure-sensitive adhesive layer was treated with a silicone-treated release sheet (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 μm, one of which was treated with silicone. The surfaces were bonded together to obtain a surface protective film (14). Aging was performed at room temperature for 5 days for evaluation. The release sheet was peeled off immediately before the evaluation. The results are shown in Table 1.
〔実施例１５〕
　ウレタンプレポリマー５０重量部、ポリオールとして、ヒドロキシル基を３個有するポリオールであるプレミノールＳ３００６（旭硝子社製、Ｍｎ＝５０００）３０重量部、ヒドロキシル基を３個有するポリオールであるサンニックスＧＰ３０００（三洋化成社製、Ｍｎ＝３０００）２０重量部、架橋剤としてイソシアネート化合物（コロネートＨＸ：Ｃ／ＨＸ、日本ポリウレタン社製）１２．７重量部、酸化防止剤として、Ｉｒｇａｎｏｘ１０１０（ＢＡＳＦ社製）０．５重量部、触媒として、ナーセム第２鉄（日本化学産業社製）０．０３重量部を、全体の固形分が５０重量％となるように酢酸エチルで希釈し、ウレタン系粘着剤溶液を得た。そして、ウレタン系粘着剤溶液を、ポリエステル樹脂からなる基材（商品名「Ｔ１００－７５Ｓ」、厚み７５μｍ、三菱ケミカル株式会社製）に乾燥後の厚みが７５μｍとなるよう塗布し、乾燥温度１３０℃、乾燥時間３分の条件でキュアーして乾燥し、粘着剤組成物（１５）からなる粘着剤層を作製した。次いで、得られた粘着剤層の表面に、一方の面にシリコーン処理を施した厚さ２５μｍのポリエステル樹脂からなる剥離シート（商品名「ＭＲＦ２５」、厚み２５μｍ、三菱ケミカル株式会社製）のシリコーン処理面を貼合せて、表面保護フィルム（１５）を得た。常温で５日間エージングを行い、評価を行った。剥離シートは評価の直前に剥離した。結果を表１に示した。 [Example 15]
50 parts by weight of urethane prepolymer, 30 parts by weight of Preminol S3006 (Mn = 5000, manufactured by Asahi Glass Co., Ltd.), which is a polyol having three hydroxyl groups, and Sanniks GP3000 (Sanyo Kasei Co., Ltd.), which is a polyol having three hydroxyl groups. , Mn = 3000) 20 parts by weight, isocyanate compound (Coronate HX: C / HX, manufactured by Nippon Polyurethane Co., Ltd.) 12.7 parts by weight as a cross-linking agent, Irganox1010 (manufactured by BASF) 0.5 parts by weight as an antioxidant. As a catalyst, 0.03 part by weight of Nasem ferrous iron (manufactured by Nippon Kagaku Sangyo Co., Ltd.) was diluted with ethyl acetate so that the total solid content was 50% by weight to obtain a urethane-based pressure-sensitive adhesive solution. Then, the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 μm, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 μm, and the drying temperature is 130 ° C. , Cure and dry under the condition of drying time of 3 minutes to prepare a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition (15). Next, the surface of the obtained pressure-sensitive adhesive layer was treated with a silicone-treated release sheet (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 μm, one of which was treated with silicone. The surfaces were bonded together to obtain a surface protective film (15). Aging was performed at room temperature for 5 days for evaluation. The release sheet was peeled off immediately before the evaluation. The results are shown in Table 1.
〔実施例１６〕
　ウレタンプレポリマー５０重量部、ポリオールとして、ヒドロキシル基を３個有するポリオールであるプレミノールＳ３０１１（旭硝子社製、Ｍｎ＝１００００）３０重量部、ヒドロキシル基を３個有するポリオールであるサンニックスＧＰ３０００（三洋化成社製、Ｍｎ＝３０００）２０重量部、架橋剤としてイソシアネート化合物（コロネートＨＸ：Ｃ／ＨＸ、日本ポリウレタン社製）１０．２重量部、イオン性化合物として１－エチル－３－メチルイミダゾリウムビス（トリフルオロメタンスルホニル）イミド（ＡＳ１１０、第一工業製薬社製）０．０５重量部、酸化防止剤として、Ｉｒｇａｎｏｘ１０１０（ＢＡＳＦ社製）０．５重量部、触媒として、ナーセム第２鉄（日本化学産業社製）０．０３重量部を、全体の固形分が５０重量％となるように酢酸エチルで希釈し、ウレタン系粘着剤溶液を得た。そして、ウレタン系粘着剤溶液を、ポリエステル樹脂からなる基材（商品名「Ｔ１００－７５Ｓ」、厚み７５μｍ、三菱ケミカル株式会社製）に乾燥後の厚みが７５μｍとなるよう塗布し、乾燥温度１３０℃、乾燥時間３分の条件でキュアーして乾燥し、粘着剤組成物（１６）からなる粘着剤層を作製した。次いで、得られた粘着剤層の表面に、一方の面にシリコーン処理を施した厚さ２５μｍのポリエステル樹脂からなる剥離シート（商品名「ＭＲＦ２５」、厚み２５μｍ、三菱ケミカル株式会社製）のシリコーン処理面を貼合せて、表面保護フィルム（１６）を得た。常温で５日間エージングを行い、評価を行った。剥離シートは評価の直前に剥離した。結果を表２に示した。 [Example 16]
50 parts by weight of urethane prepolymer, 30 parts by weight of Preminol S3011 (Mn = 10000, manufactured by Asahi Glass Co., Ltd.), which is a polyol having 3 hydroxyl groups, and Sanniks GP3000 (Sanyo Kasei Co., Ltd.), which is a polyol having 3 hydroxyl groups. , Mn = 3000) 20 parts by weight, isocyanate compound (Coronate HX: C / HX, manufactured by Nippon Polyurethane Co., Ltd.) 10.2 parts by weight as a cross-linking agent, 1-ethyl-3-methylimidazolium bis (trifluo) as an ionic compound. Lomethanesulfonyl) imide (AS110, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 0.05 parts by weight, isocyanate 1010 (manufactured by BASF) 0.5 parts by weight as an antioxidant, Nasem ferric iron (manufactured by Nippon Kagaku Sangyo Co., Ltd.) as a catalyst. ) 0.03 part by weight was diluted with ethyl acetate so that the total solid content was 50% by weight to obtain a urethane-based pressure-sensitive adhesive solution. Then, the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 μm, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 μm, and the drying temperature is 130 ° C. , Cure and dry under the condition of drying time of 3 minutes to prepare a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition (16). Next, the surface of the obtained pressure-sensitive adhesive layer was treated with a silicone-treated release sheet (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 μm, one of which was treated with silicone. The surfaces were bonded together to obtain a surface protective film (16). Aging was performed at room temperature for 5 days for evaluation. The release sheet was peeled off immediately before the evaluation. The results are shown in Table 2.
〔実施例１７〕
　ウレタンプレポリマー５０重量部、ポリオールとして、ヒドロキシル基を３個有するポリオールであるプレミノールＳ３０１１（旭硝子社製、Ｍｎ＝１００００）３０重量部、ヒドロキシル基を３個有するポリオールであるサンニックスＧＰ３０００（三洋化成社製、Ｍｎ＝３０００）２０重量部、架橋剤としてイソシアネート化合物（コロネートＨＸ：Ｃ／ＨＸ、日本ポリウレタン社製）１０．２重量部、イオン性化合物として１－エチル－３－メチルイミダゾリウムビス（トリフルオロメタンスルホニル）イミド（ＡＳ１１０、第一工業製薬社製）０．１重量部、酸化防止剤として、Ｉｒｇａｎｏｘ１０１０（ＢＡＳＦ社製）０．５重量部、触媒として、ナーセム第２鉄（日本化学産業社製）０．０３重量部を、全体の固形分が５０重量％となるように酢酸エチルで希釈し、ウレタン系粘着剤溶液を得た。そして、ウレタン系粘着剤溶液を、ポリエステル樹脂からなる基材（商品名「Ｔ１００－７５Ｓ」、厚み７５μｍ、三菱ケミカル株式会社製）に乾燥後の厚みが７５μｍとなるよう塗布し、乾燥温度１３０℃、乾燥時間３分の条件でキュアーして乾燥し、粘着剤組成物（１７）からなる粘着剤層を作製した。次いで、得られた粘着剤層の表面に、一方の面にシリコーン処理を施した厚さ２５μｍのポリエステル樹脂からなる剥離シート（商品名「ＭＲＦ２５」、厚み２５μｍ、三菱ケミカル株式会社製）のシリコーン処理面を貼合せて、表面保護フィルム（１７）を得た。常温で５日間エージングを行い、評価を行った。剥離シートは評価の直前に剥離した。結果を表２に示した。 [Example 17]
50 parts by weight of urethane prepolymer, 30 parts by weight of Preminol S3011 (Mn = 10000, manufactured by Asahi Glass Co., Ltd.), which is a polyol having 3 hydroxyl groups, and Sanniks GP3000 (Sanyo Kasei Co., Ltd.), which is a polyol having 3 hydroxyl groups. , Mn = 3000) 20 parts by weight, isocyanate compound (Coronate HX: C / HX, manufactured by Nippon Polyurethane Co., Ltd.) 10.2 parts by weight as a cross-linking agent, 1-ethyl-3-methylimidazolium bis (trifluo) as an ionic compound. Rometasulfonyl) imide (AS110, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 0.1 part by weight, isocyanate1010 (manufactured by BASF) 0.5 parts by weight as an antioxidant, Nasem ferric iron (manufactured by Nippon Kagaku Sangyo Co., Ltd.) as a catalyst. ) 0.03 part by weight was diluted with ethyl acetate so that the total solid content was 50% by weight to obtain a urethane-based pressure-sensitive adhesive solution. Then, the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 μm, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 μm, and the drying temperature is 130 ° C. , And dried under the condition of a drying time of 3 minutes to prepare a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition (17). Next, the surface of the obtained pressure-sensitive adhesive layer was treated with a silicone-treated release sheet (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 μm, one of which was treated with silicone. The surfaces were bonded together to obtain a surface protective film (17). Aging was performed at room temperature for 5 days for evaluation. The release sheet was peeled off immediately before the evaluation. The results are shown in Table 2.
〔実施例１８〕
　ウレタンプレポリマー５０重量部、ポリオールとして、ヒドロキシル基を３個有するポリオールであるプレミノールＳ３０１１（旭硝子社製、Ｍｎ＝１００００）３０重量部、ヒドロキシル基を３個有するポリオールであるサンニックスＧＰ３０００（三洋化成社製、Ｍｎ＝３０００）２０重量部、架橋剤としてイソシアネート化合物（コロネートＨＸ：Ｃ／ＨＸ、日本ポリウレタン社製）１０．２重量部、イオン性化合物として１－エチル－３－メチルイミダゾリウムビス（トリフルオロメタンスルホニル）イミド（ＡＳ１１０、第一工業製薬社製）０．５重量部、酸化防止剤として、Ｉｒｇａｎｏｘ１０１０（ＢＡＳＦ社製）０．５重量部、触媒として、ナーセム第２鉄（日本化学産業社製）０．０３重量部を、全体の固形分が５０重量％となるように酢酸エチルで希釈し、ウレタン系粘着剤溶液を得た。そして、ウレタン系粘着剤溶液を、ポリエステル樹脂からなる基材（商品名「Ｔ１００－７５Ｓ」、厚み７５μｍ、三菱ケミカル株式会社製）に乾燥後の厚みが７５μｍとなるよう塗布し、乾燥温度１３０℃、乾燥時間３分の条件でキュアーして乾燥し、粘着剤組成物（１８）からなる粘着剤層を作製した。次いで、得られた粘着剤層の表面に、一方の面にシリコーン処理を施した厚さ２５μｍのポリエステル樹脂からなる剥離シート（商品名「ＭＲＦ２５」、厚み２５μｍ、三菱ケミカル株式会社製）のシリコーン処理面を貼合せて、表面保護フィルム（１８）を得た。常温で５日間エージングを行い、評価を行った。剥離シートは評価の直前に剥離した。結果を表２に示した。 [Example 18]
50 parts by weight of urethane prepolymer, 30 parts by weight of Preminol S3011 (Mn = 10000, manufactured by Asahi Glass Co., Ltd.), which is a polyol having 3 hydroxyl groups, and Sanniks GP3000 (Sanyo Kasei Co., Ltd.), which is a polyol having 3 hydroxyl groups. , Mn = 3000) 20 parts by weight, isocyanate compound (Coronate HX: C / HX, manufactured by Nippon Polyurethane Co., Ltd.) 10.2 parts by weight as a cross-linking agent, 1-ethyl-3-methylimidazolium bis (trifluo) as an ionic compound. Lomethanesulfonyl) imide (AS110, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 0.5 parts by weight, as an antioxidant, Irganox1010 (manufactured by BASF) 0.5 parts by weight, as a catalyst, Nasem ferric iron (manufactured by Nippon Kagaku Sangyo Co., Ltd.) ) 0.03 part by weight was diluted with ethyl acetate so that the total solid content was 50% by weight to obtain a urethane-based pressure-sensitive adhesive solution. Then, the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 μm, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 μm, and the drying temperature is 130 ° C. , Cure and dry under the condition of drying time of 3 minutes to prepare a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition (18). Next, the surface of the obtained pressure-sensitive adhesive layer was treated with a silicone-treated release sheet (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 μm, one of which was treated with silicone. The surfaces were bonded together to obtain a surface protective film (18). Aging was performed at room temperature for 5 days for evaluation. The release sheet was peeled off immediately before the evaluation. The results are shown in Table 2.
〔実施例１９〕
　ウレタンプレポリマー５０重量部、ポリオールとして、ヒドロキシル基を３個有するポリオールであるプレミノールＳ３０１１（旭硝子社製、Ｍｎ＝１００００）３０重量部、ヒドロキシル基を３個有するポリオールであるサンニックスＧＰ３０００（三洋化成社製、Ｍｎ＝３０００）２０重量部、架橋剤としてイソシアネート化合物（コロネートＨＸ：Ｃ／ＨＸ、日本ポリウレタン社製）１０．２重量部、イオン性化合物として１－エチル－３－メチルイミダゾリウムビス（トリフルオロメタンスルホニル）イミド（ＡＳ１１０、第一工業製薬社製）１．０重量部、酸化防止剤として、Ｉｒｇａｎｏｘ１０１０（ＢＡＳＦ社製）０．５重量部、触媒として、ナーセム第２鉄（日本化学産業社製）０．０３重量部を、全体の固形分が５０重量％となるように酢酸エチルで希釈し、ウレタン系粘着剤溶液を得た。そして、ウレタン系粘着剤溶液を、ポリエステル樹脂からなる基材（商品名「Ｔ１００－７５Ｓ」、厚み７５μｍ、三菱ケミカル株式会社製）に乾燥後の厚みが７５μｍとなるよう塗布し、乾燥温度１３０℃、乾燥時間３分の条件でキュアーして乾燥し、粘着剤組成物（１９）からなる粘着剤層を作製した。次いで、得られた粘着剤層の表面に、一方の面にシリコーン処理を施した厚さ２５μｍのポリエステル樹脂からなる剥離シート（商品名「ＭＲＦ２５」、厚み２５μｍ、三菱ケミカル株式会社製）のシリコーン処理面を貼合せて、表面保護フィルム（１９）を得た。常温で５日間エージングを行い、評価を行った。剥離シートは評価の直前に剥離した。結果を表２に示した。 [Example 19]
50 parts by weight of urethane prepolymer, 30 parts by weight of Preminol S3011 (Mn = 10000, manufactured by Asahi Glass Co., Ltd.), which is a polyol having 3 hydroxyl groups, and Sanniks GP3000 (Sanyo Kasei Co., Ltd.), which is a polyol having 3 hydroxyl groups. , Mn = 3000) 20 parts by weight, isocyanate compound (Coronate HX: C / HX, manufactured by Nippon Polyurethane Co., Ltd.) 10.2 parts by weight as a cross-linking agent, 1-ethyl-3-methylimidazolium bis (trifluo) as an ionic compound. Lomethanesulfonyl) imide (AS110, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 1.0 part by weight, isocyanate 1010 (manufactured by BASF) 0.5 parts by weight as an antioxidant, Nasem ferric iron (manufactured by Nippon Kagaku Sangyo Co., Ltd.) as a catalyst. ) 0.03 part by weight was diluted with ethyl acetate so that the total solid content was 50% by weight to obtain a urethane-based pressure-sensitive adhesive solution. Then, the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 μm, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 μm, and the drying temperature is 130 ° C. , Cure and dry under the condition of drying time of 3 minutes to prepare a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition (19). Next, the surface of the obtained pressure-sensitive adhesive layer was treated with a silicone-treated release sheet (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 μm, one of which was treated with silicone. The surfaces were bonded together to obtain a surface protective film (19). Aging was performed at room temperature for 5 days for evaluation. The release sheet was peeled off immediately before the evaluation. The results are shown in Table 2.
〔実施例２０〕
　ウレタンプレポリマー５０重量部、ポリオールとして、ヒドロキシル基を３個有するポリオールであるプレミノールＳ３０１１（旭硝子社製、Ｍｎ＝１００００）３０重量部、ヒドロキシル基を３個有するポリオールであるサンニックスＧＰ３０００（三洋化成社製、Ｍｎ＝３０００）１５重量部、ヒドロキシル基を３個有するポリオールであるサンニックスＧＰ１０００（三洋化成社製、Ｍｎ＝１０００）５重量部、架橋剤としてイソシアネート化合物（コロネートＨＸ：Ｃ／ＨＸ、日本ポリウレタン社製）１２．９重量部、イオン性化合物として１－エチル－３－メチルイミダゾリウムビス（トリフルオロメタンスルホニル）イミド（ＡＳ１１０、第一工業製薬社製）０．５重量部、酸化防止剤として、Ｉｒｇａｎｏｘ１０１０（ＢＡＳＦ社製）０．５重量部、触媒として、ナーセム第２鉄（日本化学産業社製）０．０３重量部を、全体の固形分が５０重量％となるように酢酸エチルで希釈し、ウレタン系粘着剤溶液を得た。そして、ウレタン系粘着剤溶液を、ポリエステル樹脂からなる基材（商品名「Ｔ１００－７５Ｓ」、厚み７５μｍ、三菱ケミカル株式会社製）に乾燥後の厚みが７５μｍとなるよう塗布し、乾燥温度１３０℃、乾燥時間３分の条件でキュアーして乾燥し、粘着剤組成物（２０）からなる粘着剤層を作製した。次いで、得られた粘着剤層の表面に、一方の面にシリコーン処理を施した厚さ２５μｍのポリエステル樹脂からなる剥離シート（商品名「ＭＲＦ２５」、厚み２５μｍ、三菱ケミカル株式会社製）のシリコーン処理面を貼合せて、表面保護フィルム（２０）を得た。常温で５日間エージングを行い、評価を行った。剥離シートは評価の直前に剥離した。結果を表２に示した。 [Example 20]
50 parts by weight of urethane prepolymer, 30 parts by weight of Preminol S3011 (Mn = 10000, manufactured by Asahi Glass Co., Ltd.), which is a polyol having 3 hydroxyl groups, and Sanniks GP3000 (Sanyo Kasei Co., Ltd.), which is a polyol having 3 hydroxyl groups. Mn = 3000) 15 parts by weight, Sanniks GP1000 (Mn = 1000, manufactured by Sanyo Kasei Co., Ltd.), which is a polyol having three hydroxyl groups, 5 parts by weight, isocyanate compound (Coronate HX: C / HX, Japan) as a cross-linking agent 12.9 parts by weight of (Polymer), 0.5 part by weight of 1-ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide (AS110, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) as an ionic compound, as an antioxidant , Irganox 1010 (manufactured by BASF) 0.5 parts by weight, and 0.03 part by weight of Nasem ferric iron (manufactured by Nippon Kagaku Sangyo Co., Ltd.) as a catalyst diluted with ethyl acetate so that the total solid content is 50% by weight. Then, a urethane-based pressure-sensitive adhesive solution was obtained. Then, the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 μm, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 μm, and the drying temperature is 130 ° C. , Cure and dry under the condition of drying time of 3 minutes to prepare a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition (20). Next, the surface of the obtained pressure-sensitive adhesive layer was treated with a silicone-treated release sheet (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 μm, one of which was treated with silicone. The surfaces were bonded together to obtain a surface protective film (20). Aging was performed at room temperature for 5 days for evaluation. The release sheet was peeled off immediately before the evaluation. The results are shown in Table 2.
〔実施例２１〕
　ウレタンプレポリマー５０重量部、ポリオールとして、ヒドロキシル基を３個有するポリオールであるプレミノールＳ３０１１（旭硝子社製、Ｍｎ＝１００００）３０重量部、ヒドロキシル基を３個有するポリオールであるサンニックスＧＰ３０００（三洋化成社製、Ｍｎ＝３０００）１８重量部、ヒドロキシル基を３個有するポリオールであるサンニックスＧＰ６００（三洋化成社製、Ｍｎ＝６００）２重量部、架橋剤としてイソシアネート化合物（コロネートＨＸ：Ｃ／ＨＸ、日本ポリウレタン社製）１２．７重量部、イオン性化合物として１－エチル－３－メチルイミダゾリウムビス（トリフルオロメタンスルホニル）イミド（ＡＳ１１０、第一工業製薬社製）０．５重量部、酸化防止剤として、Ｉｒｇａｎｏｘ１０１０（ＢＡＳＦ社製）０．５重量部、触媒として、ナーセム第２鉄（日本化学産業社製）０．０３重量部を、全体の固形分が５０重量％となるように酢酸エチルで希釈し、ウレタン系粘着剤溶液を得た。そして、ウレタン系粘着剤溶液を、ポリエステル樹脂からなる基材（商品名「Ｔ１００－７５Ｓ」、厚み７５μｍ、三菱ケミカル株式会社製）に乾燥後の厚みが７５μｍとなるよう塗布し、乾燥温度１３０℃、乾燥時間３分の条件でキュアーして乾燥し、粘着剤組成物（２１）からなる粘着剤層を作製した。次いで、得られた粘着剤層の表面に、一方の面にシリコーン処理を施した厚さ２５μｍのポリエステル樹脂からなる剥離シート（商品名「ＭＲＦ２５」、厚み２５μｍ、三菱ケミカル株式会社製）のシリコーン処理面を貼合せて、表面保護フィルム（２１）を得た。常温で５日間エージングを行い、評価を行った。剥離シートは評価の直前に剥離した。結果を表２に示した。 [Example 21]
50 parts by weight of urethane prepolymer, 30 parts by weight of Preminol S3011 (Mn = 10000, manufactured by Asahi Glass Co., Ltd.), which is a polyol having 3 hydroxyl groups, and Sanniks GP3000 (Sanyo Kasei Co., Ltd.), which is a polyol having 3 hydroxyl groups. Mn = 3000) 18 parts by weight, Sanniks GP600 (Mn = 600, manufactured by Sanyo Kasei Co., Ltd.), which is a polyol having three hydroxyl groups, 2 parts by weight, isocyanate compound (Coronate HX: C / HX, Japan) as a cross-linking agent 12.7 parts by weight of (Polymer), 0.5 part by weight of 1-ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide (AS110, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) as an ionic compound, as an antioxidant , Irganox 1010 (manufactured by BASF) 0.5 parts by weight, and 0.03 part by weight of Nasem ferric iron (manufactured by Nippon Kagaku Sangyo Co., Ltd.) as a catalyst diluted with ethyl acetate so that the total solid content is 50% by weight. Then, a urethane-based pressure-sensitive adhesive solution was obtained. Then, the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 μm, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 μm, and the drying temperature is 130 ° C. , Cure and dry under the condition of drying time of 3 minutes to prepare a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition (21). Next, the surface of the obtained pressure-sensitive adhesive layer was treated with a silicone-treated release sheet (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 μm, one of which was treated with silicone. The surfaces were bonded together to obtain a surface protective film (21). Aging was performed at room temperature for 5 days for evaluation. The release sheet was peeled off immediately before the evaluation. The results are shown in Table 2.
〔実施例２２〕
　ウレタンプレポリマー５０重量部、ポリオールとして、ヒドロキシル基を３個有するポリオールであるプレミノールＳ３０１１（旭硝子社製、Ｍｎ＝１００００）３０重量部、ヒドロキシル基を３個有するポリオールであるサンニックスＧＰ３０００（三洋化成社製、Ｍｎ＝３０００）１８重量部、ヒドロキシル基を３個有するポリオールであるサンニックスＧＰ４００（三洋化成社製、Ｍｎ＝４００）２重量部、架橋剤としてイソシアネート化合物（コロネートＨＸ：Ｃ／ＨＸ、日本ポリウレタン社製）１３．８重量部、酸化防止剤として、イオン性化合物として１－エチル－３－メチルイミダゾリウムビス（トリフルオロメタンスルホニル）イミド（ＡＳ１１０、第一工業製薬社製）０．５重量部、Ｉｒｇａｎｏｘ１０１０（ＢＡＳＦ社製）０．５重量部、触媒として、ナーセム第２鉄（日本化学産業社製）０．０３重量部を、全体の固形分が５０重量％となるように酢酸エチルで希釈し、ウレタン系粘着剤溶液を得た。そして、ウレタン系粘着剤溶液を、ポリエステル樹脂からなる基材（商品名「Ｔ１００－７５Ｓ」、厚み７５μｍ、三菱ケミカル株式会社製）に乾燥後の厚みが７５μｍとなるよう塗布し、乾燥温度１３０℃、乾燥時間３分の条件でキュアーして乾燥し、粘着剤組成物（２２）からなる粘着剤層を作製した。次いで、得られた粘着剤層の表面に、一方の面にシリコーン処理を施した厚さ２５μｍのポリエステル樹脂からなる剥離シート（商品名「ＭＲＦ２５」、厚み２５μｍ、三菱ケミカル株式会社製）のシリコーン処理面を貼合せて、表面保護フィルム（２２）を得た。常温で５日間エージングを行い、評価を行った。剥離シートは評価の直前に剥離した。結果を表２に示した。 [Example 22]
50 parts by weight of urethane prepolymer, 30 parts by weight of Preminol S3011 (Mn = 10000, manufactured by Asahi Glass Co., Ltd.), which is a polyol having 3 hydroxyl groups, and Sanniks GP3000 (Sanyo Kasei Co., Ltd.), which is a polyol having 3 hydroxyl groups. Mn = 3000) 18 parts by weight, Sanniks GP400 (Sanyo Kasei Co., Ltd., Mn = 400) 2 parts by weight, which is a polyol having three hydroxyl groups, isocyanate compound (Coronate HX: C / HX, Japan) as a cross-linking agent 13.8 parts by weight of (Polymer), 0.5 part by weight of 1-ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide (AS110, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) as an antioxidant and an ionic compound. , Irganox 1010 (manufactured by BASF) 0.5 parts by weight, and 0.03 part by weight of Nasem ferric iron (manufactured by Nippon Kagaku Sangyo Co., Ltd.) as a catalyst diluted with ethyl acetate so that the total solid content is 50% by weight. Then, a urethane-based pressure-sensitive adhesive solution was obtained. Then, the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 μm, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 μm, and the drying temperature is 130 ° C. , Cure and dry under the condition of drying time of 3 minutes to prepare a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition (22). Next, the surface of the obtained pressure-sensitive adhesive layer was treated with a silicone-treated release sheet (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 μm, one of which was treated with silicone. The surfaces were bonded together to obtain a surface protective film (22). Aging was performed at room temperature for 5 days for evaluation. The release sheet was peeled off immediately before the evaluation. The results are shown in Table 2.
〔実施例２３〕
　ウレタンプレポリマー８０重量部、ポリオールとして、ヒドロキシル基を３個有するポリオールであるプレミノールＳ３０１１（旭硝子社製、Ｍｎ＝１００００）１５重量部、ヒドロキシル基を３個有するポリオールであるサンニックスＧＰ３０００（三洋化成社製、Ｍｎ＝３０００）５重量部、架橋剤としてイソシアネート化合物（コロネートＨＸ：Ｃ／ＨＸ、日本ポリウレタン社製）５．２重量部、イオン性化合物として１－エチル－３－メチルイミダゾリウムビス（トリフルオロメタンスルホニル）イミド（ＡＳ１１０、第一工業製薬社製）０．５重量部、酸化防止剤として、Ｉｒｇａｎｏｘ１０１０（ＢＡＳＦ社製）０．５重量部、触媒として、ナーセム第２鉄（日本化学産業社製）０．０３重量部を、全体の固形分が５０重量％となるように酢酸エチルで希釈し、ウレタン系粘着剤溶液を得た。そして、ウレタン系粘着剤溶液を、ポリエステル樹脂からなる基材（商品名「Ｔ１００－７５Ｓ」、厚み７５μｍ、三菱ケミカル株式会社製）に乾燥後の厚みが７５μｍとなるよう塗布し、乾燥温度１３０℃、乾燥時間３分の条件でキュアーして乾燥し、粘着剤組成物（２３）からなる粘着剤層を作製した。次いで、得られた粘着剤層の表面に、一方の面にシリコーン処理を施した厚さ２５μｍのポリエステル樹脂からなる剥離シート（商品名「ＭＲＦ２５」、厚み２５μｍ、三菱ケミカル株式会社製）のシリコーン処理面を貼合せて、表面保護フィルム（２３）を得た。常温で５日間エージングを行い、評価を行った。剥離シートは評価の直前に剥離した。結果を表２に示した。 [Example 23]
80 parts by weight of urethane prepolymer, 15 parts by weight of Preminol S3011 (Mn = 10000, manufactured by Asahi Glass Co., Ltd.), which is a polyol having 3 hydroxyl groups, and Sanniks GP3000 (Sanyo Kasei Co., Ltd.), which is a polyol having 3 hydroxyl groups. , Mn = 3000) 5 parts by weight, isocyanate compound (Coronate HX: C / HX, manufactured by Nippon Polyurethane Co., Ltd.) 5.2 parts by weight as a cross-linking agent, 1-ethyl-3-methylimidazolium bis (trifluo) as an ionic compound. Lomethanesulfonyl) imide (AS110, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 0.5 parts by weight, as an antioxidant, Irganox1010 (manufactured by BASF) 0.5 parts by weight, as a catalyst, Nasem ferric iron (manufactured by Nippon Kagaku Sangyo Co., Ltd.) ) 0.03 part by weight was diluted with ethyl acetate so that the total solid content was 50% by weight to obtain a urethane-based pressure-sensitive adhesive solution. Then, the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 μm, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 μm, and the drying temperature is 130 ° C. , Cure and dry under the condition of drying time of 3 minutes to prepare a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition (23). Next, the surface of the obtained pressure-sensitive adhesive layer was treated with a silicone-treated release sheet (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 μm, one of which was treated with silicone. The surfaces were bonded together to obtain a surface protective film (23). Aging was performed at room temperature for 5 days for evaluation. The release sheet was peeled off immediately before the evaluation. The results are shown in Table 2.
〔実施例２４〕
　ウレタンプレポリマー５０重量部、ポリオールとして、ヒドロキシル基を３個有するポリオールであるプレミノールＳ３０１１（旭硝子社製、Ｍｎ＝１００００）３０重量部、ヒドロキシル基を３個有するポリオールであるサンニックスＧＰ３０００（三洋化成社製、Ｍｎ＝３０００）２０重量部、架橋剤としてイソシアネート化合物（コロネートＨＸ：Ｃ／ＨＸ、日本ポリウレタン社製）１０．２重量部、イオン性化合物として１－エチル－３－メチルイミダゾリウムビス（トリフルオロメタンスルホニル）イミド（ＡＳ１１０、第一工業製薬社製）０．０５重量部、フッ素系オリゴマーのメガファックＦ－４７７（ＤＩＣ社製）０．１重量部、酸化防止剤として、Ｉｒｇａｎｏｘ１０１０（ＢＡＳＦ社製）０．５重量部、触媒として、ナーセム第２鉄（日本化学産業社製）０．０３重量部を、全体の固形分が５０重量％となるように酢酸エチルで希釈し、ウレタン系粘着剤溶液を得た。そして、ウレタン系粘着剤溶液を、ポリエステル樹脂からなる基材（商品名「Ｔ１００－７５Ｓ」、厚み７５μｍ、三菱ケミカル株式会社製）に乾燥後の厚みが７５μｍとなるよう塗布し、乾燥温度１３０℃、乾燥時間３分の条件でキュアーして乾燥し、粘着剤組成物（２４）からなる粘着剤層を作製した。次いで、得られた粘着剤層の表面に、一方の面にシリコーン処理を施した厚さ２５μｍのポリエステル樹脂からなる剥離シート（商品名「ＭＲＦ２５」、厚み２５μｍ、三菱ケミカル株式会社製）のシリコーン処理面を貼合せて、表面保護フィルム（２４）を得た。常温で５日間エージングを行い、評価を行った。剥離シートは評価の直前に剥離した。結果を表３に示した。 [Example 24]
Urethane prepolymer 50 parts by weight, as a polyol, Preminol S3011 (Mn = 10000, manufactured by Asahi Glass Co., Ltd.), which is a polyol having three hydroxyl groups, 30 parts by weight, Sanniks GP3000 (Sanyo Kasei Co., Ltd.), which is a polyol having three hydroxyl groups. , Mn = 3000) 20 parts by weight, isocyanate compound (Coronate HX: C / HX, manufactured by Nippon Polyurethane Co., Ltd.) 10.2 parts by weight as a cross-linking agent, 1-ethyl-3-methylimidazolium bis (trifluo) as an ionic compound. Lomethansulfonyl) imide (AS110, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 0.05 parts by weight, fluoropolymer Megafuck F-477 (manufactured by DIC) 0.1 parts by weight, Irganox 1010 (manufactured by BASF) as an antioxidant. ) 0.5 parts by weight, 0.03 parts by weight of Nasem ferrous iron (manufactured by Nippon Kagaku Sangyo Co., Ltd.) as a catalyst, diluted with ethyl acetate so that the total solid content is 50% by weight, urethane-based pressure-sensitive adhesive A solution was obtained. Then, the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 μm, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 μm, and the drying temperature is 130 ° C. , Cure and dry under the condition of drying time of 3 minutes to prepare a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition (24). Next, the surface of the obtained pressure-sensitive adhesive layer was treated with a silicone-treated release sheet (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 μm, one of which was treated with silicone. The surfaces were bonded together to obtain a surface protective film (24). Aging was performed at room temperature for 5 days for evaluation. The release sheet was peeled off immediately before the evaluation. The results are shown in Table 3.
〔実施例２５〕
　ウレタンプレポリマー５０重量部、ポリオールとして、ヒドロキシル基を３個有するポリオールであるプレミノールＳ３０１１（旭硝子社製、Ｍｎ＝１００００）３０重量部、ヒドロキシル基を３個有するポリオールであるサンニックスＧＰ３０００（三洋化成社製、Ｍｎ＝３０００）２０重量部、架橋剤としてイソシアネート化合物（コロネートＨＸ：Ｃ／ＨＸ、日本ポリウレタン社製）１０．２重量部、イオン性化合物として１－エチル－３－メチルイミダゾリウムビス（トリフルオロメタンスルホニル）イミド（ＡＳ１１０、第一工業製薬社製）０．１重量部、フッ素系オリゴマーのメガファックＦ－４７７（ＤＩＣ社製）０．１重量部、酸化防止剤として、Ｉｒｇａｎｏｘ１０１０（ＢＡＳＦ社製）０．５重量部、触媒として、ナーセム第２鉄（日本化学産業社製）０．０３重量部を、全体の固形分が５０重量％となるように酢酸エチルで希釈し、ウレタン系粘着剤溶液を得た。そして、ウレタン系粘着剤溶液を、ポリエステル樹脂からなる基材（商品名「Ｔ１００－７５Ｓ」、厚み７５μｍ、三菱ケミカル株式会社製）に乾燥後の厚みが７５μｍとなるよう塗布し、乾燥温度１３０℃、乾燥時間３分の条件でキュアーして乾燥し、粘着剤組成物（２５）からなる粘着剤層を作製した。次いで、得られた粘着剤層の表面に、一方の面にシリコーン処理を施した厚さ２５μｍのポリエステル樹脂からなる剥離シート（商品名「ＭＲＦ２５」、厚み２５μｍ、三菱ケミカル株式会社製）のシリコーン処理面を貼合せて、表面保護フィルム（２５）を得た。常温で５日間エージングを行い、評価を行った。剥離シートは評価の直前に剥離した。結果を表３に示した。 [Example 25]
50 parts by weight of urethane prepolymer, 30 parts by weight of Preminol S3011 (Mn = 10000, manufactured by Asahi Glass Co., Ltd.), which is a polyol having 3 hydroxyl groups, and Sanniks GP3000 (Sanyo Kasei Co., Ltd.), which is a polyol having 3 hydroxyl groups. , Mn = 3000) 20 parts by weight, isocyanate compound (Coronate HX: C / HX, manufactured by Nippon Polyurethane Co., Ltd.) 10.2 parts by weight as a cross-linking agent, 1-ethyl-3-methylimidazolium bis (trifluo) as an ionic compound. 0.1 part by weight of romethanesulfonyl) imide (AS110, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), 0.1 part by weight of megafuck F-477 (manufactured by DIC) of fluorine-based oligomer, Irganox1010 (manufactured by BASF) as an antioxidant. ) 0.5 parts by weight, 0.03 parts by weight of Nasem ferrous iron (manufactured by Nippon Kagaku Sangyo Co., Ltd.) as a catalyst is diluted with ethyl acetate so that the total solid content is 50% by weight, and a urethane-based pressure-sensitive adhesive is used. A solution was obtained. Then, the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 μm, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 μm, and the drying temperature is 130 ° C. , Cure and dry under the condition of drying time of 3 minutes to prepare a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition (25). Next, the surface of the obtained pressure-sensitive adhesive layer was treated with a silicone-treated release sheet (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 μm, one of which was treated with silicone. The surfaces were bonded together to obtain a surface protective film (25). Aging was performed at room temperature for 5 days for evaluation. The release sheet was peeled off immediately before the evaluation. The results are shown in Table 3.
〔実施例２６〕
　ウレタンプレポリマー５０重量部、ポリオールとして、ヒドロキシル基を３個有するポリオールであるプレミノールＳ３０１１（旭硝子社製、Ｍｎ＝１００００）３０重量部、ヒドロキシル基を３個有するポリオールであるサンニックスＧＰ３０００（三洋化成社製、Ｍｎ＝３０００）２０重量部、架橋剤としてイソシアネート化合物（コロネートＨＸ：Ｃ／ＨＸ、日本ポリウレタン社製）１０．２重量部、イオン性化合物として１－エチル－３－メチルイミダゾリウムビス（トリフルオロメタンスルホニル）イミド（ＡＳ１１０、第一工業製薬社製）０．５重量部、フッ素系オリゴマーのメガファックＦ－４７７（ＤＩＣ社製）０．１重量部、酸化防止剤として、Ｉｒｇａｎｏｘ１０１０（ＢＡＳＦ社製）０．５重量部、触媒として、ナーセム第２鉄（日本化学産業社製）０．０３重量部を、全体の固形分が５０重量％となるように酢酸エチルで希釈し、ウレタン系粘着剤溶液を得た。そして、ウレタン系粘着剤溶液を、ポリエステル樹脂からなる基材（商品名「Ｔ１００－７５Ｓ」、厚み７５μｍ、三菱ケミカル株式会社製）に乾燥後の厚みが７５μｍとなるよう塗布し、乾燥温度１３０℃、乾燥時間３分の条件でキュアーして乾燥し、粘着剤組成物（２６）からなる粘着剤層を作製した。次いで、得られた粘着剤層の表面に、一方の面にシリコーン処理を施した厚さ２５μｍのポリエステル樹脂からなる剥離シート（商品名「ＭＲＦ２５」、厚み２５μｍ、三菱ケミカル株式会社製）のシリコーン処理面を貼合せて、表面保護フィルム（２６）を得た。常温で５日間エージングを行い、評価を行った。剥離シートは評価の直前に剥離した。結果を表３に示した。 [Example 26]
50 parts by weight of urethane prepolymer, 30 parts by weight of Preminol S3011 (Mn = 10000, manufactured by Asahi Glass Co., Ltd.), which is a polyol having 3 hydroxyl groups, and Sanniks GP3000 (Sanyo Kasei Co., Ltd.), which is a polyol having 3 hydroxyl groups. , Mn = 3000) 20 parts by weight, isocyanate compound (Coronate HX: C / HX, manufactured by Nippon Polyurethane Co., Ltd.) 10.2 parts by weight as a cross-linking agent, 1-ethyl-3-methylimidazolium bis (trifluo) as an ionic compound. Romethanesulfonyl) imide (AS110, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 0.5 parts by weight, fluoropolymer Megafuck F-477 (manufactured by DIC) 0.1 parts by weight, Irganox 1010 (manufactured by BASF) as an antioxidant. ) 0.5 parts by weight, 0.03 parts by weight of Nasem ferrous iron (manufactured by Nippon Kagaku Sangyo Co., Ltd.) as a catalyst is diluted with ethyl acetate so that the total solid content is 50% by weight, and a urethane-based pressure-sensitive adhesive is used. A solution was obtained. Then, the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 μm, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 μm, and the drying temperature is 130 ° C. , Cure and dry under the condition of drying time of 3 minutes to prepare a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition (26). Next, the surface of the obtained pressure-sensitive adhesive layer was treated with a silicone-treated release sheet (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 μm, one of which was treated with silicone. The surfaces were bonded together to obtain a surface protective film (26). Aging was performed at room temperature for 5 days for evaluation. The release sheet was peeled off immediately before the evaluation. The results are shown in Table 3.
〔実施例２７〕
　ウレタンプレポリマー５０重量部、ポリオールとして、ヒドロキシル基を３個有するポリオールであるプレミノールＳ３０１１（旭硝子社製、Ｍｎ＝１００００）３０重量部、ヒドロキシル基を３個有するポリオールであるサンニックスＧＰ３０００（三洋化成社製、Ｍｎ＝３０００）２０重量部、架橋剤としてイソシアネート化合物（コロネートＨＸ：Ｃ／ＨＸ、日本ポリウレタン社製）１０．２重量部、イオン性化合物として１－エチル－３－メチルイミダゾリウムビス（トリフルオロメタンスルホニル）イミド（ＡＳ１１０、第一工業製薬社製）１．０重量部、フッ素系オリゴマーのメガファックＦ－４７７（ＤＩＣ社製）０．１重量部、酸化防止剤として、Ｉｒｇａｎｏｘ１０１０（ＢＡＳＦ社製）０．５重量部、触媒として、ナーセム第２鉄（日本化学産業社製）０．０３重量部を、全体の固形分が５０重量％となるように酢酸エチルで希釈し、ウレタン系粘着剤溶液を得た。そして、ウレタン系粘着剤溶液を、ポリエステル樹脂からなる基材（商品名「Ｔ１００－７５Ｓ」、厚み７５μｍ、三菱ケミカル株式会社製）に乾燥後の厚みが７５μｍとなるよう塗布し、乾燥温度１３０℃、乾燥時間３分の条件でキュアーして乾燥し、粘着剤組成物（２７）からなる粘着剤層を作製した。次いで、得られた粘着剤層の表面に、一方の面にシリコーン処理を施した厚さ２５μｍのポリエステル樹脂からなる剥離シート（商品名「ＭＲＦ２５」、厚み２５μｍ、三菱ケミカル株式会社製）のシリコーン処理面を貼合せて、表面保護フィルム（２７）を得た。常温で５日間エージングを行い、評価を行った。剥離シートは評価の直前に剥離した。結果を表３に示した。 [Example 27]
50 parts by weight of urethane prepolymer, 30 parts by weight of Preminol S3011 (Mn = 10000, manufactured by Asahi Glass Co., Ltd.), which is a polyol having 3 hydroxyl groups, and Sanniks GP3000 (Sanyo Kasei Co., Ltd.), which is a polyol having 3 hydroxyl groups. , Mn = 3000) 20 parts by weight, isocyanate compound (Coronate HX: C / HX, manufactured by Nippon Polyurethane Co., Ltd.) 10.2 parts by weight as a cross-linking agent, 1-ethyl-3-methylimidazolium bis (trifluo) as an ionic compound. Rometasulfonyl) imide (AS110, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 1.0 part by weight, fluorine-based oligomer Megafuck F-477 (manufactured by DIC) 0.1 part by weight, as an antioxidant, Irganox 1010 (manufactured by BASF) ) 0.5 parts by weight, 0.03 parts by weight of Nasem ferrous iron (manufactured by Nippon Kagaku Sangyo Co., Ltd.) as a catalyst is diluted with ethyl acetate so that the total solid content is 50% by weight, and a urethane-based pressure-sensitive adhesive is used. A solution was obtained. Then, the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 μm, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 μm, and the drying temperature is 130 ° C. , And dried under the condition of a drying time of 3 minutes to prepare a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition (27). Next, the surface of the obtained pressure-sensitive adhesive layer was treated with a silicone-treated release sheet (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 μm, one of which was treated with silicone. The surfaces were bonded together to obtain a surface protective film (27). Aging was performed at room temperature for 5 days for evaluation. The release sheet was peeled off immediately before the evaluation. The results are shown in Table 3.
〔実施例２８〕
　ウレタンプレポリマー５０重量部、ポリオールとして、ヒドロキシル基を３個有するポリオールであるプレミノールＳ３０１１（旭硝子社製、Ｍｎ＝１００００）３０重量部、ヒドロキシル基を３個有するポリオールであるサンニックスＧＰ３０００（三洋化成社製、Ｍｎ＝３０００）２０重量部、架橋剤としてイソシアネート化合物（コロネートＨＸ：Ｃ／ＨＸ、日本ポリウレタン社製）１０．２重量部、イオン性化合物として１－エチル－３－メチルイミダゾリウムビス（トリフルオロメタンスルホニル）イミド（ＡＳ１１０、第一工業製薬社製）０．５重量部、フッ素系オリゴマーのメガファックＦ－４７７（ＤＩＣ社製）０．０５重量部、酸化防止剤として、Ｉｒｇａｎｏｘ１０１０（ＢＡＳＦ社製）０．５重量部、触媒として、ナーセム第２鉄（日本化学産業社製）０．０３重量部を、全体の固形分が５０重量％となるように酢酸エチルで希釈し、ウレタン系粘着剤溶液を得た。そして、ウレタン系粘着剤溶液を、ポリエステル樹脂からなる基材（商品名「Ｔ１００－７５Ｓ」、厚み７５μｍ、三菱ケミカル株式会社製）に乾燥後の厚みが７５μｍとなるよう塗布し、乾燥温度１３０℃、乾燥時間３分の条件でキュアーして乾燥し、粘着剤組成物（２８）からなる粘着剤層を作製した。次いで、得られた粘着剤層の表面に、一方の面にシリコーン処理を施した厚さ２５μｍのポリエステル樹脂からなる剥離シート（商品名「ＭＲＦ２５」、厚み２５μｍ、三菱ケミカル株式会社製）のシリコーン処理面を貼合せて、表面保護フィルム（２８）を得た。常温で５日間エージングを行い、評価を行った。剥離シートは評価の直前に剥離した。結果を表３に示した。 [Example 28]
50 parts by weight of urethane prepolymer, 30 parts by weight of Preminol S3011 (Mn = 10000, manufactured by Asahi Glass Co., Ltd.), which is a polyol having three hydroxyl groups, and Sanniks GP3000 (Sanyo Kasei Co., Ltd.), which is a polyol having three hydroxyl groups. , Mn = 3000) 20 parts by weight, isocyanate compound (Coronate HX: C / HX, manufactured by Nippon Polyurethane Co., Ltd.) 10.2 parts by weight as a cross-linking agent, 1-ethyl-3-methylimidazolium bis (trifluo) as an ionic compound. Romethanesulfonyl) imide (AS110, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 0.5 parts by weight, fluoropolymer Megafuck F-477 (manufactured by DIC) 0.05 parts by weight, Irganox 1010 (manufactured by BASF) as an antioxidant. ) 0.5 parts by weight, 0.03 parts by weight of Nasem ferrous iron (manufactured by Nippon Kagaku Sangyo Co., Ltd.) as a catalyst is diluted with ethyl acetate so that the total solid content is 50% by weight, and a urethane-based pressure-sensitive adhesive is used. A solution was obtained. Then, the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 μm, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 μm, and the drying temperature is 130 ° C. , Cure and dry under the condition of drying time of 3 minutes to prepare a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition (28). Next, the surface of the obtained pressure-sensitive adhesive layer was treated with a silicone-treated release sheet (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 μm, one of which was treated with silicone. The surfaces were bonded together to obtain a surface protective film (28). Aging was performed at room temperature for 5 days for evaluation. The release sheet was peeled off immediately before the evaluation. The results are shown in Table 3.
〔実施例２９〕
　ウレタンプレポリマー５０重量部、ポリオールとして、ヒドロキシル基を３個有するポリオールであるプレミノールＳ３０１１（旭硝子社製、Ｍｎ＝１００００）３０重量部、ヒドロキシル基を３個有するポリオールであるサンニックスＧＰ３０００（三洋化成社製、Ｍｎ＝３０００）２０重量部、架橋剤としてイソシアネート化合物（コロネートＨＸ：Ｃ／ＨＸ、日本ポリウレタン社製）１０．２重量部、イオン性化合物として１－エチル－３－メチルイミダゾリウムビス（トリフルオロメタンスルホニル）イミド（ＡＳ１１０、第一工業製薬社製）０．５重量部、フッ素系オリゴマーのメガファックＦ－４７７（ＤＩＣ社製）０．５重量部、酸化防止剤として、Ｉｒｇａｎｏｘ１０１０（ＢＡＳＦ社製）０．５重量部、触媒として、ナーセム第２鉄（日本化学産業社製）０．０３重量部を、全体の固形分が５０重量％となるように酢酸エチルで希釈し、ウレタン系粘着剤溶液を得た。そして、ウレタン系粘着剤溶液を、ポリエステル樹脂からなる基材（商品名「Ｔ１００－７５Ｓ」、厚み７５μｍ、三菱ケミカル株式会社製）に乾燥後の厚みが７５μｍとなるよう塗布し、乾燥温度１３０℃、乾燥時間３分の条件でキュアーして乾燥し、粘着剤組成物（２９）からなる粘着剤層を作製した。次いで、得られた粘着剤層の表面に、一方の面にシリコーン処理を施した厚さ２５μｍのポリエステル樹脂からなる剥離シート（商品名「ＭＲＦ２５」、厚み２５μｍ、三菱ケミカル株式会社製）のシリコーン処理面を貼合せて、表面保護フィルム（２９）を得た。常温で５日間エージングを行い、評価を行った。剥離シートは評価の直前に剥離した。結果を表３に示した。 [Example 29]
50 parts by weight of urethane prepolymer, 30 parts by weight of Preminol S3011 (Mn = 10000, manufactured by Asahi Glass Co., Ltd.), which is a polyol having 3 hydroxyl groups, and Sanniks GP3000 (Sanyo Kasei Co., Ltd.), which is a polyol having 3 hydroxyl groups. , Mn = 3000) 20 parts by weight, isocyanate compound (Coronate HX: C / HX, manufactured by Nippon Polyurethane Co., Ltd.) 10.2 parts by weight as a cross-linking agent, 1-ethyl-3-methylimidazolium bis (trifluo) as an ionic compound. Romethanesulfonyl) imide (AS110, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 0.5 parts by weight, fluorinated oligomer Megafuck F-477 (manufactured by DIC) 0.5 parts by weight, as an antioxidant, Irganox 1010 (manufactured by BASF) ) 0.5 parts by weight, 0.03 parts by weight of Nasem ferrous iron (manufactured by Nippon Kagaku Sangyo Co., Ltd.) as a catalyst is diluted with ethyl acetate so that the total solid content is 50% by weight, and a urethane-based pressure-sensitive adhesive is used. A solution was obtained. Then, the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 μm, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 μm, and the drying temperature is 130 ° C. , Cure and dry under the condition of drying time of 3 minutes to prepare a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition (29). Next, the surface of the obtained pressure-sensitive adhesive layer was treated with a silicone-treated release sheet (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 μm, one of which was treated with silicone. The surfaces were bonded together to obtain a surface protective film (29). Aging was performed at room temperature for 5 days for evaluation. The release sheet was peeled off immediately before the evaluation. The results are shown in Table 3.
〔実施例３０〕
　ウレタンプレポリマー５０重量部、ポリオールとして、ヒドロキシル基を３個有するポリオールであるプレミノールＳ３０１１（旭硝子社製、Ｍｎ＝１００００）３０重量部、ヒドロキシル基を３個有するポリオールであるサンニックスＧＰ３０００（三洋化成社製、Ｍｎ＝３０００）２０重量部、架橋剤としてイソシアネート化合物（コロネートＨＸ：Ｃ／ＨＸ、日本ポリウレタン社製）１０．２重量部、イオン性化合物として１－エチル－３－メチルイミダゾリウムビス（トリフルオロメタンスルホニル）イミド（ＡＳ１１０、第一工業製薬社製）０．５重量部、フッ素系オリゴマーのメガファックＦ－４７７（ＤＩＣ社製）１．０重量部、酸化防止剤として、Ｉｒｇａｎｏｘ１０１０（ＢＡＳＦ社製）０．５重量部、触媒として、ナーセム第２鉄（日本化学産業社製）０．０３重量部を、全体の固形分が５０重量％となるように酢酸エチルで希釈し、ウレタン系粘着剤溶液を得た。そして、ウレタン系粘着剤溶液を、ポリエステル樹脂からなる基材（商品名「Ｔ１００－７５Ｓ」、厚み７５μｍ、三菱ケミカル株式会社製）に乾燥後の厚みが７５μｍとなるよう塗布し、乾燥温度１３０℃、乾燥時間３分の条件でキュアーして乾燥し、粘着剤組成物（３０）からなる粘着剤層を作製した。次いで、得られた粘着剤層の表面に、一方の面にシリコーン処理を施した厚さ２５μｍのポリエステル樹脂からなる剥離シート（商品名「ＭＲＦ２５」、厚み２５μｍ、三菱ケミカル株式会社製）のシリコーン処理面を貼合せて、表面保護フィルム（３０）を得た。常温で５日間エージングを行い、評価を行った。剥離シートは評価の直前に剥離した。結果を表３に示した。 [Example 30]
50 parts by weight of urethane prepolymer, 30 parts by weight of Preminol S3011 (Mn = 10000, manufactured by Asahi Glass Co., Ltd.), which is a polyol having 3 hydroxyl groups, and Sanniks GP3000 (Sanyo Kasei Co., Ltd.), which is a polyol having 3 hydroxyl groups. , Mn = 3000) 20 parts by weight, isocyanate compound (Coronate HX: C / HX, manufactured by Nippon Polyurethane Co., Ltd.) 10.2 parts by weight as a cross-linking agent, 1-ethyl-3-methylimidazolium bis (trifluo) as an ionic compound. Rometasulfonyl) imide (AS110, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 0.5 part by weight, fluoropolymer Megafuck F-477 (manufactured by DIC) 1.0 part by weight, Irganox1010 (manufactured by BASF) as an antioxidant. ) 0.5 parts by weight, 0.03 parts by weight of Nasem ferrous iron (manufactured by Nippon Kagaku Sangyo Co., Ltd.) as a catalyst is diluted with ethyl acetate so that the total solid content is 50% by weight, and a urethane-based pressure-sensitive adhesive is used. A solution was obtained. Then, the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 μm, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 μm, and the drying temperature is 130 ° C. , Cure and dry under the condition of drying time of 3 minutes to prepare a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition (30). Next, the surface of the obtained pressure-sensitive adhesive layer was treated with a silicone-treated release sheet (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 μm, one of which was treated with silicone. The surfaces were bonded together to obtain a surface protective film (30). Aging was performed at room temperature for 5 days for evaluation. The release sheet was peeled off immediately before the evaluation. The results are shown in Table 3.
〔実施例３１〕
　ウレタンプレポリマー５０重量部、ポリオールとして、ヒドロキシル基を３個有するポリオールであるプレミノールＳ３０１１（旭硝子社製、Ｍｎ＝１００００）３５重量部、ヒドロキシル基を３個有するポリオールであるサンニックスＧＰ３０００（三洋化成社製、Ｍｎ＝３０００）１５重量部、架橋剤としてイソシアネート化合物（コロネートＨＸ：Ｃ／ＨＸ、日本ポリウレタン社製）９．１重量部、イオン性化合物として１－エチル－３－メチルイミダゾリウムビス（トリフルオロメタンスルホニル）イミド（ＡＳ１１０、第一工業製薬社製）０．５重量部、フッ素系オリゴマーのメガファックＦ－４７７（ＤＩＣ社製）０．１重量部、酸化防止剤として、Ｉｒｇａｎｏｘ１０１０（ＢＡＳＦ社製）０．５重量部、触媒として、ナーセム第２鉄（日本化学産業社製）０．０３重量部を、全体の固形分が５０重量％となるように酢酸エチルで希釈し、ウレタン系粘着剤溶液を得た。そして、ウレタン系粘着剤溶液を、ポリエステル樹脂からなる基材（商品名「Ｔ１００－７５Ｓ」、厚み７５μｍ、三菱ケミカル株式会社製）に乾燥後の厚みが７５μｍとなるよう塗布し、乾燥温度１３０℃、乾燥時間３分の条件でキュアーして乾燥し、粘着剤組成物（３１）からなる粘着剤層を作製した。次いで、得られた粘着剤層の表面に、一方の面にシリコーン処理を施した厚さ２５μｍのポリエステル樹脂からなる剥離シート（商品名「ＭＲＦ２５」、厚み２５μｍ、三菱ケミカル株式会社製）のシリコーン処理面を貼合せて、表面保護フィルム（３１）を得た。常温で５日間エージングを行い、評価を行った。剥離シートは評価の直前に剥離した。結果を表３に示した。 [Example 31]
50 parts by weight of urethane prepolymer, 35 parts by weight of Preminol S3011 (Mn = 10000, manufactured by Asahi Glass Co., Ltd.), which is a polyol having 3 hydroxyl groups, and Sanniks GP3000 (Sanyo Kasei Co., Ltd.), which is a polyol having 3 hydroxyl groups. , Mn = 3000) 15 parts by weight, isocyanate compound (Coronate HX: C / HX, manufactured by Nippon Polyurethane Co., Ltd.) 9.1 parts by weight as a cross-linking agent, 1-ethyl-3-methylimidazolium bis (trifluo) as an ionic compound. 0.5 parts by weight of romethanesulfonyl) imide (AS110, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), 0.1 parts by weight of fluorinated oligomer Megafuck F-477 (manufactured by DIC), Irganox1010 (manufactured by BASF) as an antioxidant. ) 0.5 parts by weight, 0.03 parts by weight of Nasem ferrous iron (manufactured by Nippon Kagaku Sangyo Co., Ltd.) as a catalyst, diluted with ethyl acetate so that the total solid content is 50% by weight, urethane-based pressure-sensitive adhesive A solution was obtained. Then, the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 μm, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 μm, and the drying temperature is 130 ° C. , Cure and dry under the condition of drying time of 3 minutes to prepare a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition (31). Next, the surface of the obtained pressure-sensitive adhesive layer was treated with a silicone-treated release sheet (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 μm, one of which was treated with silicone. The surfaces were bonded together to obtain a surface protective film (31). Aging was performed at room temperature for 5 days for evaluation. The release sheet was peeled off immediately before the evaluation. The results are shown in Table 3.
〔実施例３２〕
　ウレタンプレポリマー５０重量部、ポリオールとして、ヒドロキシル基を３個有するポリオールであるプレミノールＳ３０１１（旭硝子社製、Ｍｎ＝１００００）３０重量部、ヒドロキシル基を３個有するポリオールであるサンニックスＧＰ３０００（三洋化成社製、Ｍｎ＝３０００）２０重量部、架橋剤としてイソシアネート化合物（コロネートＨＸ：Ｃ／ＨＸ、日本ポリウレタン社製）１０．２重量部、イオン性化合物として１－エチル－３－メチルイミダゾリウムビス（トリフルオロメタンスルホニル）イミド（ＡＳ１１０、第一工業製薬社製）０．５重量部、フッ素系オリゴマーのメガファックＦ－５６３（ＤＩＣ社製）０．０５重量部、酸化防止剤として、Ｉｒｇａｎｏｘ１０１０（ＢＡＳＦ社製）０．５重量部、触媒として、ナーセム第２鉄（日本化学産業社製）０．０３重量部を、全体の固形分が５０重量％となるように酢酸エチルで希釈し、ウレタン系粘着剤溶液を得た。そして、ウレタン系粘着剤溶液を、ポリエステル樹脂からなる基材（商品名「Ｔ１００－７５Ｓ」、厚み７５μｍ、三菱ケミカル株式会社製）に乾燥後の厚みが７５μｍとなるよう塗布し、乾燥温度１３０℃、乾燥時間３分の条件でキュアーして乾燥し、粘着剤組成物（３２）からなる粘着剤層を作製した。次いで、得られた粘着剤層の表面に、一方の面にシリコーン処理を施した厚さ２５μｍのポリエステル樹脂からなる剥離シート（商品名「ＭＲＦ２５」、厚み２５μｍ、三菱ケミカル株式会社製）のシリコーン処理面を貼合せて、表面保護フィルム（３２）を得た。常温で５日間エージングを行い、評価を行った。剥離シートは評価の直前に剥離した。結果を表３に示した。 [Example 32]
50 parts by weight of urethane prepolymer, 30 parts by weight of Preminol S3011 (Mn = 10000, manufactured by Asahi Glass Co., Ltd.), which is a polyol having 3 hydroxyl groups, and Sanniks GP3000 (Sanyo Kasei Co., Ltd.), which is a polyol having 3 hydroxyl groups. , Mn = 3000) 20 parts by weight, isocyanate compound (Coronate HX: C / HX, manufactured by Nippon Polyurethane Co., Ltd.) 10.2 parts by weight as a cross-linking agent, 1-ethyl-3-methylimidazolium bis (trifluo) as an ionic compound. Rometasulfonyl) imide (AS110, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 0.5 parts by weight, fluoropolymer Megafuck F-563 (manufactured by DIC) 0.05 parts by weight, Irganox 1010 (manufactured by BASF) as an antioxidant. ) 0.5 parts by weight, 0.03 parts by weight of Nasem ferrous iron (manufactured by Nippon Kagaku Sangyo Co., Ltd.) as a catalyst is diluted with ethyl acetate so that the total solid content is 50% by weight, and a urethane-based pressure-sensitive adhesive is used. A solution was obtained. Then, the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 μm, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 μm, and the drying temperature is 130 ° C. , Cure and dry under the condition of drying time of 3 minutes to prepare a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition (32). Next, the surface of the obtained pressure-sensitive adhesive layer was treated with a silicone-treated release sheet (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 μm, one of which was treated with silicone. The surfaces were bonded together to obtain a surface protective film (32). Aging was performed at room temperature for 5 days for evaluation. The release sheet was peeled off immediately before the evaluation. The results are shown in Table 3.
〔実施例３３〕
　ウレタンプレポリマー５０重量部、ポリオールとして、ヒドロキシル基を３個有するポリオールであるプレミノールＳ３０１１（旭硝子社製、Ｍｎ＝１００００）３０重量部、ヒドロキシル基を３個有するポリオールであるサンニックスＧＰ３０００（三洋化成社製、Ｍｎ＝３０００）２０重量部、架橋剤としてイソシアネート化合物（コロネートＨＸ：Ｃ／ＨＸ、日本ポリウレタン社製）１０．２重量部、イオン性化合物として１－エチル－３－メチルイミダゾリウムビス（トリフルオロメタンスルホニル）イミド（ＡＳ１１０、第一工業製薬社製）０．５重量部、フッ素系オリゴマーのメガファックＦ－５６３（ＤＩＣ社製）０．１重量部、酸化防止剤として、Ｉｒｇａｎｏｘ１０１０（ＢＡＳＦ社製）０．５重量部、触媒として、ナーセム第２鉄（日本化学産業社製）０．０３重量部を、全体の固形分が５０重量％となるように酢酸エチルで希釈し、ウレタン系粘着剤溶液を得た。そして、ウレタン系粘着剤溶液を、ポリエステル樹脂からなる基材（商品名「Ｔ１００－７５Ｓ」、厚み７５μｍ、三菱ケミカル株式会社製）に乾燥後の厚みが７５μｍとなるよう塗布し、乾燥温度１３０℃、乾燥時間３分の条件でキュアーして乾燥し、粘着剤組成物（３３）からなる粘着剤層を作製した。次いで、得られた粘着剤層の表面に、一方の面にシリコーン処理を施した厚さ２５μｍのポリエステル樹脂からなる剥離シート（商品名「ＭＲＦ２５」、厚み２５μｍ、三菱ケミカル株式会社製）のシリコーン処理面を貼合せて、表面保護フィルム（３３）を得た。常温で５日間エージングを行い、評価を行った。剥離シートは評価の直前に剥離した。結果を表３に示した。 [Example 33]
50 parts by weight of urethane prepolymer, 30 parts by weight of Preminol S3011 (Mn = 10000, manufactured by Asahi Glass Co., Ltd.), which is a polyol having three hydroxyl groups, and Sanniks GP3000 (Sanyo Kasei Co., Ltd.), which is a polyol having three hydroxyl groups. , Mn = 3000) 20 parts by weight, isocyanate compound (Coronate HX: C / HX, manufactured by Nippon Polyurethane Co., Ltd.) 10.2 parts by weight as a cross-linking agent, 1-ethyl-3-methylimidazolium bis (trifluo) as an ionic compound. Rometasulfonyl) imide (AS110, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 0.5 parts by weight, fluoropolymer Megafuck F-563 (manufactured by DIC) 0.1 parts by weight, Irganox1010 (manufactured by BASF) as an antioxidant. ) 0.5 parts by weight, 0.03 parts by weight of Nasem ferrous iron (manufactured by Nippon Kagaku Sangyo Co., Ltd.) as a catalyst is diluted with ethyl acetate so that the total solid content is 50% by weight, and a urethane-based pressure-sensitive adhesive is used. A solution was obtained. Then, the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 μm, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 μm, and the drying temperature is 130 ° C. , And dried under the condition of a drying time of 3 minutes to prepare a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition (33). Next, the surface of the obtained pressure-sensitive adhesive layer was treated with a silicone-treated release sheet (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 μm, one of which was treated with silicone. The surfaces were bonded together to obtain a surface protective film (33). Aging was performed at room temperature for 5 days for evaluation. The release sheet was peeled off immediately before the evaluation. The results are shown in Table 3.
〔実施例３４〕
　ウレタンプレポリマー５０重量部、ポリオールとして、ヒドロキシル基を３個有するポリオールであるプレミノールＳ３０１１（旭硝子社製、Ｍｎ＝１００００）３０重量部、ヒドロキシル基を３個有するポリオールであるサンニックスＧＰ３０００（三洋化成社製、Ｍｎ＝３０００）２０重量部、架橋剤としてイソシアネート化合物（コロネートＨＸ：Ｃ／ＨＸ、日本ポリウレタン社製）１０．２重量部、イオン性化合物として１－エチル－３－メチルイミダゾリウムビス（トリフルオロメタンスルホニル）イミド（ＡＳ１１０、第一工業製薬社製）０．５重量部、フッ素系オリゴマーのメガファックＦ－５６３（ＤＩＣ社製）０．５重量部、酸化防止剤として、Ｉｒｇａｎｏｘ１０１０（ＢＡＳＦ社製）０．５重量部、触媒として、ナーセム第２鉄（日本化学産業社製）０．０３重量部を、全体の固形分が５０重量％となるように酢酸エチルで希釈し、ウレタン系粘着剤溶液を得た。そして、ウレタン系粘着剤溶液を、ポリエステル樹脂からなる基材（商品名「Ｔ１００－７５Ｓ」、厚み７５μｍ、三菱ケミカル株式会社製）に乾燥後の厚みが７５μｍとなるよう塗布し、乾燥温度１３０℃、乾燥時間３分の条件でキュアーして乾燥し、粘着剤組成物（３４）からなる粘着剤層を作製した。次いで、得られた粘着剤層の表面に、一方の面にシリコーン処理を施した厚さ２５μｍのポリエステル樹脂からなる剥離シート（商品名「ＭＲＦ２５」、厚み２５μｍ、三菱ケミカル株式会社製）のシリコーン処理面を貼合せて、表面保護フィルム（３４）を得た。常温で５日間エージングを行い、評価を行った。剥離シートは評価の直前に剥離した。結果を表３に示した。 [Example 34]
50 parts by weight of urethane prepolymer, 30 parts by weight of Preminol S3011 (Mn = 10000, manufactured by Asahi Glass Co., Ltd.), which is a polyol having three hydroxyl groups, and Sanniks GP3000 (Sanyo Kasei Co., Ltd.), which is a polyol having three hydroxyl groups. , Mn = 3000) 20 parts by weight, isocyanate compound (Coronate HX: C / HX, manufactured by Nippon Polyurethane Co., Ltd.) 10.2 parts by weight as a cross-linking agent, 1-ethyl-3-methylimidazolium bis (trifluo) as an ionic compound. Rometasulfonyl) imide (AS110, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 0.5 parts by weight, fluoropolymer Megafuck F-563 (manufactured by DIC) 0.5 parts by weight, Irganox1010 (manufactured by BASF) as an antioxidant. ) 0.5 parts by weight, 0.03 parts by weight of Nasem ferrous iron (manufactured by Nippon Kagaku Sangyo Co., Ltd.) as a catalyst is diluted with ethyl acetate so that the total solid content is 50% by weight, and a urethane-based pressure-sensitive adhesive is used. A solution was obtained. Then, the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 μm, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 μm, and the drying temperature is 130 ° C. , Cure and dry under the condition of drying time of 3 minutes to prepare a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition (34). Next, the surface of the obtained pressure-sensitive adhesive layer was treated with a silicone-treated release sheet (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 μm, one of which was treated with silicone. The surfaces were bonded together to obtain a surface protective film (34). Aging was performed at room temperature for 5 days for evaluation. The release sheet was peeled off immediately before the evaluation. The results are shown in Table 3.
〔実施例３５〕
　ウレタンプレポリマー５０重量部、ポリオールとして、ヒドロキシル基を３個有するポリオールであるプレミノールＳ３０１１（旭硝子社製、Ｍｎ＝１００００）３０重量部、ヒドロキシル基を３個有するポリオールであるサンニックスＧＰ３０００（三洋化成社製、Ｍｎ＝３０００）２０重量部、架橋剤としてイソシアネート化合物（コロネートＨＸ：Ｃ／ＨＸ、日本ポリウレタン社製）１０．２重量部、イオン性化合物として１－エチル－３－メチルイミダゾリウムビス（トリフルオロメタンスルホニル）イミド（ＡＳ１１０、第一工業製薬社製）０．５重量部、フッ素系オリゴマーのメガファックＦ－５６３（ＤＩＣ社製）１．０重量部、酸化防止剤として、Ｉｒｇａｎｏｘ１０１０（ＢＡＳＦ社製）０．５重量部、触媒として、ナーセム第２鉄（日本化学産業社製）０．０３重量部を、全体の固形分が５０重量％となるように酢酸エチルで希釈し、ウレタン系粘着剤溶液を得た。そして、ウレタン系粘着剤溶液を、ポリエステル樹脂からなる基材（商品名「Ｔ１００－７５Ｓ」、厚み７５μｍ、三菱ケミカル株式会社製）に乾燥後の厚みが７５μｍとなるよう塗布し、乾燥温度１３０℃、乾燥時間３分の条件でキュアーして乾燥し、粘着剤組成物（３５）からなる粘着剤層を作製した。次いで、得られた粘着剤層の表面に、一方の面にシリコーン処理を施した厚さ２５μｍのポリエステル樹脂からなる剥離シート（商品名「ＭＲＦ２５」、厚み２５μｍ、三菱ケミカル株式会社製）のシリコーン処理面を貼合せて、表面保護フィルム（３５）を得た。常温で５日間エージングを行い、評価を行った。剥離シートは評価の直前に剥離した。結果を表３に示した。 [Example 35]
Urethane prepolymer 50 parts by weight, as a polyol, Preminol S3011 (Mn = 10000, manufactured by Asahi Glass Co., Ltd.), which is a polyol having three hydroxyl groups, 30 parts by weight, Sanniks GP3000 (Sanyo Kasei Co., Ltd.), which is a polyol having three hydroxyl groups. , Mn = 3000) 20 parts by weight, isocyanate compound (Coronate HX: C / HX, manufactured by Nippon Polyurethane Co., Ltd.) 10.2 parts by weight as a cross-linking agent, 1-ethyl-3-methylimidazolium bis (trifluo) as an ionic compound. 0.5 parts by weight of romethanesulfonyl) imide (AS110, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), 1.0 part by weight of fluorinated oligomer Megafuck F-563 (manufactured by DIC), Irganox1010 (manufactured by BASF) as an antioxidant. ) 0.5 parts by weight, 0.03 parts by weight of Nasem ferrous iron (manufactured by Nippon Kagaku Sangyo Co., Ltd.) as a catalyst, diluted with ethyl acetate so that the total solid content is 50% by weight, urethane-based pressure-sensitive adhesive A solution was obtained. Then, the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 μm, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 μm, and the drying temperature is 130 ° C. , Cure and dry under the condition of drying time of 3 minutes to prepare a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition (35). Next, the surface of the obtained pressure-sensitive adhesive layer was treated with a silicone-treated release sheet (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 μm, one of which was treated with silicone. The surfaces were bonded together to obtain a surface protective film (35). Aging was performed at room temperature for 5 days for evaluation. The release sheet was peeled off immediately before the evaluation. The results are shown in Table 3.
〔実施例３６〕
　ウレタンプレポリマー５０重量部、ポリオールとして、ヒドロキシル基を３個有するポリオールであるプレミノールＳ３０１１（旭硝子社製、Ｍｎ＝１００００）３０重量部、ヒドロキシル基を３個有するポリオールであるサンニックスＧＰ３０００（三洋化成社製、Ｍｎ＝３０００）２０重量部、架橋剤としてイソシアネート化合物（コロネートＨＸ：Ｃ／ＨＸ、日本ポリウレタン社製）１０．２重量部、イオン性化合物として１－エチル－３－メチルイミダゾリウムビス（トリフルオロメタンスルホニル）イミド（ＡＳ１１０、第一工業製薬社製）０．５重量部、フッ素系オリゴマーのメガファックＦ－５６９（ＤＩＣ社製）０．５重量部、酸化防止剤として、Ｉｒｇａｎｏｘ１０１０（ＢＡＳＦ社製）０．５重量部、触媒として、ナーセム第２鉄（日本化学産業社製）０．０３重量部を、全体の固形分が５０重量％となるように酢酸エチルで希釈し、ウレタン系粘着剤溶液を得た。そして、ウレタン系粘着剤溶液を、ポリエステル樹脂からなる基材（商品名「Ｔ１００－７５Ｓ」、厚み７５μｍ、三菱ケミカル株式会社製）に乾燥後の厚みが７５μｍとなるよう塗布し、乾燥温度１３０℃、乾燥時間３分の条件でキュアーして乾燥し、粘着剤組成物（３６）からなる粘着剤層を作製した。次いで、得られた粘着剤層の表面に、一方の面にシリコーン処理を施した厚さ２５μｍのポリエステル樹脂からなる剥離シート（商品名「ＭＲＦ２５」、厚み２５μｍ、三菱ケミカル株式会社製）のシリコーン処理面を貼合せて、表面保護フィルム（３６）を得た。常温で５日間エージングを行い、評価を行った。剥離シートは評価の直前に剥離した。結果を表３に示した。 [Example 36]
50 parts by weight of urethane prepolymer, 30 parts by weight of Preminol S3011 (Mn = 10000, manufactured by Asahi Glass Co., Ltd.), which is a polyol having three hydroxyl groups, and Sanniks GP3000 (Sanyo Kasei Co., Ltd.), which is a polyol having three hydroxyl groups. , Mn = 3000) 20 parts by weight, isocyanate compound (Coronate HX: C / HX, manufactured by Nippon Polyurethane Co., Ltd.) 10.2 parts by weight as a cross-linking agent, 1-ethyl-3-methylimidazolium bis (trifluo) as an ionic compound. Rometasulfonyl) imide (AS110, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 0.5 parts by weight, fluoropolymer Megafuck F-569 (manufactured by DIC) 0.5 parts by weight, Irganox 1010 (manufactured by BASF) as an antioxidant. ) 0.5 parts by weight, 0.03 parts by weight of Nasem ferrous iron (manufactured by Nippon Kagaku Sangyo Co., Ltd.) as a catalyst is diluted with ethyl acetate so that the total solid content is 50% by weight, and a urethane-based pressure-sensitive adhesive is used. A solution was obtained. Then, the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 μm, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 μm, and the drying temperature is 130 ° C. , Cure and dry under the condition of drying time of 3 minutes to prepare a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition (36). Next, the surface of the obtained pressure-sensitive adhesive layer was treated with a silicone-treated release sheet (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 μm, one of which was treated with silicone. The surfaces were bonded together to obtain a surface protective film (36). Aging was performed at room temperature for 5 days for evaluation. The release sheet was peeled off immediately before the evaluation. The results are shown in Table 3.
〔実施例３７〕
　ウレタンプレポリマー５０重量部、ポリオールとして、ヒドロキシル基を３個有するポリオールであるプレミノールＳ３０１１（旭硝子社製、Ｍｎ＝１００００）３０重量部、ヒドロキシル基を３個有するポリオールであるサンニックスＧＰ３０００（三洋化成社製、Ｍｎ＝３０００）２０重量部、架橋剤としてイソシアネート化合物（コロネートＨＸ：Ｃ／ＨＸ、日本ポリウレタン社製）１０．２重量部、イオン性化合物として１－エチル－３－メチルイミダゾリウムビス（トリフルオロメタンスルホニル）イミド（ＡＳ１１０、第一工業製薬社製）０．５重量部、フッ素系オリゴマーのメガファックＦ－５５２（ＤＩＣ社製）０．５重量部、酸化防止剤として、Ｉｒｇａｎｏｘ１０１０（ＢＡＳＦ社製）０．５重量部、触媒として、ナーセム第２鉄（日本化学産業社製）０．０３重量部を、全体の固形分が５０重量％となるように酢酸エチルで希釈し、ウレタン系粘着剤溶液を得た。そして、ウレタン系粘着剤溶液を、ポリエステル樹脂からなる基材（商品名「Ｔ１００－７５Ｓ」、厚み７５μｍ、三菱ケミカル株式会社製）に乾燥後の厚みが７５μｍとなるよう塗布し、乾燥温度１３０℃、乾燥時間３分の条件でキュアーして乾燥し、粘着剤組成物（３７）からなる粘着剤層を作製した。次いで、得られた粘着剤層の表面に、一方の面にシリコーン処理を施した厚さ２５μｍのポリエステル樹脂からなる剥離シート（商品名「ＭＲＦ２５」、厚み２５μｍ、三菱ケミカル株式会社製）のシリコーン処理面を貼合せて、表面保護フィルム（３７）を得た。常温で５日間エージングを行い、評価を行った。剥離シートは評価の直前に剥離した。結果を表３に示した。 [Example 37]
Urethane prepolymer 50 parts by weight, as a polyol, Preminol S3011 (Mn = 10000, manufactured by Asahi Glass Co., Ltd.), which is a polyol having three hydroxyl groups, 30 parts by weight, Sanniks GP3000 (Sanyo Kasei Co., Ltd.), which is a polyol having three hydroxyl groups. , Mn = 3000) 20 parts by weight, isocyanate compound (Coronate HX: C / HX, manufactured by Nippon Polyurethane Co., Ltd.) 10.2 parts by weight as a cross-linking agent, 1-ethyl-3-methylimidazolium bis (trifluo) as an ionic compound. Rometasulfonyl) imide (AS110, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 0.5 parts by weight, fluoropolymer Megafuck F-552 (manufactured by DIC) 0.5 parts by weight, Irganox1010 (manufactured by BASF) as an antioxidant. ) 0.5 parts by weight, 0.03 parts by weight of Nasem ferrous iron (manufactured by Nippon Kagaku Sangyo Co., Ltd.) as a catalyst, diluted with ethyl acetate so that the total solid content is 50% by weight, urethane-based pressure-sensitive adhesive A solution was obtained. Then, the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 μm, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 μm, and the drying temperature is 130 ° C. , Cure and dry under the condition of drying time of 3 minutes to prepare a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition (37). Next, the surface of the obtained pressure-sensitive adhesive layer was treated with a silicone-treated release sheet (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 μm, one of which was treated with silicone. The surfaces were bonded together to obtain a surface protective film (37). Aging was performed at room temperature for 5 days for evaluation. The release sheet was peeled off immediately before the evaluation. The results are shown in Table 3.
〔実施例３８〕
　ウレタンプレポリマー５０重量部、ポリオールとして、ヒドロキシル基を３個有するポリオールであるプレミノールＳ３０１１（旭硝子社製、Ｍｎ＝１００００）３０重量部、ヒドロキシル基を３個有するポリオールであるサンニックスＧＰ３０００（三洋化成社製、Ｍｎ＝３０００）２０重量部、架橋剤としてイソシアネート化合物（コロネートＨＸ：Ｃ／ＨＸ、日本ポリウレタン社製）１０．２重量部、イオン性化合物として１－エチル－３－メチルイミダゾリウムビス（トリフルオロメタンスルホニル）イミド（ＡＳ１１０、第一工業製薬社製）０．５重量部、フッ素系オリゴマーのメガファックＦ－５５９（ＤＩＣ社製）０．５重量部、酸化防止剤として、Ｉｒｇａｎｏｘ１０１０（ＢＡＳＦ社製）０．５重量部、触媒として、ナーセム第２鉄（日本化学産業社製）０．０３重量部を、全体の固形分が５０重量％となるように酢酸エチルで希釈し、ウレタン系粘着剤溶液を得た。そして、ウレタン系粘着剤溶液を、ポリエステル樹脂からなる基材（商品名「Ｔ１００－７５Ｓ」、厚み７５μｍ、三菱ケミカル株式会社製）に乾燥後の厚みが７５μｍとなるよう塗布し、乾燥温度１３０℃、乾燥時間３分の条件でキュアーして乾燥し、粘着剤組成物（３８）からなる粘着剤層を作製した。次いで、得られた粘着剤層の表面に、一方の面にシリコーン処理を施した厚さ２５μｍのポリエステル樹脂からなる剥離シート（商品名「ＭＲＦ２５」、厚み２５μｍ、三菱ケミカル株式会社製）のシリコーン処理面を貼合せて、表面保護フィルム（３８）を得た。常温で５日間エージングを行い、評価を行った。剥離シートは評価の直前に剥離した。結果を表３に示した。 [Example 38]
Urethane prepolymer 50 parts by weight, as a polyol, Preminol S3011 (Mn = 10000, manufactured by Asahi Glass Co., Ltd.), which is a polyol having three hydroxyl groups, 30 parts by weight, Sanniks GP3000 (Sanyo Kasei Co., Ltd.), which is a polyol having three hydroxyl groups. , Mn = 3000) 20 parts by weight, isocyanate compound (Coronate HX: C / HX, manufactured by Nippon Polyurethane Co., Ltd.) 10.2 parts by weight as a cross-linking agent, 1-ethyl-3-methylimidazolium bis (trifluo) as an ionic compound. Rometasulfonyl) imide (AS110, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 0.5 parts by weight, fluoropolymer Megafuck F-559 (manufactured by DIC) 0.5 parts by weight, Irganox1010 (manufactured by BASF) as an antioxidant. ) 0.5 parts by weight, 0.03 parts by weight of Nasem ferrous iron (manufactured by Nippon Kagaku Sangyo Co., Ltd.) as a catalyst, diluted with ethyl acetate so that the total solid content is 50% by weight, urethane-based pressure-sensitive adhesive A solution was obtained. Then, the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 μm, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 μm, and the drying temperature is 130 ° C. , Cure and dry under the condition of drying time of 3 minutes to prepare a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition (38). Next, the surface of the obtained pressure-sensitive adhesive layer was treated with a silicone-treated release sheet (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 μm, one of which was treated with silicone. The surfaces were bonded together to obtain a surface protective film (38). Aging was performed at room temperature for 5 days for evaluation. The release sheet was peeled off immediately before the evaluation. The results are shown in Table 3.
〔実施例３９〕
　ウレタンプレポリマー５０重量部、ポリオールとして、ヒドロキシル基を３個有するポリオールであるプレミノールＳ３０１１（旭硝子社製、Ｍｎ＝１００００）３０重量部、ヒドロキシル基を３個有するポリオールであるサンニックスＧＰ３０００（三洋化成社製、Ｍｎ＝３０００）２０重量部、架橋剤としてイソシアネート化合物（コロネートＨＸ：Ｃ／ＨＸ、日本ポリウレタン社製）１０．２重量部、イオン性化合物として１－エチル－３－メチルイミダゾリウムビス（トリフルオロメタンスルホニル）イミド（ＡＳ１１０、第一工業製薬社製）０．５重量部、フッ素系オリゴマーのメガファックＦ－５５６（ＤＩＣ社製）０．５重量部、酸化防止剤として、Ｉｒｇａｎｏｘ１０１０（ＢＡＳＦ社製）０．５重量部、触媒として、ナーセム第２鉄（日本化学産業社製）０．０３重量部を、全体の固形分が５０重量％となるように酢酸エチルで希釈し、ウレタン系粘着剤溶液を得た。そして、ウレタン系粘着剤溶液を、ポリエステル樹脂からなる基材（商品名「Ｔ１００－７５Ｓ」、厚み７５μｍ、三菱ケミカル株式会社製）に乾燥後の厚みが７５μｍとなるよう塗布し、乾燥温度１３０℃、乾燥時間３分の条件でキュアーして乾燥し、粘着剤組成物（３９）からなる粘着剤層を作製した。次いで、得られた粘着剤層の表面に、一方の面にシリコーン処理を施した厚さ２５μｍのポリエステル樹脂からなる剥離シート（商品名「ＭＲＦ２５」、厚み２５μｍ、三菱ケミカル株式会社製）のシリコーン処理面を貼合せて、表面保護フィルム（３９）を得た。常温で５日間エージングを行い、評価を行った。剥離シートは評価の直前に剥離した。結果を表３に示した。 [Example 39]
50 parts by weight of urethane prepolymer, 30 parts by weight of Preminol S3011 (Mn = 10000, manufactured by Asahi Glass Co., Ltd.), which is a polyol having three hydroxyl groups, and Sanniks GP3000 (Sanyo Kasei Co., Ltd.), which is a polyol having three hydroxyl groups. , Mn = 3000) 20 parts by weight, isocyanate compound (Coronate HX: C / HX, manufactured by Nippon Polyurethane Co., Ltd.) 10.2 parts by weight as a cross-linking agent, 1-ethyl-3-methylimidazolium bis (trifluo) as an ionic compound. Rometasulfonyl) imide (AS110, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 0.5 parts by weight, fluoropolymer Megafuck F-556 (manufactured by DIC) 0.5 parts by weight, Irganox 1010 (manufactured by BASF) as an antioxidant. ) 0.5 parts by weight, 0.03 parts by weight of Nasem ferrous iron (manufactured by Nippon Kagaku Sangyo Co., Ltd.) as a catalyst is diluted with ethyl acetate so that the total solid content is 50% by weight, and a urethane-based pressure-sensitive adhesive is used. A solution was obtained. Then, the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 μm, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 μm, and the drying temperature is 130 ° C. , And dried under the condition of a drying time of 3 minutes to prepare a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition (39). Next, the surface of the obtained pressure-sensitive adhesive layer was treated with a silicone-treated release sheet (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 μm, one of which was treated with silicone. The surfaces were bonded together to obtain a surface protective film (39). Aging was performed at room temperature for 5 days for evaluation. The release sheet was peeled off immediately before the evaluation. The results are shown in Table 3.
〔実施例４０〕
　ウレタンプレポリマー５０重量部、ポリオールとして、ヒドロキシル基を３個有するポリオールであるプレミノールＳ３０１１（旭硝子社製、Ｍｎ＝１００００）３０重量部、ヒドロキシル基を３個有するポリオールであるサンニックスＧＰ３０００（三洋化成社製、Ｍｎ＝３０００）２０重量部、架橋剤としてイソシアネート化合物（コロネートＨＸ：Ｃ／ＨＸ、日本ポリウレタン社製）１０．２重量部、イオン性化合物として１－エチル－３－メチルイミダゾリウムビス（トリフルオロメタンスルホニル）イミド（ＡＳ１１０、第一工業製薬社製）０．５重量部、水酸基含有の反応性シリコーンオイルＸ－２２－４０１５（信越化学工業社製）０．１重量部、酸化防止剤として、Ｉｒｇａｎｏｘ１０１０（ＢＡＳＦ社製）０．５重量部、触媒として、ナーセム第２鉄（日本化学産業社製）０．０３重量部を、全体の固形分が５０重量％となるように酢酸エチルで希釈し、ウレタン系粘着剤溶液を得た。そして、ウレタン系粘着剤溶液を、ポリエステル樹脂からなる基材（商品名「Ｔ１００－７５Ｓ」、厚み７５μｍ、三菱ケミカル株式会社製）に乾燥後の厚みが７５μｍとなるよう塗布し、乾燥温度１３０℃、乾燥時間３分の条件でキュアーして乾燥し、粘着剤組成物（４０）からなる粘着剤層を作製した。次いで、得られた粘着剤層の表面に、一方の面にシリコーン処理を施した厚さ２５μｍのポリエステル樹脂からなる剥離シート（商品名「ＭＲＦ２５」、厚み２５μｍ、三菱ケミカル株式会社製）のシリコーン処理面を貼合せて、表面保護フィルム（４０）を得た。常温で５日間エージングを行い、評価を行った。剥離シートは評価の直前に剥離した。結果を表４に示した。 [Example 40]
Preminol S3011 (Mn = 10000, manufactured by Asahi Glass Co., Ltd.), which is a polyol having 3 hydroxyl groups, and Sanniks GP3000 (Sanyo Kasei Co., Ltd.), which is a polyol having 3 hydroxyl groups and 50 parts by weight of urethane prepolymer. , Mn = 3000) 20 parts by weight, isocyanate compound (Coronate HX: C / HX, manufactured by Nippon Polyurethane Co., Ltd.) 10.2 parts by weight as a cross-linking agent, 1-ethyl-3-methylimidazolium bis (trifluo) as an ionic compound Lomethanesulfonyl) imide (AS110, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 0.5 parts by weight, hydroxyl group-containing reactive silicone oil X-22-4015 (manufactured by Shinetsu Chemical Industry Co., Ltd.) 0.1 parts by weight, as an antioxidant. Irganox 1010 (manufactured by BASF) 0.5 parts by weight and 0.03 part by weight of Nasem ferric iron (manufactured by Nippon Kagaku Sangyo Co., Ltd.) as a catalyst are diluted with ethyl acetate so that the total solid content is 50% by weight. , Urethane-based pressure-sensitive adhesive solution was obtained. Then, the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 μm, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 μm, and the drying temperature is 130 ° C. , Cure and dry under the condition of drying time of 3 minutes to prepare a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition (40). Next, the surface of the obtained pressure-sensitive adhesive layer was treated with a silicone-treated release sheet (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 μm, one of which was treated with silicone. The surfaces were bonded together to obtain a surface protective film (40). Aging was performed at room temperature for 5 days for evaluation. The release sheet was peeled off immediately before the evaluation. The results are shown in Table 4.
〔実施例４１〕
　ウレタンプレポリマー５０重量部、ポリオールとして、ヒドロキシル基を３個有するポリオールであるプレミノールＳ３０１１（旭硝子社製、Ｍｎ＝１００００）３０重量部、ヒドロキシル基を３個有するポリオールであるサンニックスＧＰ３０００（三洋化成社製、Ｍｎ＝３０００）２０重量部、架橋剤としてイソシアネート化合物（コロネートＨＸ：Ｃ／ＨＸ、日本ポリウレタン社製）１０．２重量部、イオン性化合物として１－エチル－３－メチルイミダゾリウムビス（トリフルオロメタンスルホニル）イミド（ＡＳ１１０、第一工業製薬社製）０．５重量部、水酸基含有の反応性シリコーンオイルＫＦ６００１（信越化学工業社製）０．１重量部、酸化防止剤として、Ｉｒｇａｎｏｘ１０１０（ＢＡＳＦ社製）０．５重量部、触媒として、ナーセム第２鉄（日本化学産業社製）０．０３重量部を、全体の固形分が５０重量％となるように酢酸エチルで希釈し、ウレタン系粘着剤溶液を得た。そして、ウレタン系粘着剤溶液を、ポリエステル樹脂からなる基材（商品名「Ｔ１００－７５Ｓ」、厚み７５μｍ、三菱ケミカル株式会社製）に乾燥後の厚みが７５μｍとなるよう塗布し、乾燥温度１３０℃、乾燥時間３分の条件でキュアーして乾燥し、粘着剤組成物（４１）からなる粘着剤層を作製した。次いで、得られた粘着剤層の表面に、一方の面にシリコーン処理を施した厚さ２５μｍのポリエステル樹脂からなる剥離シート（商品名「ＭＲＦ２５」、厚み２５μｍ、三菱ケミカル株式会社製）のシリコーン処理面を貼合せて、表面保護フィルム（４１）を得た。常温で５日間エージングを行い、評価を行った。剥離シートは評価の直前に剥離した。結果を表４に示した。 [Example 41]
Preminol S3011 (Mn = 10000, manufactured by Asahi Glass Co., Ltd.), which is a polyol having 3 hydroxyl groups, and Sanniks GP3000 (Sanyo Kasei Co., Ltd.), which is a polyol having 3 hydroxyl groups and 50 parts by weight of urethane prepolymer. , Mn = 3000) 20 parts by weight, isocyanate compound (Coronate HX: C / HX, manufactured by Nippon Polyurethane Co., Ltd.) 10.2 parts by weight as a cross-linking agent, 1-ethyl-3-methylimidazolium bis (trifluo) as an ionic compound Lomethanesulfonyl) imide (AS110, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 0.5 parts by weight, hydroxyl group-containing reactive silicone oil KF6001 (manufactured by Shinetsu Chemical Industry Co., Ltd.) 0.1 parts by weight, as an antioxidant, Irganox1010 (BASF) (Manufactured) 0.5 parts by weight, 0.03 parts by weight of Nasem ferrous iron (manufactured by Nippon Kagaku Sangyo Co., Ltd.) as a catalyst is diluted with ethyl acetate so that the total solid content is 50% by weight, and urethane-based adhesive A solution of the agent was obtained. Then, the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 μm, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 μm, and the drying temperature is 130 ° C. , Cure and dry under the condition of drying time of 3 minutes to prepare a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition (41). Next, the surface of the obtained pressure-sensitive adhesive layer was treated with a silicone-treated release sheet (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 μm, one of which was treated with silicone. The surfaces were bonded together to obtain a surface protective film (41). Aging was performed at room temperature for 5 days for evaluation. The release sheet was peeled off immediately before the evaluation. The results are shown in Table 4.
〔実施例４２〕
　ウレタンプレポリマー５０重量部、ポリオールとして、ヒドロキシル基を３個有するポリオールであるプレミノールＳ３０１１（旭硝子社製、Ｍｎ＝１００００）３０重量部、ヒドロキシル基を３個有するポリオールであるサンニックスＧＰ３０００（三洋化成社製、Ｍｎ＝３０００）２０重量部、架橋剤としてイソシアネート化合物（コロネートＨＸ：Ｃ／ＨＸ、日本ポリウレタン社製）１０．２重量部、イオン性化合物として１－エチル－３－メチルイミダゾリウムビス（トリフルオロメタンスルホニル）イミド（ＡＳ１１０、第一工業製薬社製）０．５重量部、水酸基含有の反応性シリコーンオイルＫＦ６００２（信越化学工業社製）０．１重量部、酸化防止剤として、Ｉｒｇａｎｏｘ１０１０（ＢＡＳＦ社製）０．５重量部、触媒として、ナーセム第２鉄（日本化学産業社製）０．０３重量部、全体の固形分が５０重量％となるように酢酸エチルで希釈し、ウレタン系粘着剤溶液を得た。そして、ウレタン系粘着剤溶液を、ポリエステル樹脂からなる基材（商品名「Ｔ１００－７５Ｓ」、厚み７５μｍ、三菱ケミカル株式会社製）に乾燥後の厚みが７５μｍとなるよう塗布し、乾燥温度１３０℃、乾燥時間３分の条件でキュアーして乾燥し、粘着剤組成物（４２）からなる粘着剤層を作製した。次いで、得られた粘着剤層の表面に、一方の面にシリコーン処理を施した厚さ２５μｍのポリエステル樹脂からなる剥離シート（商品名「ＭＲＦ２５」、厚み２５μｍ、三菱ケミカル株式会社製）のシリコーン処理面を貼合せて、表面保護フィルム（４２）を得た。常温で５日間エージングを行い、評価を行った。剥離シートは評価の直前に剥離した。結果を表４に示した。 [Example 42]
Preminol S3011 (Mn = 10000, manufactured by Asahi Glass Co., Ltd.), which is a polyol having 3 hydroxyl groups, and Sanniks GP3000 (Sanyo Kasei Co., Ltd.), which is a polyol having 3 hydroxyl groups and 50 parts by weight of urethane prepolymer. , Mn = 3000) 20 parts by weight, isocyanate compound (Coronate HX: C / HX, manufactured by Nippon Polyurethane Co., Ltd.) 10.2 parts by weight as a cross-linking agent, 1-ethyl-3-methylimidazolium bis (trifluo) as an ionic compound Lomethanesulfonyl) imide (AS110, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 0.5 parts by weight, hydroxyl group-containing reactive silicone oil KF6002 (manufactured by Shinetsu Chemical Industry Co., Ltd.) 0.1 parts by weight, as an antioxidant, Irganox1010 (BASF) (Manufactured) 0.5 parts by weight, as a catalyst, Nasem ferrous iron (manufactured by Nippon Kagaku Sangyo Co., Ltd.) 0.03 parts by weight, diluted with ethyl acetate so that the total solid content is 50% by weight, urethane adhesive A solution was obtained. Then, the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 μm, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 μm, and the drying temperature is 130 ° C. , And dried under the condition of a drying time of 3 minutes to prepare a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition (42). Next, the surface of the obtained pressure-sensitive adhesive layer was treated with a silicone-treated release sheet (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 μm, one of which was treated with silicone. The surfaces were bonded together to obtain a surface protective film (42). Aging was performed at room temperature for 5 days for evaluation. The release sheet was peeled off immediately before the evaluation. The results are shown in Table 4.
〔実施例４３〕
　ウレタンプレポリマー５０重量部、ポリオールとして、ヒドロキシル基を３個有するポリオールであるプレミノールＳ３０１１（旭硝子社製、Ｍｎ＝１００００）３０重量部、ヒドロキシル基を３個有するポリオールであるサンニックスＧＰ３０００（三洋化成社製、Ｍｎ＝３０００）２０重量部、架橋剤としてイソシアネート化合物（コロネートＨＸ：Ｃ／ＨＸ、日本ポリウレタン社製）１０．２重量部、イオン性化合物として１－エチル－３－メチルイミダゾリウムビス（トリフルオロメタンスルホニル）イミド（ＡＳ１１０、第一工業製薬社製）０．５重量部、水酸基含有の反応性シリコーンオイルＫＦ６０２８（信越化学工業社製）０．１重量部、酸化防止剤として、Ｉｒｇａｎｏｘ１０１０（ＢＡＳＦ社製）０．５重量部、触媒として、ナーセム第２鉄（日本化学産業社製）０．０３重量部を、全体の固形分が５０重量％となるように酢酸エチルで希釈し、ウレタン系粘着剤溶液を得た。そして、ウレタン系粘着剤溶液を、ポリエステル樹脂からなる基材（商品名「Ｔ１００－７５Ｓ」、厚み７５μｍ、三菱ケミカル株式会社製）に乾燥後の厚みが７５μｍとなるよう塗布し、乾燥温度１３０℃、乾燥時間３分の条件でキュアーして乾燥し、粘着剤組成物（４３）からなる粘着剤層を作製した。次いで、得られた粘着剤層の表面に、一方の面にシリコーン処理を施した厚さ２５μｍのポリエステル樹脂からなる剥離シート（商品名「ＭＲＦ２５」、厚み２５μｍ、三菱ケミカル株式会社製）のシリコーン処理面を貼合せて、表面保護フィルム（４３）を得た。常温で５日間エージングを行い、評価を行った。剥離シートは評価の直前に剥離した。結果を表４に示した。 [Example 43]
50 parts by weight of urethane prepolymer, 30 parts by weight of Preminol S3011 (Mn = 10000, manufactured by Asahi Glass Co., Ltd.), which is a polyol having 3 hydroxyl groups, and Sanniks GP3000 (Sanyo Kasei Co., Ltd.), which is a polyol having 3 hydroxyl groups. , Mn = 3000) 20 parts by weight, isocyanate compound (Coronate HX: C / HX, manufactured by Nippon Polyurethane Co., Ltd.) 10.2 parts by weight as a cross-linking agent, 1-ethyl-3-methylimidazolium bis (trifluo) as an ionic compound Lomethanesulfonyl) imide (AS110, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 0.5 parts by weight, hydroxyl group-containing reactive silicone oil KF6028 (manufactured by Shinetsu Chemical Industry Co., Ltd.) 0.1 parts by weight, as an antioxidant, Irganox 1010 (BASF) (Manufactured) 0.5 parts by weight, 0.03 parts by weight of Nasem ferrous iron (manufactured by Nippon Kagaku Sangyo Co., Ltd.) as a catalyst, diluted with ethyl acetate so that the total solid content is 50% by weight, urethane-based adhesive A solution of the agent was obtained. Then, the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 μm, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 μm, and the drying temperature is 130 ° C. , Cure and dry under the condition of drying time of 3 minutes to prepare a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition (43). Next, the surface of the obtained pressure-sensitive adhesive layer was treated with a silicone-treated release sheet (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 μm, one of which was treated with silicone. The surfaces were bonded together to obtain a surface protective film (43). Aging was performed at room temperature for 5 days for evaluation. The release sheet was peeled off immediately before the evaluation. The results are shown in Table 4.
〔実施例４４〕
　ウレタンプレポリマー５０重量部、ポリオールとして、ヒドロキシル基を３個有するポリオールであるプレミノールＳ３０１１（旭硝子社製、Ｍｎ＝１００００）３０重量部、ヒドロキシル基を３個有するポリオールであるサンニックスＧＰ３０００（三洋化成社製、Ｍｎ＝３０００）２０重量部、架橋剤としてイソシアネート化合物（コロネートＨＸ：Ｃ／ＨＸ、日本ポリウレタン社製）１０．２重量部、イオン性化合物として１－エチル－３－メチルイミダゾリウムビス（トリフルオロメタンスルホニル）イミド（ＡＳ１１０、第一工業製薬社製）０．５重量部、水酸基非含有の非反応性シリコーンオイルＫＦ６４３（信越化学工業社製）０．１重量部、酸化防止剤として、Ｉｒｇａｎｏｘ１０１０（ＢＡＳＦ社製）０．５重量部、触媒として、ナーセム第２鉄（日本化学産業社製）０．０３重量部を、全体の固形分が５０重量％となるように酢酸エチルで希釈し、ウレタン系粘着剤溶液を得た。そして、ウレタン系粘着剤溶液を、ポリエステル樹脂からなる基材（商品名「Ｔ１００－７５Ｓ」、厚み７５μｍ、三菱ケミカル株式会社製）に乾燥後の厚みが７５μｍとなるよう塗布し、乾燥温度１３０℃、乾燥時間３分の条件でキュアーして乾燥し、粘着剤組成物（４４）からなる粘着剤層を作製した。次いで、得られた粘着剤層の表面に、一方の面にシリコーン処理を施した厚さ２５μｍのポリエステル樹脂からなる剥離シート（商品名「ＭＲＦ２５」、厚み２５μｍ、三菱ケミカル株式会社製）のシリコーン処理面を貼合せて、表面保護フィルム（４４）を得た。常温で５日間エージングを行い、評価を行った。剥離シートは評価の直前に剥離した。結果を表４に示した。 [Example 44]
Preminol S3011 (Mn = 10000, manufactured by Asahi Glass Co., Ltd.), which is a polyol having 3 hydroxyl groups, and Sanniks GP3000 (Sanyo Kasei Co., Ltd.), which is a polyol having 3 hydroxyl groups and 50 parts by weight of urethane prepolymer. , Mn = 3000) 20 parts by weight, isocyanate compound (Coronate HX: C / HX, manufactured by Nippon Polyurethane Co., Ltd.) 10.2 parts by weight as a cross-linking agent, 1-ethyl-3-methylimidazolium bis (trifluo) as an ionic compound Lomethanesulfonyl) imide (AS110, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 0.5 part by weight, hydroxyl group-free non-reactive silicone oil KF643 (manufactured by Shinetsu Chemical Industry Co., Ltd.) 0.1 part by weight, as an antioxidant, Irganox1010 ( BASF) 0.5 part by weight, as a catalyst 0.03 part by weight of Nasem ferrous iron (manufactured by Nippon Kagaku Sangyo Co., Ltd.), diluted with ethyl acetate so that the total solid content is 50% by weight, urethane A system pressure-sensitive adhesive solution was obtained. Then, the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 μm, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 μm, and the drying temperature is 130 ° C. , Cure and dry under the condition of drying time of 3 minutes to prepare a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition (44). Next, the surface of the obtained pressure-sensitive adhesive layer was treated with a silicone-treated release sheet (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 μm, one of which was treated with silicone. The surfaces were bonded together to obtain a surface protective film (44). Aging was performed at room temperature for 5 days for evaluation. The release sheet was peeled off immediately before the evaluation. The results are shown in Table 4.
〔実施例４５〕
　ウレタンプレポリマー５０重量部、ポリオールとして、ヒドロキシル基を３個有するポリオールであるプレミノールＳ３０１１（旭硝子社製、Ｍｎ＝１００００）３０重量部、ヒドロキシル基を３個有するポリオールであるサンニックスＧＰ３０００（三洋化成社製、Ｍｎ＝３０００）２０重量部、架橋剤としてイソシアネート化合物（コロネートＨＸ：Ｃ／ＨＸ、日本ポリウレタン社製）１０．２重量部、イオン性化合物として１－エチル－３－メチルイミダゾリウムビス（トリフルオロメタンスルホニル）イミド（ＡＳ１１０、第一工業製薬社製）０．５重量部、水酸基非含有の非反応性シリコーンオイルＫＦ６４０（信越化学工業社製）０．１重量部、酸化防止剤として、Ｉｒｇａｎｏｘ１０１０（ＢＡＳＦ社製）０．５重量部、触媒として、ナーセム第２鉄（日本化学産業社製）０．０３重量部を、全体の固形分が５０重量％となるように酢酸エチルで希釈し、ウレタン系粘着剤溶液を得た。そして、ウレタン系粘着剤溶液を、ポリエステル樹脂からなる基材（商品名「Ｔ１００－７５Ｓ」、厚み７５μｍ、三菱ケミカル株式会社製）に乾燥後の厚みが７５μｍとなるよう塗布し、乾燥温度１３０℃、乾燥時間３分の条件でキュアーして乾燥し、粘着剤組成物（４５）からなる粘着剤層を作製した。次いで、得られた粘着剤層の表面に、一方の面にシリコーン処理を施した厚さ２５μｍのポリエステル樹脂からなる剥離シート（商品名「ＭＲＦ２５」、厚み２５μｍ、三菱ケミカル株式会社製）のシリコーン処理面を貼合せて、表面保護フィルム（４５）を得た。常温で５日間エージングを行い、評価を行った。剥離シートは評価の直前に剥離した。結果を表４に示した。 [Example 45]
Preminol S3011 (Mn = 10000, manufactured by Asahi Glass Co., Ltd.), which is a polyol having 3 hydroxyl groups, and Sanniks GP3000 (Sanyo Kasei Co., Ltd.), which is a polyol having 3 hydroxyl groups and 50 parts by weight of urethane prepolymer. , Mn = 3000) 20 parts by weight, isocyanate compound (Coronate HX: C / HX, manufactured by Nippon Polyurethane Co., Ltd.) 10.2 parts by weight as a cross-linking agent, 1-ethyl-3-methylimidazolium bis (trifluo) as an ionic compound Lomethanesulfonyl) imide (AS110, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 0.5 part by weight, hydroxyl group-free non-reactive silicone oil KF640 (manufactured by Shinetsu Chemical Industry Co., Ltd.) 0.1 part by weight, as an antioxidant, Irganox1010 (manufactured by Shinetsu Chemical Industry Co., Ltd.) BASF) 0.5 part by weight, as a catalyst 0.03 part by weight of Nasem ferrous iron (manufactured by Nippon Kagaku Sangyo Co., Ltd.), diluted with ethyl acetate so that the total solid content is 50% by weight, urethane A system pressure-sensitive adhesive solution was obtained. Then, the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 μm, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 μm, and the drying temperature is 130 ° C. , Cure and dry under the condition of drying time of 3 minutes to prepare a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition (45). Next, the surface of the obtained pressure-sensitive adhesive layer was treated with a silicone-treated release sheet (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 μm, one of which was treated with silicone. The surfaces were bonded together to obtain a surface protective film (45). Aging was performed at room temperature for 5 days for evaluation. The release sheet was peeled off immediately before the evaluation. The results are shown in Table 4.
〔実施例４６〕
　ウレタンプレポリマー５０重量部、ポリオールとして、ヒドロキシル基を３個有するポリオールであるプレミノールＳ３０１１（旭硝子社製、Ｍｎ＝１００００）３０重量部、ヒドロキシル基を３個有するポリオールであるサンニックスＧＰ３０００（三洋化成社製、Ｍｎ＝３０００）２０重量部、架橋剤としてイソシアネート化合物（コロネートＨＸ：Ｃ／ＨＸ、日本ポリウレタン社製）１０．２重量部、イオン性化合物として１－エチル－３－メチルイミダゾリウムビス（トリフルオロメタンスルホニル）イミド（ＡＳ１１０、第一工業製薬社製）０．５重量部、水酸基非含有の非反応性シリコーンオイルＫＦ６１５Ａ（信越化学工業社製）０．１重量部、酸化防止剤として、Ｉｒｇａｎｏｘ１０１０（ＢＡＳＦ社製）０．５重量部、触媒として、ナーセム第２鉄（日本化学産業社製）０．０３重量部を、全体の固形分が５０重量％となるように酢酸エチルで希釈し、ウレタン系粘着剤溶液を得た。そして、ウレタン系粘着剤溶液を、ポリエステル樹脂からなる基材（商品名「Ｔ１００－７５Ｓ」、厚み７５μｍ、三菱ケミカル株式会社製）に乾燥後の厚みが７５μｍとなるよう塗布し、乾燥温度１３０℃、乾燥時間３分の条件でキュアーして乾燥し、粘着剤組成物（４６）からなる粘着剤層を作製した。次いで、得られた粘着剤層の表面に、一方の面にシリコーン処理を施した厚さ２５μｍのポリエステル樹脂からなる剥離シート（商品名「ＭＲＦ２５」、厚み２５μｍ、三菱ケミカル株式会社製）のシリコーン処理面を貼合せて、表面保護フィルム（４６）を得た。常温で５日間エージングを行い、評価を行った。剥離シートは評価の直前に剥離した。結果を表４に示した。 [Example 46]
Preminol S3011 (Mn = 10000, manufactured by Asahi Glass Co., Ltd.), which is a polyol having 3 hydroxyl groups, and Sanniks GP3000 (Sanyo Kasei Co., Ltd.), which is a polyol having 3 hydroxyl groups and 50 parts by weight of urethane prepolymer. , Mn = 3000) 20 parts by weight, isocyanate compound (Coronate HX: C / HX, manufactured by Nippon Polyurethane Co., Ltd.) 10.2 parts by weight as a cross-linking agent, 1-ethyl-3-methylimidazolium bis (trifluo) as an ionic compound Lomethanesulfonyl) imide (AS110, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 0.5 part by weight, hydroxyl group-free non-reactive silicone oil KF615A (manufactured by Shinetsu Chemical Industry Co., Ltd.) 0.1 part by weight, as an antioxidant, Irganox1010 (manufactured by Shinetsu Chemical Industry Co., Ltd.) BASF) 0.5 part by weight, as a catalyst 0.03 part by weight of Nasem ferrous iron (manufactured by Nippon Kagaku Sangyo Co., Ltd.), diluted with ethyl acetate so that the total solid content is 50% by weight, urethane A system pressure-sensitive adhesive solution was obtained. Then, the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 μm, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 μm, and the drying temperature is 130 ° C. , And dried under the condition of a drying time of 3 minutes to prepare a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition (46). Next, the surface of the obtained pressure-sensitive adhesive layer was treated with a silicone-treated release sheet (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 μm, one of which was treated with silicone. The surfaces were bonded together to obtain a surface protective film (46). Aging was performed at room temperature for 5 days for evaluation. The release sheet was peeled off immediately before the evaluation. The results are shown in Table 4.
〔実施例４７〕
　ウレタンプレポリマー５０重量部、ポリオールとして、ヒドロキシル基を３個有するポリオールであるプレミノールＳ３０１１（旭硝子社製、Ｍｎ＝１００００）３０重量部、ヒドロキシル基を３個有するポリオールであるサンニックスＧＰ３０００（三洋化成社製、Ｍｎ＝３０００）２０重量部、架橋剤としてイソシアネート化合物（コロネートＨＸ：Ｃ／ＨＸ、日本ポリウレタン社製）１０．２重量部、イオン性化合物として１－エチル－３－メチルイミダゾリウムビス（トリフルオロメタンスルホニル）イミド（ＡＳ１１０、第一工業製薬社製）０．５重量部、水酸基非含有の非反応性シリコーンオイルＫＦ３５２Ａ（信越化学工業社製）０．１重量部、酸化防止剤として、Ｉｒｇａｎｏｘ１０１０（ＢＡＳＦ社製）０．５重量部、触媒として、ナーセム第２鉄（日本化学産業社製）０．０３重量部を、全体の固形分が５０重量％となるように酢酸エチルで希釈し、ウレタン系粘着剤溶液を得た。そして、ウレタン系粘着剤溶液を、ポリエステル樹脂からなる基材（商品名「Ｔ１００－７５Ｓ」、厚み７５μｍ、三菱ケミカル株式会社製）に乾燥後の厚みが７５μｍとなるよう塗布し、乾燥温度１３０℃、乾燥時間３分の条件でキュアーして乾燥し、粘着剤組成物（４７）からなる粘着剤層を作製した。次いで、得られた粘着剤層の表面に、一方の面にシリコーン処理を施した厚さ２５μｍのポリエステル樹脂からなる剥離シート（商品名「ＭＲＦ２５」、厚み２５μｍ、三菱ケミカル株式会社製）のシリコーン処理面を貼合せて、表面保護フィルム（４７）を得た。常温で５日間エージングを行い、評価を行った。剥離シートは評価の直前に剥離した。結果を表４に示した。 [Example 47]
Preminol S3011 (Mn = 10000, manufactured by Asahi Glass Co., Ltd.), which is a polyol having 3 hydroxyl groups, and Sanniks GP3000 (Sanyo Kasei Co., Ltd.), which is a polyol having 3 hydroxyl groups and 50 parts by weight of urethane prepolymer. , Mn = 3000) 20 parts by weight, isocyanate compound (Coronate HX: C / HX, manufactured by Nippon Polyurethane Co., Ltd.) 10.2 parts by weight as a cross-linking agent, 1-ethyl-3-methylimidazolium bis (trifluo) as an ionic compound Lomethanesulfonyl) imide (AS110, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 0.5 part by weight, hydroxyl group-free non-reactive silicone oil KF352A (manufactured by Shinetsu Chemical Industry Co., Ltd.) 0.1 part by weight, as an antioxidant, Irganox1010 ( BASF) 0.5 part by weight, as a catalyst, Nasem ferric iron (manufactured by Nippon Kagaku Sangyo Co., Ltd.) 0.03 part by weight, diluted with ethyl acetate so that the total solid content is 50% by weight, urethane A system pressure-sensitive adhesive solution was obtained. Then, the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 μm, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 μm, and the drying temperature is 130 ° C. , And dried under the condition of a drying time of 3 minutes to prepare a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition (47). Next, the surface of the obtained pressure-sensitive adhesive layer was treated with a silicone-treated release sheet (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 μm, one of which was treated with silicone. The surfaces were bonded together to obtain a surface protective film (47). Aging was performed at room temperature for 5 days for evaluation. The release sheet was peeled off immediately before the evaluation. The results are shown in Table 4.
〔実施例４８〕
　ウレタンプレポリマー５０重量部、ポリオールとして、ヒドロキシル基を３個有するポリオールであるプレミノールＳ３０１１（旭硝子社製、Ｍｎ＝１００００）３０重量部、ヒドロキシル基を３個有するポリオールであるサンニックスＧＰ３０００（三洋化成社製、Ｍｎ＝３０００）２０重量部、架橋剤としてイソシアネート化合物（コロネートＨＸ：Ｃ／ＨＸ、日本ポリウレタン社製）１０．２重量部、イオン性化合物として１－エチル－３－メチルイミダゾリウムビス（トリフルオロメタンスルホニル）イミド（ＡＳ１１０、第一工業製薬社製）０．５重量部、水酸基非含有の非反応性シリコーンオイルＫＦ９４５（信越化学工業社製）０．１重量部、酸化防止剤として、Ｉｒｇａｎｏｘ１０１０（ＢＡＳＦ社製）０．５重量部、触媒として、ナーセム第２鉄（日本化学産業社製）０．０３重量部を、全体の固形分が５０重量％となるように酢酸エチルで希釈し、ウレタン系粘着剤溶液を得た。そして、ウレタン系粘着剤溶液を、ポリエステル樹脂からなる基材（商品名「Ｔ１００－７５Ｓ」、厚み７５μｍ、三菱ケミカル株式会社製）に乾燥後の厚みが７５μｍとなるよう塗布し、乾燥温度１３０℃、乾燥時間３分の条件でキュアーして乾燥し、粘着剤組成物（４８）からなる粘着剤層を作製した。次いで、得られた粘着剤層の表面に、一方の面にシリコーン処理を施した厚さ２５μｍのポリエステル樹脂からなる剥離シート（商品名「ＭＲＦ２５」、厚み２５μｍ、三菱ケミカル株式会社製）のシリコーン処理面を貼合せて、表面保護フィルム（４８）を得た。常温で５日間エージングを行い、評価を行った。剥離シートは評価の直前に剥離した。結果を表４に示した。 [Example 48]
50 parts by weight of urethane prepolymer, 30 parts by weight of Preminol S3011 (Mn = 10000, manufactured by Asahi Glass Co., Ltd.), which is a polyol having 3 hydroxyl groups, and Sanniks GP3000 (Sanyo Kasei Co., Ltd.), which is a polyol having 3 hydroxyl groups. , Mn = 3000) 20 parts by weight, isocyanate compound (Coronate HX: C / HX, manufactured by Nippon Polyurethane Co., Ltd.) 10.2 parts by weight as a cross-linking agent, 1-ethyl-3-methylimidazolium bis (trifluo) as an ionic compound Lomethanesulfonyl) imide (AS110, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 0.5 part by weight, hydroxyl group-free non-reactive silicone oil KF945 (manufactured by Shinetsu Chemical Industry Co., Ltd.) 0.1 part by weight, as an antioxidant, Irganox1010 ( BASF) 0.5 part by weight, as a catalyst, Nasem ferric iron (manufactured by Nippon Kagaku Sangyo Co., Ltd.) 0.03 part by weight, diluted with ethyl acetate so that the total solid content is 50% by weight, urethane A system pressure-sensitive adhesive solution was obtained. Then, the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 μm, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 μm, and the drying temperature is 130 ° C. , Cure and dry under the condition of drying time of 3 minutes to prepare a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition (48). Next, the surface of the obtained pressure-sensitive adhesive layer was treated with a silicone-treated release sheet (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 μm, one of which was treated with silicone. The surfaces were bonded together to obtain a surface protective film (48). Aging was performed at room temperature for 5 days for evaluation. The release sheet was peeled off immediately before the evaluation. The results are shown in Table 4.
〔実施例４９〕
　ウレタンプレポリマー５０重量部、ポリオールとして、ヒドロキシル基を３個有するポリオールであるプレミノールＳ３０１１（旭硝子社製、Ｍｎ＝１００００）３０重量部、ヒドロキシル基を３個有するポリオールであるサンニックスＧＰ３０００（三洋化成社製、Ｍｎ＝３０００）２０重量部、架橋剤としてイソシアネート化合物（コロネートＨＸ：Ｃ／ＨＸ、日本ポリウレタン社製）１０．２重量部、イオン性化合物として１－エチル－３－メチルイミダゾリウムビス（トリフルオロメタンスルホニル）イミド（ＡＳ１１０、第一工業製薬社製）０．５重量部、水酸基非含有の非反応性シリコーンオイルＫＦ６１５Ａ（信越化学工業社製）０．０５重量部、酸化防止剤として、Ｉｒｇａｎｏｘ１０１０（ＢＡＳＦ社製）０．５重量部、触媒として、ナーセム第２鉄（日本化学産業社製）０．０３重量部を、全体の固形分が５０重量％となるように酢酸エチルで希釈し、ウレタン系粘着剤溶液を得た。そして、ウレタン系粘着剤溶液を、ポリエステル樹脂からなる基材（商品名「Ｔ１００－７５Ｓ」、厚み７５μｍ、三菱ケミカル株式会社製）に乾燥後の厚みが７５μｍとなるよう塗布し、乾燥温度１３０℃、乾燥時間３分の条件でキュアーして乾燥し、粘着剤組成物（４９）からなる粘着剤層を作製した。次いで、得られた粘着剤層の表面に、一方の面にシリコーン処理を施した厚さ２５μｍのポリエステル樹脂からなる剥離シート（商品名「ＭＲＦ２５」、厚み２５μｍ、三菱ケミカル株式会社製）のシリコーン処理面を貼合せて、表面保護フィルム（４９）を得た。常温で５日間エージングを行い、評価を行った。剥離シートは評価の直前に剥離した。結果を表４に示した。 [Example 49]
Preminol S3011 (Mn = 10000, manufactured by Asahi Glass Co., Ltd.), which is a polyol having 3 hydroxyl groups, and Sanniks GP3000 (Sanyo Kasei Co., Ltd.), which is a polyol having 3 hydroxyl groups and 50 parts by weight of urethane prepolymer. , Mn = 3000) 20 parts by weight, isocyanate compound (Coronate HX: C / HX, manufactured by Nippon Polyurethane Co., Ltd.) 10.2 parts by weight as a cross-linking agent, 1-ethyl-3-methylimidazolium bis (trifluo) as an ionic compound Lomethanesulfonyl) imide (AS110, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 0.5 parts by weight, hydroxyl group-free non-reactive silicone oil KF615A (manufactured by Shinetsu Chemical Industry Co., Ltd.) 0.05 parts by weight, as an antioxidant, Irganox1010 (manufactured by Shinetsu Chemical Industry Co., Ltd.) BASF) 0.5 part by weight, as a catalyst 0.03 part by weight of Nasem ferrous iron (manufactured by Nippon Kagaku Sangyo Co., Ltd.), diluted with ethyl acetate so that the total solid content is 50% by weight, urethane A system pressure-sensitive adhesive solution was obtained. Then, the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 μm, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 μm, and the drying temperature is 130 ° C. , Cure and dry under the condition of drying time of 3 minutes to prepare a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition (49). Next, the surface of the obtained pressure-sensitive adhesive layer was treated with a silicone-treated release sheet (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 μm, one of which was treated with silicone. The surfaces were bonded together to obtain a surface protective film (49). Aging was performed at room temperature for 5 days for evaluation. The release sheet was peeled off immediately before the evaluation. The results are shown in Table 4.
〔実施例５０〕
　ウレタンプレポリマー５０重量部、ポリオールとして、ヒドロキシル基を３個有するポリオールであるプレミノールＳ３０１１（旭硝子社製、Ｍｎ＝１００００）３０重量部、ヒドロキシル基を３個有するポリオールであるサンニックスＧＰ３０００（三洋化成社製、Ｍｎ＝３０００）２０重量部、架橋剤としてイソシアネート化合物（コロネートＨＸ：Ｃ／ＨＸ、日本ポリウレタン社製）１０．２重量部、イオン性化合物として１－エチル－３－メチルイミダゾリウムビス（トリフルオロメタンスルホニル）イミド（ＡＳ１１０、第一工業製薬社製）０．５重量部、水酸基非含有の非反応性シリコーンオイルＫＦ６１５Ａ（信越化学工業社製）０．０２５重量部、酸化防止剤として、Ｉｒｇａｎｏｘ１０１０（ＢＡＳＦ社製）０．５重量部、触媒として、ナーセム第２鉄（日本化学産業社製）０．０３重量部を、全体の固形分が５０重量％となるように酢酸エチルで希釈し、ウレタン系粘着剤溶液を得た。そして、ウレタン系粘着剤溶液を、ポリエステル樹脂からなる基材（商品名「Ｔ１００－７５Ｓ」、厚み７５μｍ、三菱ケミカル株式会社製）に乾燥後の厚みが７５μｍとなるよう塗布し、乾燥温度１３０℃、乾燥時間３分の条件でキュアーして乾燥し、粘着剤組成物（５０）からなる粘着剤層を作製した。次いで、得られた粘着剤層の表面に、一方の面にシリコーン処理を施した厚さ２５μｍのポリエステル樹脂からなる剥離シート（商品名「ＭＲＦ２５」、厚み２５μｍ、三菱ケミカル株式会社製）のシリコーン処理面を貼合せて、表面保護フィルム（５０）を得た。常温で５日間エージングを行い、評価を行った。剥離シートは評価の直前に剥離した。結果を表４に示した。 [Example 50]
Preminol S3011 (Mn = 10000, manufactured by Asahi Glass Co., Ltd.), which is a polyol having 3 hydroxyl groups, and Sanniks GP3000 (Sanyo Kasei Co., Ltd.), which is a polyol having 3 hydroxyl groups and 50 parts by weight of urethane prepolymer. , Mn = 3000) 20 parts by weight, isocyanate compound (Coronate HX: C / HX, manufactured by Nippon Polyurethane Co., Ltd.) 10.2 parts by weight as a cross-linking agent, 1-ethyl-3-methylimidazolium bis (trifluo) as an ionic compound Lomethanesulfonyl) imide (AS110, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 0.5 parts by weight, hydroxyl group-free non-reactive silicone oil KF615A (manufactured by Shinetsu Chemical Industry Co., Ltd.) 0.025 parts by weight, as an antioxidant, Irganox 1010 (manufactured by Shinetsu Chemical Industry Co., Ltd.) BASF) 0.5 part by weight, as a catalyst, Nasem ferric iron (manufactured by Nippon Kagaku Sangyo Co., Ltd.) 0.03 part by weight, diluted with ethyl acetate so that the total solid content is 50% by weight, urethane A system pressure-sensitive adhesive solution was obtained. Then, the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 μm, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 μm, and the drying temperature is 130 ° C. , Cure and dry under the condition of drying time of 3 minutes to prepare a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition (50). Next, the surface of the obtained pressure-sensitive adhesive layer was treated with a silicone-treated release sheet (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 μm, one of which was treated with silicone. The surfaces were bonded together to obtain a surface protective film (50). Aging was performed at room temperature for 5 days for evaluation. The release sheet was peeled off immediately before the evaluation. The results are shown in Table 4.
〔実施例５１〕
　ウレタンプレポリマー５０重量部、ポリオールとして、ヒドロキシル基を３個有するポリオールであるプレミノールＳ３０１１（旭硝子社製、Ｍｎ＝１００００）３０重量部、ヒドロキシル基を３個有するポリオールであるサンニックスＧＰ３０００（三洋化成社製、Ｍｎ＝３０００）２０重量部、架橋剤としてイソシアネート化合物（コロネートＨＸ：Ｃ／ＨＸ、日本ポリウレタン社製）１０．２重量部、イオン性化合物として１－エチル－３－メチルイミダゾリウムビス（トリフルオロメタンスルホニル）イミド（ＡＳ１１０、第一工業製薬社製）０．５重量部、水酸基非含有の非反応性シリコーンオイルＫＦ６１５Ａ（信越化学工業社製）０．０１重量部、酸化防止剤として、Ｉｒｇａｎｏｘ１０１０（ＢＡＳＦ社製）０．５重量部、触媒として、ナーセム第２鉄（日本化学産業社製）０．０３重量部を、全体の固形分が５０重量％となるように酢酸エチルで希釈し、ウレタン系粘着剤溶液を得た。そして、ウレタン系粘着剤溶液を、ポリエステル樹脂からなる基材（商品名「Ｔ１００－７５Ｓ」、厚み７５μｍ、三菱ケミカル株式会社製）に乾燥後の厚みが７５μｍとなるよう塗布し、乾燥温度１３０℃、乾燥時間３分の条件でキュアーして乾燥し、粘着剤組成物（５１）からなる粘着剤層を作製した。次いで、得られた粘着剤層の表面に、一方の面にシリコーン処理を施した厚さ２５μｍのポリエステル樹脂からなる剥離シート（商品名「ＭＲＦ２５」、厚み２５μｍ、三菱ケミカル株式会社製）のシリコーン処理面を貼合せて、表面保護フィルム（５１）を得た。常温で５日間エージングを行い、評価を行った。剥離シートは評価の直前に剥離した。結果を表４に示した。 [Example 51]
Preminol S3011 (Mn = 10000, manufactured by Asahi Glass Co., Ltd.), which is a polyol having 3 hydroxyl groups, and Sanniks GP3000 (Sanyo Kasei Co., Ltd.), which is a polyol having 3 hydroxyl groups and 50 parts by weight of urethane prepolymer. , Mn = 3000) 20 parts by weight, isocyanate compound (Coronate HX: C / HX, manufactured by Nippon Polyurethane Co., Ltd.) 10.2 parts by weight as a cross-linking agent, 1-ethyl-3-methylimidazolium bis (trifluo) as an ionic compound Lomethanesulfonyl) imide (AS110, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 0.5 part by weight, hydroxyl group-free non-reactive silicone oil KF615A (manufactured by Shinetsu Chemical Industry Co., Ltd.) 0.01 part by weight, as an antioxidant, Irganox1010 (manufactured by Shinetsu Chemical Industry Co., Ltd.) BASF) 0.5 part by weight, as a catalyst 0.03 part by weight of Nasem ferrous iron (manufactured by Nippon Kagaku Sangyo Co., Ltd.), diluted with ethyl acetate so that the total solid content is 50% by weight, urethane A system pressure-sensitive adhesive solution was obtained. Then, the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 μm, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 μm, and the drying temperature is 130 ° C. , Cure and dry under the condition of drying time of 3 minutes to prepare a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition (51). Next, the surface of the obtained pressure-sensitive adhesive layer was treated with a silicone-treated release sheet (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 μm, one of which was treated with silicone. The surfaces were bonded together to obtain a surface protective film (51). Aging was performed at room temperature for 5 days for evaluation. The release sheet was peeled off immediately before the evaluation. The results are shown in Table 4.
〔実施例５２〕
　ウレタンプレポリマー５０重量部、ポリオールとして、ヒドロキシル基を３個有するポリオールであるプレミノールＳ３０１１（旭硝子社製、Ｍｎ＝１００００）３０重量部、ヒドロキシル基を３個有するポリオールであるサンニックスＧＰ３０００（三洋化成社製、Ｍｎ＝３０００）２０重量部、架橋剤としてイソシアネート化合物（コロネートＨＸ：Ｃ／ＨＸ、日本ポリウレタン社製）１０．２重量部、イオン性化合物として１－エチル－３－メチルイミダゾリウムビス（トリフルオロメタンスルホニル）イミド（ＡＳ１１０、第一工業製薬社製）０．５重量部、フッ素系オリゴマーのメガファックＦ－５６３（ＤＩＣ社製）０．１重量部、水酸基非含有の非反応性シリコーンオイルＫＦ６１５Ａ（信越化学工業社製）０．０２５重量部、酸化防止剤として、Ｉｒｇａｎｏｘ１０１０（ＢＡＳＦ社製）０．５重量部、触媒として、ナーセム第２鉄（日本化学産業社製）０．０３重量部を、全体の固形分が５０重量％となるように酢酸エチルで希釈し、ウレタン系粘着剤溶液を得た。そして、ウレタン系粘着剤溶液を、ポリエステル樹脂からなる基材（商品名「Ｔ１００－７５Ｓ」、厚み７５μｍ、三菱ケミカル株式会社製）に乾燥後の厚みが７５μｍとなるよう塗布し、乾燥温度１３０℃、乾燥時間３分の条件でキュアーして乾燥し、粘着剤組成物（５２）からなる粘着剤層を作製した。次いで、得られた粘着剤層の表面に、一方の面にシリコーン処理を施した厚さ２５μｍのポリエステル樹脂からなる剥離シート（商品名「ＭＲＦ２５」、厚み２５μｍ、三菱ケミカル株式会社製）のシリコーン処理面を貼合せて、表面保護フィルム（５２）を得た。常温で５日間エージングを行い、評価を行った。剥離シートは評価の直前に剥離した。結果を表４に示した。 [Example 52]
Preminol S3011 (Mn = 10000, manufactured by Asahi Glass Co., Ltd.), which is a polyol having 3 hydroxyl groups, and Sanniks GP3000 (Sanyo Kasei Co., Ltd.), which is a polyol having 3 hydroxyl groups and 50 parts by weight of urethane prepolymer. , Mn = 3000) 20 parts by weight, isocyanate compound (Coronate HX: C / HX, manufactured by Nippon Polyurethane Co., Ltd.) 10.2 parts by weight as a cross-linking agent, 1-ethyl-3-methylimidazolium bis (trifluo) as an ionic compound Lomethansulfonyl) imide (AS110, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 0.5 parts by weight, fluorine-based oligomer Megafuck F-563 (manufactured by DIC) 0.1 parts by weight, hydroxyl group-free non-reactive silicone oil KF615A 0.025 parts by weight (manufactured by Shin-Etsu Chemical Industry Co., Ltd.), 0.5 parts by weight of Irganox1010 (manufactured by BASF) as an antioxidant, 0.03 parts by weight of Nasem ferrous iron (manufactured by Nippon Chemical Industry Co., Ltd.) as a catalyst. , Diluted with ethyl acetate so that the total solid content was 50% by weight to obtain a urethane-based pressure-sensitive adhesive solution. Then, the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 μm, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 μm, and the drying temperature is 130 ° C. , Cure and dry under the condition of drying time of 3 minutes to prepare a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition (52). Next, the surface of the obtained pressure-sensitive adhesive layer was treated with a silicone-treated release sheet (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 μm, one of which was treated with silicone. The surfaces were bonded together to obtain a surface protective film (52). Aging was performed at room temperature for 5 days for evaluation. The release sheet was peeled off immediately before the evaluation. The results are shown in Table 4.
〔比較例１〕
　ウレタンプレポリマー１００重量部、架橋剤としてイソシアネート化合物（コロネートＨＸ：Ｃ／ＨＸ、日本ポリウレタン社製）２．９重量部、酸化防止剤として、Ｉｒｇａｎｏｘ１０１０（ＢＡＳＦ社製）０．５重量部、触媒として、ナーセム第２鉄（日本化学産業社製）０．０３重量部を、全体の固形分が５０重量％となるように酢酸エチルで希釈し、ウレタン系粘着剤溶液を得た。そして、ウレタン系粘着剤溶液を、ポリエステル樹脂からなる基材（商品名「Ｔ１００－７５Ｓ」、厚み７５μｍ、三菱ケミカル株式会社製）に乾燥後の厚みが７５μｍとなるよう塗布し、乾燥温度１３０℃、乾燥時間３分の条件でキュアーして乾燥し、粘着剤組成物（Ｃ１）からなる粘着剤層を作製した。次いで、得られた粘着剤層の表面に、一方の面にシリコーン処理を施した厚さ２５μｍのポリエステル樹脂からなる剥離シート（商品名「ＭＲＦ２５」、厚み２５μｍ、三菱ケミカル株式会社製）のシリコーン処理面を貼合せて、表面保護フィルム（Ｃ１）を得た。常温で５日間エージングを行い、評価を行った。剥離シートは評価の直前に剥離した。結果を表５に示した。 [Comparative Example 1]
100 parts by weight of urethane prepolymer, 2.9 parts by weight of isocyanate compound (Coronate HX: C / HX, manufactured by Nippon Polyurethane) as a cross-linking agent, 0.5 parts by weight of Irganox 1010 (manufactured by BASF) as an antioxidant, as a catalyst , 0.03 part by weight of Nasem ferrous iron (manufactured by Nippon Kagaku Sangyo Co., Ltd.) was diluted with ethyl acetate so that the total solid content was 50% by weight to obtain a urethane-based pressure-sensitive adhesive solution. Then, the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 μm, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 μm, and the drying temperature is 130 ° C. , Cure and dry under the condition of drying time of 3 minutes to prepare a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition (C1). Next, the surface of the obtained pressure-sensitive adhesive layer was treated with a silicone-treated release sheet (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 μm, one of which was treated with silicone. The surfaces were bonded together to obtain a surface protective film (C1). Aging was performed at room temperature for 5 days for evaluation. The release sheet was peeled off immediately before the evaluation. The results are shown in Table 5.
〔比較例２〕
　ウレタンプレポリマー５０重量部、ポリオールとして、ヒドロキシル基を３個有するポリオールであるプレミノールＳ３０１１（旭硝子社製、Ｍｎ＝１００００）３５重量部、ヒドロキシル基を３個有するポリオールであるサンニックスＧＰ３０００（三洋化成社製、Ｍｎ＝３０００）１３重量部、ヒドロキシル基を３個有するポリオールであるサンニックスＧＰ２５０（三洋化成社製、Ｍｎ＝２５０）１３重量部、架橋剤としてイソシアネート化合物（コロネートＨＸ：Ｃ／ＨＸ、日本ポリウレタン社製）１５．６重量部、酸化防止剤として、Ｉｒｇａｎｏｘ１０１０（ＢＡＳＦ社製）０．５重量部、触媒として、ナーセム第２鉄（日本化学産業社製）０．０３重量部を、全体の固形分が５０重量％となるように酢酸エチルで希釈し、ウレタン系粘着剤溶液を得た。そして、ウレタン系粘着剤溶液を、ポリエステル樹脂からなる基材（商品名「Ｔ１００－７５Ｓ」、厚み７５μｍ、三菱ケミカル株式会社製）に乾燥後の厚みが７５μｍとなるよう塗布し、乾燥温度１３０℃、乾燥時間３分の条件でキュアーして乾燥し、粘着剤組成物（Ｃ２）からなる粘着剤層を作製した。次いで、得られた粘着剤層の表面に、一方の面にシリコーン処理を施した厚さ２５μｍのポリエステル樹脂からなる剥離シート（商品名「ＭＲＦ２５」、厚み２５μｍ、三菱ケミカル株式会社製）のシリコーン処理面を貼合せて、表面保護フィルム（Ｃ２）を得た。常温で５日間エージングを行い、評価を行った。剥離シートは評価の直前に剥離した。結果を表５に示した。 [Comparative Example 2]
50 parts by weight of urethane prepolymer, 35 parts by weight of Preminol S3011 (Mn = 10000, manufactured by Asahi Glass Co., Ltd.), which is a polyol having 3 hydroxyl groups, and Sanniks GP3000 (Sanyo Kasei Co., Ltd.), which is a polyol having 3 hydroxyl groups. Mn = 3000) 13 parts by weight, Sanniks GP250 (Mn = 250, manufactured by Sanyo Kasei Co., Ltd.), which is a polyol having three hydroxyl groups, 13 parts by weight, isocyanate compound (Coronate HX: C / HX, Japan) as a cross-linking agent 15.6 parts by weight of polyurethane (manufactured by Polyurethane), 0.5 parts by weight of Irganox1010 (manufactured by BASF) as an antioxidant, and 0.03 parts by weight of Nasem ferrous iron (manufactured by Nippon Kagaku Sangyo) as a catalyst. It was diluted with ethyl acetate so that the solid content was 50% by weight to obtain a urethane-based pressure-sensitive adhesive solution. Then, the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 μm, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 μm, and the drying temperature is 130 ° C. , Cure and dry under the condition of drying time of 3 minutes to prepare a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition (C2). Next, the surface of the obtained pressure-sensitive adhesive layer was treated with a silicone-treated release sheet (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 μm, one of which was treated with silicone. The surfaces were bonded together to obtain a surface protective film (C2). Aging was performed at room temperature for 5 days for evaluation. The release sheet was peeled off immediately before the evaluation. The results are shown in Table 5.
〔比較例３〕
　ウレタンプレポリマー５０重量部、ポリオールとして、ヒドロキシル基を３個有するポリオールであるプレミノールＳ３０１１（旭硝子社製、Ｍｎ＝１００００）４０重量部、ヒドロキシル基を３個有するポリオールであるサンニックスＧＰ３０００（三洋化成社製、Ｍｎ＝３０００）１０重量部、架橋剤としてイソシアネート化合物（コロネートＨＸ：Ｃ／ＨＸ、日本ポリウレタン社製）８．１重量部、酸化防止剤として、Ｉｒｇａｎｏｘ１０１０（ＢＡＳＦ社製）０．５重量部、触媒として、ナーセム第２鉄（日本化学産業社製）０．０３重量部を、全体の固形分が５０重量％となるように酢酸エチルで希釈し、ウレタン系粘着剤溶液を得た。そして、ウレタン系粘着剤溶液を、ポリエステル樹脂からなる基材（商品名「Ｔ１００－７５Ｓ」、厚み７５μｍ、三菱ケミカル株式会社製）に乾燥後の厚みが７５μｍとなるよう塗布し、乾燥温度１３０℃、乾燥時間３分の条件でキュアーして乾燥し、粘着剤組成物（Ｃ３）からなる粘着剤層を作製した。次いで、得られた粘着剤層の表面に、一方の面にシリコーン処理を施した厚さ２５μｍのポリエステル樹脂からなる剥離シート（商品名「ＭＲＦ２５」、厚み２５μｍ、三菱ケミカル株式会社製）のシリコーン処理面を貼合せて、表面保護フィルム（Ｃ３）を得た。常温で５日間エージングを行い、評価を行った。剥離シートは評価の直前に剥離した。結果を表５に示した。 [Comparative Example 3]
50 parts by weight of urethane prepolymer, 40 parts by weight of Preminol S3011 (Mn = 10000, manufactured by Asahi Glass Co., Ltd.), which is a polyol having 3 hydroxyl groups, and Sanniks GP3000 (Sanyo Kasei Co., Ltd.), which is a polyol having 3 hydroxyl groups. , Mn = 3000) 10 parts by weight, isocyanate compound (Coronate HX: C / HX, manufactured by Nippon Polyurethane Co., Ltd.) 8.1 parts by weight as a cross-linking agent, Irganox 1010 (manufactured by BASF) 0.5 parts by weight as an antioxidant. As a catalyst, 0.03 part by weight of Nasem ferrous iron (manufactured by Nippon Kagaku Sangyo Co., Ltd.) was diluted with ethyl acetate so that the total solid content was 50% by weight to obtain a urethane-based pressure-sensitive adhesive solution. Then, the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 μm, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 μm, and the drying temperature is 130 ° C. , Cure and dry under the condition of drying time of 3 minutes to prepare a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition (C3). Next, the surface of the obtained pressure-sensitive adhesive layer was treated with a silicone-treated release sheet (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 μm, one of which was treated with silicone. The surfaces were bonded together to obtain a surface protective film (C3). Aging was performed at room temperature for 5 days for evaluation. The release sheet was peeled off immediately before the evaluation. The results are shown in Table 5.
〔比較例４〕
　ウレタンプレポリマー５０重量部、ポリオールとして、ヒドロキシル基を３個有するポリオールであるプレミノールＳ３０１１（旭硝子社製、Ｍｎ＝１００００）４０重量部、ヒドロキシル基を３個有するポリオールであるサンニックスＧＰ３０００（三洋化成社製、Ｍｎ＝３０００）５重量部、ヒドロキシル基を３個有するポリオールであるサンニックスＧＰ１０００（三洋化成社製、Ｍｎ＝１０００）５重量部、架橋剤としてイソシアネート化合物（コロネートＨＸ：Ｃ／ＨＸ、日本ポリウレタン社製）１０．８重量部、酸化防止剤として、Ｉｒｇａｎｏｘ１０１０（ＢＡＳＦ社製）０．５重量部、触媒として、ナーセム第２鉄（日本化学産業社製）０．０３重量部を、全体の固形分が５０重量％となるように酢酸エチルで希釈し、ウレタン系粘着剤溶液を得た。そして、ウレタン系粘着剤溶液を、ポリエステル樹脂からなる基材（商品名「Ｔ１００－７５Ｓ」、厚み７５μｍ、三菱ケミカル株式会社製）に乾燥後の厚みが７５μｍとなるよう塗布し、乾燥温度１３０℃、乾燥時間３分の条件でキュアーして乾燥し、粘着剤組成物（Ｃ４）からなる粘着剤層を作製した。次いで、得られた粘着剤層の表面に、一方の面にシリコーン処理を施した厚さ２５μｍのポリエステル樹脂からなる剥離シート（商品名「ＭＲＦ２５」、厚み２５μｍ、三菱ケミカル株式会社製）のシリコーン処理面を貼合せて、表面保護フィルム（Ｃ４）を得た。常温で５日間エージングを行い、評価を行った。剥離シートは評価の直前に剥離した。結果を表５に示した。 [Comparative Example 4]
50 parts by weight of urethane prepolymer, 40 parts by weight of Preminol S3011 (Mn = 10000, manufactured by Asahi Glass Co., Ltd.), which is a polyol having 3 hydroxyl groups, and Sanniks GP3000 (Sanyo Kasei Co., Ltd.), which is a polyol having 3 hydroxyl groups. Mn = 3000) 5 parts by weight, Sanniks GP1000 (Mn = 1000, manufactured by Sanyo Kasei Co., Ltd.), which is a polyol having three hydroxyl groups, 5 parts by weight, isocyanate compound (Coronate HX: C / HX, Japan) as a cross-linking agent 10.8 parts by weight of polyurethane (manufactured by Polyurethane), 0.5 parts by weight of Irganox1010 (manufactured by BASF) as an antioxidant, and 0.03 parts by weight of Nasem ferrous iron (manufactured by Nippon Kagaku Sangyo) as a catalyst. It was diluted with ethyl acetate so that the solid content was 50% by weight to obtain a urethane-based pressure-sensitive adhesive solution. Then, the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 μm, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 μm, and the drying temperature is 130 ° C. , Cure and dry under the condition of drying time of 3 minutes to prepare a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition (C4). Next, the surface of the obtained pressure-sensitive adhesive layer was treated with a silicone-treated release sheet (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 μm, one of which was treated with silicone. The surfaces were bonded together to obtain a surface protective film (C4). Aging was performed at room temperature for 5 days for evaluation. The release sheet was peeled off immediately before the evaluation. The results are shown in Table 5.
〔比較例５〕
　ウレタンプレポリマー５０重量部、ポリオールとして、ヒドロキシル基を３個有するポリオールであるプレミノールＳ３０１１（旭硝子社製、Ｍｎ＝１００００）２４重量部、ヒドロキシル基を３個有するポリオールであるサンニックスＧＰ３０００（三洋化成社製、Ｍｎ＝３０００）２６重量部、架橋剤としてイソシアネート化合物（コロネートＨＸ：Ｃ／ＨＸ、日本ポリウレタン社製）１１．３重量部、酸化防止剤として、Ｉｒｇａｎｏｘ１０１０（ＢＡＳＦ社製）０．５重量部、触媒として、ナーセム第２鉄（日本化学産業社製）０．０３重量部を、全体の固形分が５０重量％となるように酢酸エチルで希釈し、ウレタン系粘着剤溶液を得た。そして、ウレタン系粘着剤溶液を、ポリエステル樹脂からなる基材（商品名「Ｔ１００－７５Ｓ」、厚み７５μｍ、三菱ケミカル株式会社製）に乾燥後の厚みが７５μｍとなるよう塗布し、乾燥温度１３０℃、乾燥時間３分の条件でキュアーして乾燥し、粘着剤組成物（Ｃ５）からなる粘着剤層を作製した。次いで、得られた粘着剤層の表面に、一方の面にシリコーン処理を施した厚さ２５μｍのポリエステル樹脂からなる剥離シート（商品名「ＭＲＦ２５」、厚み２５μｍ、三菱ケミカル株式会社製）のシリコーン処理面を貼合せて、表面保護フィルム（Ｃ５）を得た。常温で５日間エージングを行い、評価を行った。剥離シートは評価の直前に剥離した。結果を表５に示した。 [Comparative Example 5]
Urethane prepolymer 50 parts by weight, as a polyol, Preminol S3011 (Mn = 10000, manufactured by Asahi Glass Co., Ltd.), which is a polyol having three hydroxyl groups, 24 parts by weight, Sanniks GP3000 (Sanyo Kasei Co., Ltd.), which is a polyol having three hydroxyl groups. , Mn = 3000) 26 parts by weight, isocyanate compound (Coronate HX: C / HX, manufactured by Nippon Polyurethane Co., Ltd.) 11.3 parts by weight as a cross-linking agent, Irganox 1010 (manufactured by BASF) 0.5 parts by weight as an antioxidant. As a catalyst, 0.03 part by weight of Nasem ferrous iron (manufactured by Nippon Kagaku Sangyo Co., Ltd.) was diluted with ethyl acetate so that the total solid content was 50% by weight to obtain a urethane-based pressure-sensitive adhesive solution. Then, the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 μm, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 μm, and the drying temperature is 130 ° C. , Cure and dry under the condition of drying time of 3 minutes to prepare a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition (C5). Next, the surface of the obtained pressure-sensitive adhesive layer was treated with silicone on a release sheet (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 μm, one of which was treated with silicone. The surfaces were bonded together to obtain a surface protective film (C5). Aging was performed at room temperature for 5 days for evaluation. The release sheet was peeled off immediately before the evaluation. The results are shown in Table 5.
〔比較例６〕
　ウレタンプレポリマー５０重量部、ポリオールとして、ヒドロキシル基を３個有するポリオールであるプレミノールＳ３０１１（旭硝子社製、Ｍｎ＝１００００）５０重量部、架橋剤としてイソシアネート化合物（コロネートＨＸ：Ｃ／ＨＸ、日本ポリウレタン社製）６．０重量部、酸化防止剤として、Ｉｒｇａｎｏｘ１０１０（ＢＡＳＦ社製）０．５重量部、触媒として、ナーセム第２鉄（日本化学産業社製）０．０３重量部を、全体の固形分が５０重量％となるように酢酸エチルで希釈し、ウレタン系粘着剤溶液を得た。そして、ウレタン系粘着剤溶液を、ポリエステル樹脂からなる基材（商品名「Ｔ１００－７５Ｓ」、厚み７５μｍ、三菱ケミカル株式会社製）に乾燥後の厚みが７５μｍとなるよう塗布し、乾燥温度１３０℃、乾燥時間３分の条件でキュアーして乾燥し、粘着剤組成物（Ｃ６）からなる粘着剤層を作製した。次いで、得られた粘着剤層の表面に、一方の面にシリコーン処理を施した厚さ２５μｍのポリエステル樹脂からなる剥離シート（商品名「ＭＲＦ２５」、厚み２５μｍ、三菱ケミカル株式会社製）のシリコーン処理面を貼合せて、表面保護フィルム（Ｃ６）を得た。常温で５日間エージングを行い、評価を行った。剥離シートは評価の直前に剥離した。結果を表５に示した。 [Comparative Example 6]
50 parts by weight of urethane prepolymer, 50 parts by weight of Preminol S3011 (Mn = 10000, manufactured by Asahi Glass Co., Ltd.), which is a polyol having three hydroxyl groups as a polyol, and an isocyanate compound (Coronate HX: C / HX, Polyurethane Japan) as a cross-linking agent. (Manufactured) 6.0 parts by weight, Irganox 1010 (manufactured by BASF) 0.5 parts by weight as an antioxidant, and Nasem ferrous iron (manufactured by Nippon Kagaku Sangyo Co., Ltd.) 0.03 parts by weight as a catalyst, as a whole solid content. Was diluted with ethyl acetate so as to be 50% by weight to obtain a urethane-based pressure-sensitive adhesive solution. Then, the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 μm, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 μm, and the drying temperature is 130 ° C. , Cure and dry under the condition of drying time of 3 minutes to prepare a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition (C6). Next, the surface of the obtained pressure-sensitive adhesive layer was treated with a silicone-treated release sheet (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 μm, one of which was treated with silicone. The surfaces were bonded together to obtain a surface protective film (C6). Aging was performed at room temperature for 5 days for evaluation. The release sheet was peeled off immediately before the evaluation. The results are shown in Table 5.
〔比較例７〕
　ウレタンプレポリマー３０重量部、ポリオールとして、ヒドロキシル基を３個有するポリオールであるプレミノールＳ３０１１（旭硝子社製、Ｍｎ＝１００００）７０重量部、架橋剤としてイソシアネート化合物（コロネートＨＸ：Ｃ／ＨＸ、日本ポリウレタン社製）７．２重量部、酸化防止剤として、Ｉｒｇａｎｏｘ１０１０（ＢＡＳＦ社製）０．５重量部、触媒として、ナーセム第２鉄（日本化学産業社製）０．０３重量部を、全体の固形分が５０重量％となるように酢酸エチルで希釈し、ウレタン系粘着剤溶液を得た。そして、ウレタン系粘着剤溶液を、ポリエステル樹脂からなる基材（商品名「Ｔ１００－７５Ｓ」、厚み７５μｍ、三菱ケミカル株式会社製）に乾燥後の厚みが７５μｍとなるよう塗布し、乾燥温度１３０℃、乾燥時間３分の条件でキュアーして乾燥し、粘着剤組成物（Ｃ７）からなる粘着剤層を作製した。次いで、得られた粘着剤層の表面に、一方の面にシリコーン処理を施した厚さ２５μｍのポリエステル樹脂からなる剥離シート（商品名「ＭＲＦ２５」、厚み２５μｍ、三菱ケミカル株式会社製）のシリコーン処理面を貼合せて、表面保護フィルム（Ｃ７）を得た。常温で５日間エージングを行い、評価を行った。剥離シートは評価の直前に剥離した。結果を表５に示した。 [Comparative Example 7]
30 parts by weight of urethane prepolymer, 70 parts by weight of Preminol S3011 (Mn = 10000, manufactured by Asahi Glass Co., Ltd.), which is a polyol having three hydroxyl groups as a polyol, and an isocyanate compound (Coronate HX: C / HX, Polyurethane Japan) as a cross-linking agent. (Manufactured) 7.2 parts by weight, Irganox1010 (manufactured by BASF) 0.5 parts by weight as an antioxidant, and 0.03 parts by weight of Nasem ferrous iron (manufactured by Nippon Kagaku Sangyo Co., Ltd.) as a catalyst, as a whole solid content. Was diluted with ethyl acetate so as to be 50% by weight to obtain a urethane-based pressure-sensitive adhesive solution. Then, the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 μm, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 μm, and the drying temperature is 130 ° C. , Cure and dry under the condition of drying time of 3 minutes to prepare a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition (C7). Next, the surface of the obtained pressure-sensitive adhesive layer was treated with a silicone-treated release sheet (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 μm, one of which was treated with silicone. The surfaces were bonded together to obtain a surface protective film (C7). Aging was performed at room temperature for 5 days for evaluation. The release sheet was peeled off immediately before the evaluation. The results are shown in Table 5.
〔比較例８〕
　ウレタンプレポリマー１０重量部、ポリオールとして、ヒドロキシル基を３個有するポリオールであるプレミノールＳ３０１１（旭硝子社製、Ｍｎ＝１００００）９０重量部、架橋剤としてイソシアネート化合物（コロネートＨＸ：Ｃ／ＨＸ、日本ポリウレタン社製）８．５重量部、酸化防止剤として、Ｉｒｇａｎｏｘ１０１０（ＢＡＳＦ社製）０．５重量部、触媒として、ナーセム第２鉄（日本化学産業社製）０．０３重量部を、全体の固形分が５０重量％となるように酢酸エチルで希釈し、ウレタン系粘着剤溶液を得た。そして、ウレタン系粘着剤溶液を、ポリエステル樹脂からなる基材（商品名「Ｔ１００－７５Ｓ」、厚み７５μｍ、三菱ケミカル株式会社製）に乾燥後の厚みが７５μｍとなるよう塗布し、乾燥温度１３０℃、乾燥時間３分の条件でキュアーして乾燥し、粘着剤組成物（Ｃ８）からなる粘着剤層を作製した。次いで、得られた粘着剤層の表面に、一方の面にシリコーン処理を施した厚さ２５μｍのポリエステル樹脂からなる剥離シート（商品名「ＭＲＦ２５」、厚み２５μｍ、三菱ケミカル株式会社製）のシリコーン処理面を貼合せて、表面保護フィルム（Ｃ８）を得た。常温で５日間エージングを行い、評価を行った。剥離シートは評価の直前に剥離した。結果を表５に示した。 [Comparative Example 8]
10 parts by weight of urethane prepolymer, 90 parts by weight of Preminol S3011 (Mn = 10000, manufactured by Asahi Glass Co., Ltd.), which is a polyol having three hydroxyl groups as a polyol, and an isocyanate compound (Coronate HX: C / HX, Polyurethane Japan) as a cross-linking agent. ) 8.5 parts by weight, Irganox 1010 (manufactured by BASF) 0.5 parts by weight as an antioxidant, and 0.03 parts by weight of Nasem ferrous iron (manufactured by Nippon Kagaku Sangyo Co., Ltd.) as a catalyst, as a whole solid content. Was diluted with ethyl acetate so as to be 50% by weight to obtain a urethane-based pressure-sensitive adhesive solution. Then, the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 μm, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 μm, and the drying temperature is 130 ° C. , Cure and dry under the condition of drying time of 3 minutes to prepare a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition (C8). Next, the surface of the obtained pressure-sensitive adhesive layer was treated with a silicone-treated release sheet (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 μm, one of which was treated with silicone. The surfaces were bonded together to obtain a surface protective film (C8). Aging was performed at room temperature for 5 days for evaluation. The release sheet was peeled off immediately before the evaluation. The results are shown in Table 5.
〔比較例９〕
　ウレタンプレポリマー３０重量部、ポリオールとして、ヒドロキシル基を３個有するポリオールであるプレミノールＳ３０１１（旭硝子社製、Ｍｎ＝１００００）４０重量部、ヒドロキシル基を３個有するポリオールであるサンニックスＧＰ３０００（三洋化成社製、Ｍｎ＝３０００）３０重量部、架橋剤としてイソシアネート化合物（コロネートＨＸ：Ｃ／ＨＸ、日本ポリウレタン社製）１３．４重量部、酸化防止剤として、Ｉｒｇａｎｏｘ１０１０（ＢＡＳＦ社製）０．５重量部、触媒として、ナーセム第２鉄（日本化学産業社製）０．０３重量部を、全体の固形分が５０重量％となるように酢酸エチルで希釈し、ウレタン系粘着剤溶液を得た。そして、ウレタン系粘着剤溶液を、ポリエステル樹脂からなる基材（商品名「Ｔ１００－７５Ｓ」、厚み７５μｍ、三菱ケミカル株式会社製）に乾燥後の厚みが７５μｍとなるよう塗布し、乾燥温度１３０℃、乾燥時間３分の条件でキュアーして乾燥し、粘着剤組成物（Ｃ９）からなる粘着剤層を作製した。次いで、得られた粘着剤層の表面に、一方の面にシリコーン処理を施した厚さ２５μｍのポリエステル樹脂からなる剥離シート（商品名「ＭＲＦ２５」、厚み２５μｍ、三菱ケミカル株式会社製）のシリコーン処理面を貼合せて、表面保護フィルム（Ｃ９）を得た。常温で５日間エージングを行い、評価を行った。剥離シートは評価の直前に剥離した。結果を表５に示した。 [Comparative Example 9]
30 parts by weight of urethane prepolymer, 40 parts by weight of Preminol S3011 (Mn = 10000, manufactured by Asahi Glass Co., Ltd.), which is a polyol having 3 hydroxyl groups, and Sanniks GP3000 (Sanyo Kasei Co., Ltd.), which is a polyol having 3 hydroxyl groups. , Mn = 3000) 30 parts by weight, isocyanate compound (Coronate HX: C / HX, manufactured by Nippon Polyurethane Co., Ltd.) 13.4 parts by weight as a cross-linking agent, Irganox 1010 (manufactured by BASF) 0.5 parts by weight as an antioxidant. As a catalyst, 0.03 part by weight of Nasem ferrous iron (manufactured by Nippon Kagaku Sangyo Co., Ltd.) was diluted with ethyl acetate so that the total solid content was 50% by weight to obtain a urethane-based pressure-sensitive adhesive solution. Then, the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 μm, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 μm, and the drying temperature is 130 ° C. , Cure and dry under the condition of drying time of 3 minutes to prepare a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition (C9). Next, the surface of the obtained pressure-sensitive adhesive layer was treated with a silicone-treated release sheet (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 μm, one of which was treated with silicone. The surfaces were bonded together to obtain a surface protective film (C9). Aging was performed at room temperature for 5 days for evaluation. The release sheet was peeled off immediately before the evaluation. The results are shown in Table 5.
〔比較例１０〕
　ウレタンプレポリマー１０重量部、ポリオールとして、ヒドロキシル基を３個有するポリオールであるプレミノールＳ３０１１（旭硝子社製、Ｍｎ＝１００００）５０重量部、ヒドロキシル基を３個有するポリオールであるサンニックスＧＰ３０００（三洋化成社製、Ｍｎ＝３０００）４０重量部、架橋剤としてイソシアネート化合物（コロネートＨＸ：Ｃ／ＨＸ、日本ポリウレタン社製）１６．７重量部、酸化防止剤として、Ｉｒｇａｎｏｘ１０１０（ＢＡＳＦ社製）０．５重量部、触媒として、ナーセム第２鉄（日本化学産業社製）０．０３重量部を、全体の固形分が５０重量％となるように酢酸エチルで希釈し、ウレタン系粘着剤溶液を得た。そして、ウレタン系粘着剤溶液を、ポリエステル樹脂からなる基材（商品名「Ｔ１００－７５Ｓ」、厚み７５μｍ、三菱ケミカル株式会社製）に乾燥後の厚みが７５μｍとなるよう塗布し、乾燥温度１３０℃、乾燥時間３分の条件でキュアーして乾燥し、粘着剤組成物（Ｃ１０）からなる粘着剤層を作製した。次いで、得られた粘着剤層の表面に、一方の面にシリコーン処理を施した厚さ２５μｍのポリエステル樹脂からなる剥離シート（商品名「ＭＲＦ２５」、厚み２５μｍ、三菱ケミカル株式会社製）のシリコーン処理面を貼合せて、表面保護フィルム（Ｃ１０）を得た。常温で５日間エージングを行い、評価を行った。剥離シートは評価の直前に剥離した。結果を表５に示した。 [Comparative Example 10]
10 parts by weight of urethane prepolymer, 50 parts by weight of Preminol S3011 (Mn = 10000, manufactured by Asahi Glass Co., Ltd.), which is a polyol having 3 hydroxyl groups, and Sanniks GP3000 (Sanyo Kasei Co., Ltd.), which is a polyol having 3 hydroxyl groups. , Mn = 3000) 40 parts by weight, isocyanate compound (Coronate HX: C / HX, manufactured by Nippon Polyurethane Co., Ltd.) 16.7 parts by weight as a cross-linking agent, Irganox1010 (manufactured by BASF) 0.5 parts by weight as an antioxidant. As a catalyst, 0.03 part by weight of Nasem ferrous iron (manufactured by Nippon Kagaku Sangyo Co., Ltd.) was diluted with ethyl acetate so that the total solid content was 50% by weight to obtain a urethane-based pressure-sensitive adhesive solution. Then, the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 μm, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 μm, and the drying temperature is 130 ° C. , Cure and dry under the condition of drying time of 3 minutes to prepare a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition (C10). Next, the surface of the obtained pressure-sensitive adhesive layer was treated with a silicone-treated release sheet (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin having a thickness of 25 μm, one of which was treated with silicone. The surfaces were bonded together to obtain a surface protective film (C10). Aging was performed at room temperature for 5 days for evaluation. The release sheet was peeled off immediately before the evaluation. The results are shown in Table 5.
〔比較例１１〕
　ポリオールとして、ヒドロキシル基を３個有するポリオールであるプレミノールＳ３０１１（旭硝子社製、Ｍｎ＝１００００）５０重量部、ヒドロキシル基を３個有するポリオールであるサンニックスＧＰ３０００（三洋化成社製、Ｍｎ＝３０００）５０重量部、架橋剤としてイソシアネート化合物（コロネートＨＸ：Ｃ／ＨＸ、日本ポリウレタン社製）１９．３重量部、酸化防止剤として、Ｉｒｇａｎｏｘ１０１０（ＢＡＳＦ社製）０．５重量部、触媒として、ナーセム第２鉄（日本化学産業社製）０．０３重量部を、全体の固形分が５０重量％となるように酢酸エチルで希釈し、ウレタン系粘着剤溶液を得た。そして、ウレタン系粘着剤溶液を、ポリエステル樹脂からなる基材（商品名「Ｔ１００－７５Ｓ」、厚み７５μｍ、三菱ケミカル株式会社製）に塗布して乾燥させて厚みが７５μｍの粘着剤層を作製しようとしたが、ウレタン系粘着剤溶液の粘度が低く、このような厚膜化ができなかった。結果を表５に示した。 [Comparative Example 11]
As the polyol, 50 parts by weight of Preminol S3011 (Mn = 10000, manufactured by Asahi Glass Co., Ltd.), which is a polyol having three hydroxyl groups, and Sanniks GP3000 (Mn = 3000, Mn = 3000, manufactured by Sanyo Kasei Co., Ltd.), which is a polyol having three hydroxyl groups. By weight part, isocyanate compound (Coronate HX: C / HX, manufactured by Nippon Polyurethane Co., Ltd.) 19.3 parts by weight as a cross-linking agent, Irganox1010 (manufactured by BASF) 0.5 parts by weight as an antioxidant, Nasem No. 2 as a catalyst. 0.03 part by weight of iron (manufactured by Nippon Kagaku Sangyo Co., Ltd.) was diluted with ethyl acetate so that the total solid content was 50% by weight to obtain a urethane-based pressure-sensitive adhesive solution. Then, let's apply a urethane-based pressure-sensitive adhesive solution to a base material made of polyester resin (trade name "T100-75S", thickness 75 μm, manufactured by Mitsubishi Chemical Co., Ltd.) and dry it to prepare a pressure-sensitive adhesive layer having a thickness of 75 μm. However, the viscosity of the urethane-based adhesive solution was low, and such a thick film could not be formed. The results are shown in Table 5.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006
〔実施例５３～１０４〕
　実施例１～５２で得られたセパレーター付の表面保護フィルムのそれぞれについて、セパレーターを剥がし、光学部材である偏光板（日東電工株式会社製、商品名「ＴＥＧ１４６５ＤＵＨＣ」）に貼着し、表面保護フィルムが貼着された光学部材を得た。 [Examples 53 to 104]
For each of the surface protective films with separators obtained in Examples 1 to 52, the separator was peeled off and attached to a polarizing plate (manufactured by Nitto Denko Corporation, trade name "TEG1465DUHC") which is an optical member, and the surface protective film was attached. An optical member to which was attached was obtained.
〔実施例１０５～１５６〕
　実施例１～５２で得られたセパレーター付の表面保護フィルムのそれぞれについて、セパレーターを剥がし、電子部材である導電性フィルム（日東電工株式会社製、商品名「エレクリスタＶ２７０Ｌ－ＴＦＭＰ」）に貼着し、表面保護フィルムが貼着された電子部材を得た。 [Examples 105 to 156]
For each of the surface protective films with separators obtained in Examples 1 to 52, the separator was peeled off and attached to a conductive film (manufactured by Nitto Denko Corporation, trade name "Electrica V270L-TFMP") which is an electronic member. , An electronic member to which a surface protective film was attached was obtained.
　本発明の表面保護フィルムは、任意の適切な用途に用い得る。好ましくは、本発明の表面保護フィルムは、光学部材や電子部材の表面保護に好ましく用いられる。 The surface protective film of the present invention can be used for any suitable application. Preferably, the surface protective film of the present invention is preferably used for surface protection of optical members and electronic members.
　１　　　　　　基材層
　２　　　　　　粘着剤層
１０　　　　　　表面保護フィルム
 
  1 Base material layer 2 Adhesive layer 10 Surface protective film

Claims (8)

  1. 　ウレタン系粘着剤層を含む表面保護フィルムであって、
    　該ウレタン系粘着剤層は、ウレタン系粘着剤組成物から形成されるウレタン系粘着剤から構成され、
    　該ウレタン系粘着剤組成物が、ウレタンプレポリマーＰとポリオールＡと多官能イソシアネート化合物Ｂを含み、
    　該ウレタンプレポリマーＰと該ポリオールＡの重量比が、Ｐ：Ａ＝（５０～９９）：（１～５０）であり、
    　該ポリオールＡは、数平均分子量Ｍｎが５０００～２００００の第１のポリオールＡ１と数平均分子量Ｍｎが３００～４９９９の第２のポリオールＡ２を含み、
    　該第１のポリオールＡ１と該第２のポリオールＡ２との重量比率が、１．０≦（Ａ１／Ａ２）≦３．５である、
    　表面保護フィルム。     A surface protective film containing a urethane-based adhesive layer,
    The urethane-based pressure-sensitive adhesive layer is composed of a urethane-based pressure-sensitive adhesive formed from a urethane-based pressure-sensitive adhesive composition.
    The urethane-based pressure-sensitive adhesive composition contains a urethane prepolymer P, a polyol A, and a polyfunctional isocyanate compound B.
    The weight ratio of the urethane prepolymer P to the polyol A is P: A = (50 to 99) :( 1 to 50).
    The polyol A contains a first polyol A1 having a number average molecular weight Mn of 5000 to 20000 and a second polyol A2 having a number average molecular weight Mn of 300 to 4999.
    The weight ratio of the first polyol A1 to the second polyol A2 is 1.0 ≦ (A1 / A2) ≦ 3.5.
    Surface protection film.
  2. 　前記ウレタン系粘着剤組成物がイオン性化合物を含み、前記ウレタンプレポリマーＰと前記ポリオールＡの合計量に対する該イオン性化合物の含有割合が、０．０５重量％以上である、請求項１に記載の表面保護フィルム。 The first aspect of claim 1, wherein the urethane-based pressure-sensitive adhesive composition contains an ionic compound, and the content ratio of the ionic compound to the total amount of the urethane prepolymer P and the polyol A is 0.05% by weight or more. Surface protective film.
  3. 　前記ウレタン系粘着剤組成物がフッ素系添加剤およびシリコーン系添加剤からなる群から選ばれる少なくとも１種を含み、前記ウレタンプレポリマーＰと前記ポリオールＡの合計量に対する該フッ素系添加剤および該シリコーン系添加剤の合計量の含有割合が、０．０１重量％以上である、請求項１または２に記載の表面保護フィルム。 The urethane-based pressure-sensitive adhesive composition contains at least one selected from the group consisting of a fluorine-based additive and a silicone-based additive, and the fluorine-based additive and the silicone with respect to the total amount of the urethane prepolymer P and the polyol A. The surface protective film according to claim 1 or 2, wherein the content ratio of the total amount of the system additives is 0.01% by weight or more.
  4. 　前記第１のポリオールＡ１と前記第２のポリオールＡ２との重量比率が、１．０≦（Ａ１／Ａ２）≦２．０である、請求項１から３までのいずれかに記載の表面保護フィルム。 The surface protective film according to any one of claims 1 to 3, wherein the weight ratio of the first polyol A1 to the second polyol A2 is 1.0 ≦ (A1 / A2) ≦ 2.0. ..
  5. 　前記ウレタン系粘着剤層をガラス板に貼り合わせて２３℃で３０分後に、該ガラス板から剥離角度１８０度、剥離速度３００ｍｍ／分によって剥離した際の剥離力が、０．５ｇｆ／２５ｍｍ～２．０ｇｆ／２５ｍｍである、請求項１から４までのいずれかに記載の表面保護フィルム。 After 30 minutes at 23 ° C. after the urethane adhesive layer was attached to the glass plate, the peeling force when peeled from the glass plate at a peeling angle of 180 degrees and a peeling speed of 300 mm / min was 0.5 gf / 25 mm to 2. The surface protective film according to any one of claims 1 to 4, which is 0.0 gf / 25 mm.
  6. 　前記ウレタン系粘着剤層をガラス板に貼り合わせて２３℃で２４時間後に該ガラス板から剥離角度１８０度、剥離速度０．３ｍ／分によって剥離した後の、該ガラス板に対する残留接着率が、８０％以上である、請求項１から５までのいずれかに記載の表面保護フィルム。 After 24 hours after the urethane adhesive layer was attached to the glass plate and peeled from the glass plate at a peeling angle of 180 degrees and a peeling speed of 0.3 m / min, the residual adhesion rate to the glass plate was determined. The surface protective film according to any one of claims 1 to 5, which is 80% or more.
  7. 　請求項１から６までのいずれかに記載の表面保護フィルムが貼着された光学部材。 An optical member to which the surface protective film according to any one of claims 1 to 6 is attached.
  8. 　請求項１から６までのいずれかに記載の表面保護フィルムが貼着された電子部材。 An electronic member to which the surface protective film according to any one of claims 1 to 6 is attached.
PCT/JP2021/044740 2020-12-21 2021-12-06 Surface protective film WO2022138113A1 (en)

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Citations (6)

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Publication number Priority date Publication date Assignee Title
JP2014111701A (en) * 2012-08-31 2014-06-19 Nitto Denko Corp Urethane-based pressure-sensitive adhesive agent and surface protective film using the same
JP2016017109A (en) * 2014-07-07 2016-02-01 リンテック株式会社 Surface protective film
JP2016108442A (en) * 2014-12-05 2016-06-20 日東電工株式会社 Surface protective film
JP2016176068A (en) * 2015-03-20 2016-10-06 東洋インキＳｃホールディングス株式会社 Adhesive and adhesive tape
JP2017160422A (en) * 2016-03-04 2017-09-14 日東電工株式会社 Surface protective film
JP2018062595A (en) * 2016-10-14 2018-04-19 東洋インキＳｃホールディングス株式会社 Adhesive and adhesive sheet

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014111701A (en) * 2012-08-31 2014-06-19 Nitto Denko Corp Urethane-based pressure-sensitive adhesive agent and surface protective film using the same
JP2016017109A (en) * 2014-07-07 2016-02-01 リンテック株式会社 Surface protective film
JP2016108442A (en) * 2014-12-05 2016-06-20 日東電工株式会社 Surface protective film
JP2016176068A (en) * 2015-03-20 2016-10-06 東洋インキＳｃホールディングス株式会社 Adhesive and adhesive tape
JP2017160422A (en) * 2016-03-04 2017-09-14 日東電工株式会社 Surface protective film
JP2018062595A (en) * 2016-10-14 2018-04-19 東洋インキＳｃホールディングス株式会社 Adhesive and adhesive sheet

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