WO2025047321A1 - 表面保護フィルム - Google Patents

表面保護フィルム Download PDF

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Publication number
WO2025047321A1
WO2025047321A1 PCT/JP2024/027966 JP2024027966W WO2025047321A1 WO 2025047321 A1 WO2025047321 A1 WO 2025047321A1 JP 2024027966 W JP2024027966 W JP 2024027966W WO 2025047321 A1 WO2025047321 A1 WO 2025047321A1
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WO
WIPO (PCT)
Prior art keywords
urethane
weight
sensitive adhesive
polyol
surface protection
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/JP2024/027966
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English (en)
French (fr)
Japanese (ja)
Inventor
翔悟 佐々木
千尋 舟木
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nitto Denko Corp
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Nitto Denko Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nitto Denko Corp filed Critical Nitto Denko Corp
Priority to JP2025542849A priority Critical patent/JPWO2025047321A1/ja
Priority to CN202480055651.2A priority patent/CN121752682A/zh
Priority to KR1020267007206A priority patent/KR20260056181A/ko
Publication of WO2025047321A1 publication Critical patent/WO2025047321A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C08L83/06—Polysiloxanes containing silicon bound to oxygen-containing groups
    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/06—Polyurethanes from polyesters
    • 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
    • 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]
    • 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

Definitions

  • the present invention relates to a surface protection film.
  • a surface protective film is generally applied to the exposed surfaces of the optical and electronic components to prevent the surfaces of the optical and electronic components from being damaged during processing, assembly, inspection, transportation, etc.
  • Such a surface protective film is peeled off from the optical and electronic components when surface protection is no longer necessary (Patent Document 1).
  • the film When peeling a surface protection film from an optical or electronic component to which it is attached, the film must be able to peel off smoothly only at the interface between the film and the optical or electronic component, i.e., it must have easy peelability.
  • Patent Documents 2 and 3 As a means of imparting easy peelability to a surface protection film, a technique of adding a fluorine-based compound or a silicone-based compound to an adhesive composition that forms the adhesive that constitutes the adhesive layer has been reported (Patent Documents 2 and 3).
  • Patent Documents 2 and 3 such conventional additives for imparting easy peelability tend to be unevenly distributed not only on the surface side of the adhesive layer but also on the substrate side, resulting in a problem of reduced anchoring strength between the substrate and the adhesive layer.
  • urethane-based adhesives are known as preferred adhesives that constitute the adhesive layer of surface protection films whose main purpose is to attach them to the exposed surfaces of optical or electronic components (Patent Documents 1 to 3).
  • Patent Documents 1 to 3 urethane-based adhesives
  • conventional surface protection films that include an adhesive layer made of a urethane-based adhesive can produce glue residue when cut, which can easily lead to process defects.
  • the object of the present invention is to provide a surface protection film that includes an adhesive layer and that can simultaneously exhibit excellent anchoring power and suppress the generation of glue residue when cut.
  • a surface protection film is a surface protection film including a pressure-sensitive adhesive layer composed of a urethane-based pressure-sensitive adhesive, the urethane-based pressure-sensitive adhesive including a urethane polymer, the urethane-based pressure-sensitive adhesive being formed from a urethane-based pressure-sensitive adhesive composition, the urethane-based pressure-sensitive adhesive composition including a base polymer (A) and a silicone-based compound (B), the base polymer (A) being a urethane prepolymer obtained by reacting a polyol with a polyfunctional isocyanate compound, the polyol including a polyester polyol (a1) and a polyether polyol (a2), the polyether polyol (a2) including a polyol (a3) including three or more groups of at least one type selected from the group consisting of a methylene group and a methine group.
  • the content of the polyester polyol (a1) in the polyol may be 0.01% by weight to 10.0% by weight.
  • the urethane-based pressure-sensitive adhesive composition may contain a catalyst, and the catalyst may be at least one selected from the group consisting of zinc-based catalysts and titanium-based catalysts.
  • the average peel strength is defined as adhesive strength (I)
  • adhesive strength (II) when the pressure-sensitive adhesive layer is attached to a glass plate, left for 1 day at an environmental temperature of 50° C., and then the average peel strength is peeled from the glass plate at a peel angle of 180° and a peel speed of 300 mm/min, the rate of increase over time of adhesion to the glass plate, defined as [adhesive strength (II)/adhesive strength (I)] ⁇ 100(%), may be less than 210%.
  • the silicone-based compound (B) may contain at least one selected from the group consisting of reactive silicone oils having at least one selected from the group consisting of polyether structures and carbinol structures, and non-reactive silicone oils having a polyether structure and an HLB value of 15 or less.
  • the surface of the pressure-sensitive adhesive layer may have a surface free energy with respect to diiodomethane of 2.5 mJ/m 2 to 20.0 mJ/m 2 .
  • the content of the silicone-based compound (B) relative to 100 parts by weight of the base polymer (A) may be 0.01 parts by weight to 0.48 parts by weight.
  • An optical member according to an embodiment of the present invention includes the surface protection film according to any one of [1] to [7] above.
  • An electronic device according to an embodiment of the present invention includes the surface protection film according to any one of [1] to [7] above.
  • the present invention provides a surface protection film that includes an adhesive layer and that exhibits both excellent anchoring power and reduced generation of glue residue when cut.
  • FIG. 1 is a schematic cross-sectional view of a surface protection film according to one embodiment of the present invention.
  • weight Whenever the term “weight” appears in this specification, it may be read as “mass,” which is the commonly used SI unit for indicating weight.
  • the surface protection film according to the embodiment of the present invention includes a pressure-sensitive adhesive layer composed of a urethane-based pressure-sensitive adhesive.
  • the urethane-based pressure-sensitive adhesive includes a urethane polymer.
  • the urethane-based adhesive is formed from a urethane-based adhesive composition, which contains a base polymer (A) and a silicone-based compound (B).
  • the content of the base polymer (A) in the urethane-based adhesive composition is preferably 50% by weight to 100% by weight, more preferably 70% by weight to 99% by weight, even more preferably 80% by weight to 98% by weight, and particularly preferably 90% by weight to 97% by weight, calculated as solid content.
  • the content of the base polymer (A) in the urethane-based adhesive composition is preferably 60% by weight to 99.9% by weight, more preferably 70% by weight to 99% by weight, even more preferably 80% by weight to 98% by weight, and particularly preferably 90% by weight to 97% by weight, calculated as solids. If the content of the base polymer (A) in the urethane-based adhesive composition is within the above range, calculated as solids, the effects of the present invention can be more effectively achieved.
  • the surface protection film according to an embodiment of the present invention may contain any other appropriate components as long as the effects of the present invention are not impaired, so long as it contains an adhesive layer composed of a urethane-based adhesive.
  • the surface protection film according to an embodiment of the present invention contains a substrate and the above-mentioned adhesive layer.
  • the surface of the adhesive layer opposite the substrate may be provided with any appropriate release liner (sometimes called a release sheet or separator) for protection until use, etc.
  • FIG. 1 is a schematic cross-sectional view of a surface protection film according to one embodiment of the present invention.
  • the surface protection film 10 comprises a substrate 1 and an adhesive layer 2.
  • the substrate 1 and the adhesive layer 2 are directly laminated together.
  • the surface of the adhesive layer 2 opposite the substrate 1 may be provided with any suitable release liner (sometimes called a release sheet or separator) for protection until use (not shown).
  • release liners include release liners in which the surface of a substrate (liner substrate) such as paper or plastic film is silicone-treated, and release liners in which the surface of a substrate (liner substrate) such as paper or plastic film is laminated with a polyolefin resin.
  • the thickness of the release liner is preferably 1 ⁇ m to 500 ⁇ m, more preferably 3 ⁇ m to 450 ⁇ m, even more preferably 5 ⁇ m to 400 ⁇ m, and particularly preferably 10 ⁇ m to 300 ⁇ m.
  • the thickness of the surface protection film according to the embodiment of the present invention may be any appropriate thickness within a range that does not impair the effects of the present invention.
  • Such a thickness is preferably 5 ⁇ m to 500 ⁇ m, more preferably 10 ⁇ m to 450 ⁇ m, even more preferably 15 ⁇ m to 400 ⁇ m, and particularly preferably 20 ⁇ m to 300 ⁇ m.
  • the adhesive layer is attached to a glass plate, left for 30 minutes at an environmental temperature of 23° C., and then the surface protection film is peeled from the glass plate at a peel angle of 180 degrees and a peel speed of 300 mm/min.
  • the adhesive strength (I) is preferably 5.0 gf/25 mm or less, more preferably 4.0 gf/25 mm or less, even more preferably 3.5 gf/25 mm or less, even more preferably 3.0 gf/25 mm or less, particularly preferably 2.5 gf/25 mm or less, and most preferably 2.0 gf/25 mm or less.
  • the lower limit of the adhesive strength (I) is preferably 0.3 gf/25 mm or more in reality. If the adhesive strength (I) is within the above range, a surface protection film that adheres appropriately to an adherend and is easy to peel off can be provided. If the adhesive strength (I) is too large outside the above range, for example, the adhesive strength to the adherend may be too high, resulting in a surface protection film that is difficult to peel off. Details of the method for measuring the adhesive strength (I) will be described later.
  • the average peel strength is defined as adhesive strength (II), and the degree of increase in adhesive strength from the adhesive strength (I), i.e., the rate of increase in adhesive strength to the glass plate over time defined as [adhesive strength (II)/adhesive strength (I)] x 100 (%) is preferably less than 210%, more preferably 200% or less, even more preferably 190% or less, even more preferably 180% or less, even more preferably 170% or less, even more preferably 160% or less, even more preferably 150% or less, even more preferably 140% or less, particularly preferably 135% or less, and most preferably 130% or less.
  • the lower limit of the rate of increase in adhesive strength to the glass plate over time is preferably 100% or more. If the rate of increase in adhesive strength to glass plate over time is within the above range, the increase in adhesive strength to the adherend over time is suppressed, and a surface protection film that adheres appropriately even after a long time has passed after being attached to the adherend and is easy to peel off can be provided. If the rate of increase in adhesive strength to glass plate over time is too large outside the above range, for example, the adhesive strength to the adherend may increase over time, and after a long time has passed after being attached to the adherend, the adhesive strength may become strong and difficult to peel off. Details of the method for measuring the adhesive strength (II) will be described later.
  • the surface free energy of the pressure-sensitive adhesive layer surface to diiodomethane is preferably 2.5 mJ/m 2 to 20.0 mJ/m 2 , more preferably 3.0 mJ/m 2 to 18.0 mJ/m 2 , even more preferably 3.3 mJ/m 2 to 16.0 mJ/m 2 , and particularly preferably 3.5 mJ/m 2 to 15.0 mJ/m 2.
  • the adhesive strength of the pressure-sensitive adhesive layer (for example, the adhesive strength (I) described in this specification) may be too high, and the surface protection film may be difficult to peel off. If the surface free energy of the pressure-sensitive adhesive layer surface with respect to diiodomethane is too large, for example, there is a concern that the haze will become high.
  • the method for measuring the surface free energy of the pressure-sensitive adhesive layer surface with respect to diiodomethane will be described in detail below.
  • the haze of the surface protection film according to the embodiment of the present invention is preferably 7.0% or less, more preferably 6.0% or less, even more preferably 5.0% or less, even more preferably 4.0% or less, even more preferably 3.0% or less, particularly preferably 2.0% or less, and most preferably 1.5% or less.
  • the lower limit of the haze is preferably 0% or more. If the haze is within the above range, the transparency of the surface protection film is high, and it becomes possible to accurately perform inspections, for example, when the surface protection film is attached to the surface of an adherend such as an optical member or electronic member. If the haze is too large outside the above range, for example, the transparency of the surface protection film decreases, which may cause problems in the above-mentioned inspections. The method for measuring the haze will be described in detail later.
  • the surface protective film according to the embodiment of the present invention can be produced by any suitable method.
  • a production method include (1) A method of applying a solution or a hot melt of a material for forming the adhesive layer onto a substrate, (2) A method of applying a solution or a hot melt of a material for forming an adhesive layer onto a release liner to form an adhesive layer, and then transferring the adhesive layer onto a substrate; (3) A method of forming and coating a pressure-sensitive adhesive layer by extruding a material for forming the pressure-sensitive adhesive layer onto a substrate; (4) A method of extruding a substrate and a pressure-sensitive adhesive layer in two or more layers, (5) A method of laminating a single layer of a pressure-sensitive adhesive layer on a substrate, or a method of laminating a double layer of a pressure-sensitive adhesive layer together with a laminate layer, (6) A method of laminating a pressure-sensitive adhesive layer and a substrate-forming material such as a film or a laminate layer in a two-
  • the 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 pressure-sensitive adhesive layer is composed of a urethane-based pressure-sensitive adhesive, and the urethane-based pressure-sensitive adhesive is formed from a urethane-based pressure-sensitive adhesive composition.
  • the urethane-based pressure-sensitive adhesive formed from the urethane-based pressure-sensitive adhesive composition forms a layer shape to become the pressure-sensitive adhesive layer.
  • the adhesive layer may be formed by any suitable method.
  • a method may be used in which a urethane adhesive composition is applied to any suitable substrate, heated and dried as necessary, and cured as necessary to form an adhesive layer on the substrate.
  • the application method, heating and drying conditions, curing conditions, etc. may be appropriately selected from methods commonly known for forming adhesive layers.
  • the thickness of the adhesive layer can be set appropriately according to the purpose of the present invention, as long as it does not impair the effects of the present invention.
  • the thickness of the adhesive layer is typically 5 ⁇ m to 150 ⁇ m, preferably 10 ⁇ m to 120 ⁇ m, more preferably 20 ⁇ m to 110 ⁇ m, even more preferably 30 ⁇ m to 100 ⁇ m, and particularly preferably 40 ⁇ m to 90 ⁇ m.
  • the urethane-based adhesive contains a urethane polymer.
  • the urethane polymer in the urethane-based adhesive may be of only one type, or of two or more types.
  • the content of the urethane polymer in the urethane adhesive is preferably 60% by weight to 99.9% by weight, more preferably 70% by weight to 99.9% by weight, even more preferably 80% by weight to 99.9% by weight, particularly preferably 85% by weight to 99.9% by weight, and most preferably 90% by weight to 99.9% by weight, calculated as solids. If the content of the urethane polymer in the urethane adhesive is within the above range, calculated as solids, the effects of the present invention can be more effectively achieved.
  • the urethane polymer contained in the urethane-based adhesive is typically a prepolymer-type urethane polymer. There may be only one type of prepolymer-type urethane polymer, or two or more types.
  • known urethane polymers include "prepolymer-type urethane polymers” produced by reacting a urethane prepolymer with a polyfunctional isocyanate compound, and "one-shot-type urethane polymers” produced by directly reacting a polyol with a polyfunctional isocyanate compound without using a urethane prepolymer.
  • a urethane prepolymer is typically obtained by reacting a polyol with an excess of a polyfunctional isocyanate compound, and has an isocyanate group at the molecular end.
  • the prepolymer-type urethane polymer which is the urethane polymer contained in the urethane-based adhesive, is different from the one-shot-type urethane polymer.
  • the prepolymer type urethane polymer is obtained by reacting a urethane prepolymer as the base polymer (A) contained in the urethane-based adhesive composition with a polyfunctional isocyanate compound. Therefore, in the surface protection film according to an embodiment of the present invention, the urethane-based adhesive composition that forms the urethane-based adhesive typically contains a urethane prepolymer as the base polymer (A), a polyfunctional isocyanate compound, and a silicone-based compound (B).
  • the prepolymer type urethane polymer can be prepared by any appropriate method that is used in the urethane reaction between the urethane prepolymer as the base polymer (A) and the polyfunctional isocyanate compound, as long as the effect of the present invention is not impaired.
  • the urethane prepolymer may be of one type or of two or more types.
  • the number average molecular weight Mn of the urethane prepolymer is, for example, 3,000 to 1,000,000.
  • the urethane prepolymer is obtained by reacting a polyol with a polyfunctional isocyanate compound.
  • the polyol contains polyester polyol (a1) and polyether polyol (a2).
  • polyester polyol (a2) in particular, by containing not only polyether polyol (a2) but also polyester polyol (a1), it is possible to provide a surface protection film that can simultaneously exhibit excellent anchoring power and suppress the generation of glue residue when cut. In particular, it is possible to effectively exhibit excellent anchoring power.
  • the total content of polyester polyol (a1) and polyether polyol (a2) in the polyol is preferably 50% by weight to 100% by weight, more preferably 70% by weight to 100% by weight, even 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, in order to further exert the effects of the present invention.
  • the polyol typically consists of polyester polyol (a1) and polyether polyol (a2).
  • the polyester polyol (a1) may be of only one type or of two or more types.
  • the polyether polyol (a2) may be of only one type or of two or more types.
  • polyester polyol (a1) polyester polyols that can be normally used in the preparation of urethane prepolymers can be appropriately used.
  • polyester polyols include polyester polyols obtained by reacting an acid component with a glycol component.
  • the acid component include terephthalic acid, adipic acid, azelaic acid, sebacic acid, phthalic anhydride, isophthalic acid, and trimellitic acid.
  • glycol component examples include ethylene glycol, propylene glycol, diethylene glycol, butylene glycol, 1,6-hexane glycol, 3-methyl-1,5-pentanediol, 3,3'-dimethylolheptane, polyoxyethylene glycol, polyoxypropylene glycol, 1,4-butanediol, neopentyl glycol, butylethylpentanediol, glycerin, trimethylolpropane, and pentaerythritol.
  • polyester polyols 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 (a1) can range from low to high.
  • the number average molecular weight Mn of the polyester polyol (a1) is, for example, 100 to 100,000, preferably 100 to 10,000, more preferably 100 to 7,000, even more preferably 500 to 5,000, and particularly preferably 1,000 to 4,000.
  • the content of polyester polyol (a1) in the polyol is preferably 0.01% by weight to 10.0% by weight, more preferably 0.05% by weight to 5.0% by weight, even more preferably 0.08% by weight to 3.0% by weight, even more preferably 0.1% by weight to 2.0% by weight, particularly preferably 0.2% by weight to 1.5% by weight, and most preferably 0.3% by weight to 1.0% by weight. If the content of polyester polyol (a1) in the polyol is within the above range, it is possible to provide a surface protection film that can simultaneously exhibit excellent anchoring power and suppress the generation of glue residue when cut. In particular, it is possible to effectively exhibit excellent anchoring power.
  • the polyether polyol (a2) is typically a polyether polyol containing two or more of at least one type of group selected from the group consisting of methylene groups and methine groups, such as a polyether polyol containing two of at least one type of group selected from the group consisting of methylene groups and methine groups, or a polyether polyol containing three or more of at least one type of group selected from the group consisting of methylene groups and methine groups. If necessary, polyether polyol (a2) can be used in combination by replacing a part of it with glycols such as ethylene glycol or polyamines such as ethylenediamine.
  • polyether polyols containing two of at least one type of group selected from the group consisting of methylene groups and methine groups include polyethylene glycol and polypropylene glycol.
  • polyether polyol containing three or more groups of at least one type selected from the group consisting of methylene groups and methine groups is polytetramethylene glycol.
  • the molecular weight of the polyether polyol (a2) can range from low to high.
  • the molecular weight of the polyether polyol (a2) is, for example, a number average molecular weight Mn of 100 to 100,000, preferably 100 to 10,000, more preferably 100 to 7,000, even more preferably 500 to 5,000, and particularly preferably 1,000 to 4,000.
  • the content of polyether polyol (a2) in the polyol is preferably 90.0% by weight to 99.99% by weight, more preferably 95.0% by weight to 99.95% by weight, even more preferably 97.0% by weight to 99.92% by weight, even more preferably 98.0% by weight to 99.9% by weight, particularly preferably 98.5% by weight to 99.8% by weight, and most preferably 99.0% by weight to 99.7% by weight.
  • the polyether polyol (a2) contains a polyether polyol (a3) containing three or more of at least one type of group selected from the group consisting of methylene groups and methine groups.
  • a polyether polyol (a3) containing three or more of at least one type of group selected from the group consisting of methylene groups and methine groups in the polyether polyol (a2), it is possible to provide a surface protective film that can simultaneously exhibit excellent anchoring power and suppression of the generation of glue residue when cut. In particular, it is possible to effectively suppress the generation of glue residue when cut.
  • the content of polyether polyol (a3) containing three or more groups of at least one type selected from the group consisting of methylene groups and methine groups in polyether polyol (a2) is preferably 40.0% by weight to 80.0% by weight, more preferably 42.5% by weight to 77.5% by weight, even more preferably 45.0% by weight to 75.0% by weight, particularly preferably 47.5% by weight to 72.5% by weight, and most preferably 50% by weight to 70% by weight, in order to further exert the effects of the present invention.
  • the polyfunctional isocyanate compound that is reacted with the polyol may be of only one type, or of two or more types.
  • polyfunctional isocyanate compound any suitable polyfunctional isocyanate compound that can be used in the preparation of a urethane prepolymer can be used.
  • polyfunctional isocyanate compounds include polyfunctional aliphatic isocyanate compounds, polyfunctional alicyclic isocyanate compounds, polyfunctional aromatic isocyanate compounds, and polyfunctional aromatic aliphatic isocyanate compounds.
  • polyfunctional aliphatic isocyanate compounds include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,3-butylene diisocyanate, 2,3-butylene diisocyanate, dodecamethylene diisocyanate, and 2,4,4-trimethylhexamethylene diisocyanate.
  • polyfunctional alicyclic isocyanate compounds include 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate, 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, isophorone diisocyanate, methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4'-methylenebis(cyclohexyl isocyanate), 1,4-bis(isocyanatomethyl)cyclohexane, 1,4-bis(isocyanatomethyl)cyclohexane, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated tolylene diisocyanate, and hydrogenated tetramethylxylylene diisocyanate.
  • polyfunctional aromatic isocyanate compounds include 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,2'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-toluidine diisocyanate, 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate benzene, 4,4'-diphenylether diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 4,4',4"-triphenylmethane triisocyanate, dianisidine diisocyanate, and xylylene diisocyanate.
  • polyfunctional aromatic aliphatic isocyanate compounds include ⁇ , ⁇ '-diisocyanate-1,3-dimethylbenzene, ⁇ , ⁇ '-diisocyanate-1,4-dimethylbenzene, ⁇ , ⁇ '-diisocyanate-1,4-diethylbenzene, 1,4-tetramethylxylylene diisocyanate, and 1,3-tetramethylxylylene diisocyanate.
  • the polyfunctional isocyanate compound is preferably used in an equivalent ratio such that the isocyanate groups (NCO groups) of the compound are in excess of the hydroxyl groups (OH groups) of the polyol.
  • an equivalent ratio of NCO groups/OH groups ([NCO]/[OH]) is preferably 1.01 to 5.0, more preferably 1.1 to 3.0, even more preferably 1.1 to 2.0, particularly preferably 1.1 to 1.8, and most preferably 1.2 to 1.6.
  • a catalyst When preparing the urethane prepolymer, a catalyst may be used. Any appropriate catalyst may be used as long as it does not impair the effects of the present invention. Examples of such catalysts include tertiary amine catalysts and organometallic catalysts. Only one type of catalyst may be used, or two or more types may be used.
  • Tertiary amine catalysts include, for example, triethylamine, triethylenediamine, and 1,8-diazabicyclo(5,4,0)-undecene-7 (DBU).
  • DBU 1,8-diazabicyclo(5,4,0)-undecene-7
  • Organometallic catalysts include, for example, bismuth-based catalysts such as bismuth octoate, bismuth neodecanoate, bismuth naphthenate, and bismuth rosinate; tin-based catalysts such as dibutyltin dilaurate (DBTDL) and dioctyltin dilaurate (DOTDL); titanium-based catalysts such as dibutyltitanium dichloride, tetrabutyl titanate, butoxytitanium trichloride, and titanium tetraacetylacetonate; iron-based catalysts such as iron 2-ethylhexanoate and iron acetylacetonate; cobalt-based catalysts such as cobalt benzoate and cobalt 2-ethylhexanoate; zinc-based catalysts such as zinc octoate, zinc naphthenate, and zinc 2-ethylhexanoate; and zirconium
  • the amount of catalyst used is preferably 0.0001% by weight to 1.0% by weight, more preferably 0.001% by weight to 1.0% by weight, even more preferably 0.003% by weight to 1.0% by weight, and particularly preferably 0.005% by weight to 1.0% by weight, based on the total amount of the polyol and the polyfunctional isocyanate compound.
  • the reaction temperature is preferably less than 100°C, and more preferably 85°C to 95°C. If the temperature is above 100°C, it may become difficult to control the reaction rate and crosslinking structure.
  • the reaction temperature is preferably 100°C or higher, and more preferably 110°C or higher.
  • Any appropriate method may be used to prepare the urethane prepolymer as long as it does not impair the effects of the present invention.
  • Examples of such methods include 1) a method in which the entire amount of polyol, catalyst, and polyfunctional isocyanate compound are charged into a reaction vessel, and 2) a method in which the polyol and catalyst are charged into a reaction vessel and the polyfunctional isocyanate compound is added dropwise.
  • method 2) after the polyfunctional isocyanate compound has been added dropwise, additional polyol and polyfunctional isocyanate compound may be added.
  • Any suitable solvent may be used to prepare the urethane prepolymer.
  • suitable solvents include methyl ethyl ketone, ethyl acetate, toluene, xylene, and acetone.
  • any appropriate other components may be used as long as they do not impair the effects of the present invention.
  • other components include antioxidants, UV absorbers, light stabilizers, resin components, tackifiers, crosslinking retarders, inorganic fillers, organic fillers, metal powders, pigments, foil-like materials, softeners, anti-aging agents, conductive agents, surface lubricants, leveling agents, corrosion inhibitors, heat stabilizers, polymerization inhibitors, and lubricants.
  • the other components may be one type only, or two or more types.
  • antioxidants, UV absorbers, and light stabilizers are preferred embodiments.
  • antioxidants include radical chain inhibitors and peroxide decomposers.
  • radical chain inhibitors include phenol-based antioxidants and amine-based antioxidants.
  • peroxide decomposers include sulfur-based antioxidants and phosphorus-based antioxidants.
  • ultraviolet absorbers examples include benzophenone-based ultraviolet absorbers, benzotriazole-based ultraviolet absorbers, salicylic acid-based ultraviolet absorbers, anilide oxalate-based ultraviolet absorbers, cyanoacrylate-based ultraviolet absorbers, and triazine-based ultraviolet absorbers.
  • Examples of light stabilizers include hindered amine light stabilizers.
  • the urethane-based pressure-sensitive adhesive composition typically contains a polyfunctional isocyanate compound.
  • the polyfunctional isocyanate compound reacts with the base polymer (A) to form a urethane polymer.
  • the polyfunctional isocyanate compound reacts with the urethane prepolymer as the base polymer (A) to form a prepolymer-type urethane polymer.
  • the polyfunctional isocyanate compound that reacts with the base polymer (A) may be of only one type, or of two or more types.
  • any suitable polyfunctional isocyanate compound that can be used in a urethane reaction can be used.
  • a polyfunctional isocyanate compound for example, the polyfunctional isocyanate compound that can be used in the preparation of a urethane prepolymer, as described above, can be used.
  • the equivalent ratio ([NCO]/[OH]) of the isocyanate group (NCO group) of the polyfunctional isocyanate compound to the hydroxyl group (OH group) of the urethane prepolymer is preferably 2.00 or less, more preferably 1.70 or less, even more preferably 0.60 to 1.70, and even more preferably 0.75 to 1.7 0, more preferably 0.90 to 1.70, even more preferably 1.00 to 1.70, even more preferably 1.10 to 1.65, particularly preferably 1.15 to 1.62, most preferably 1.15 to 1.60, and even 1.20 to 1.60, 1.25 to 1.60, 1.30 to 1.60, 1.35 to 1.60, 1.40 to 1.60, or 1.45 to 1.60.
  • the proportion of the polyfunctional isocyanate compound used per 100 parts by weight of the urethane prepolymer is preferably 0.5 to 15 parts by weight, more preferably 1.0 to 10 parts by weight, even more preferably 1.5 to 8.0 parts by weight, particularly preferably 1.7 to 6.0 parts by weight, and most preferably 2.0 to 5.0 parts by weight.
  • Any appropriate method may be used to prepare the urethane polymer, so long as it is a method of curing a urethane-based adhesive composition containing a base polymer (A) and a polyfunctional isocyanate compound to form a urethane polymer, as long as the effects of the present invention are not impaired.
  • Such a method includes, for example, a method in which a urethane-based adhesive composition containing a base polymer (A) and a polyfunctional isocyanate compound is applied to any appropriate substrate, heated and dried as necessary, and cured as necessary, to prepare the urethane polymer in an adhesive layer formed on the substrate.
  • the application method, heating and drying conditions, curing conditions, etc. may be appropriately selected from methods commonly known for forming adhesive layers.
  • the urethane-based pressure-sensitive adhesive composition may contain a catalyst to promote the reaction between the base polymer (A) and the polyfunctional isocyanate compound.
  • a catalyst to promote the reaction between the base polymer (A) and the polyfunctional isocyanate compound.
  • Any suitable catalyst may be used as the catalyst as long as it does not impair the effects of the present invention. Examples of such catalyst include the catalysts that can be used in the preparation of the urethane prepolymer described above.
  • the catalyst contained in the urethane-based adhesive composition is preferably an organometallic compound, and more preferably at least one selected from the group consisting of zinc-based catalysts and titanium-based catalysts, in that it can further exert the effects of the present invention.
  • Examples of zinc-based catalysts include zinc octoate, zinc naphthenate, and zinc 2-ethylhexanoate.
  • Titanium catalysts include, for example, dibutyltitanium dichloride, tetrabutyltitanate, butoxytitanium trichloride, and titanium tetraacetylacetonate.
  • the content of the catalyst in the urethane-based adhesive composition is, in terms of solid content, preferably 0.0001 to 1.0 parts by weight, more preferably 0.001 to 1.0 parts by weight, even more preferably 0.003 to 1.0 parts by weight, and particularly preferably 0.005 to 1.0 parts by weight, per 100 parts by weight of the base polymer (A).
  • the urethane-based pressure-sensitive adhesive composition contains a silicone-based compound (B).
  • the silicone-based compound (B) may be of only one type, or of two or more types.
  • the content of the silicone compound (B) in the urethane-based adhesive composition is, in terms of solid content, preferably 0.001 to 20 parts by weight, more preferably 0.005 to 10 parts by weight, even more preferably 0.01 to 7 parts by weight, even more preferably 0.01 to 4 parts by weight, even more preferably 0.01 to 2 parts by weight, particularly preferably 0.01 to 1 part by weight, and most preferably 0.01 to 0.80 parts by weight, per 100 parts by weight of the base polymer (A). If the content of the silicone compound (B) in the urethane-based adhesive composition is within the above range, the effects of the present invention can be more effectively achieved. If the content of the silicone compound (B) in the urethane-based adhesive composition is too high, for example, there is a risk of high haze.
  • the silicone-based compound (B) typically contains at least one selected from the group consisting of reactive silicone oils and non-reactive silicone oils.
  • the content of at least one selected from the group consisting of reactive silicone oils and non-reactive silicone oils in the silicone-based compound (B) is preferably 50% to 100% by weight, more preferably 70% to 100% by weight, even more preferably 90% to 100% by weight, particularly preferably 95% to 100% by weight, and most preferably 98% to 100% by weight.
  • the silicone-based compound (B) may contain at least one type selected from the group consisting of reactive silicone oils and non-reactive silicone oils, as well as any other appropriate silicone-based compound within a range that does not impair the effects of the present invention.
  • reactive silicone oils examples include side-chain reactive silicone oils in which an organic group is bonded as a side chain to a Si atom that is used for siloxane bonding; both-end reactive silicone oils in which an organic group is bonded to a Si atom located at both ends of the structure; one-end reactive silicone oils in which an organic group is bonded to only one of the Si atoms located at both ends of the structure; and both-end side-chain reactive silicone oils in which an organic group is bonded as a side chain to a Si atom that is used for siloxane bonding and an organic group is bonded to a Si atom located at both ends of the structure.
  • Side-chain reactive silicone oils include, for example, amino-modified side-chain reactive silicone oils, epoxy-modified side-chain reactive silicone oils, carbinol-modified side-chain reactive silicone oils, mercapto-modified side-chain reactive silicone oils, carboxyl-modified side-chain reactive silicone oils, and methylhydrogen silicone oil-type side-chain reactive silicone oils.
  • Commercially available products include, for example, the various silicone oils sold as side-chain reactive silicone oils manufactured by Shin-Etsu Chemical Co., Ltd.
  • both-end reactive silicone oils examples include amino-modified both-end reactive silicone oils, epoxy-modified both-end reactive silicone oils, carbinol-modified both-end reactive silicone oils, methacrylic-modified both-end reactive silicone oils, polyether-modified both-end reactive silicone oils, mercapto-modified both-end reactive silicone oils, carboxyl-modified both-end reactive silicone oils, phenol-modified both-end reactive silicone oils, silanol-end reactive silicone oils, acrylic-modified both-end reactive silicone oils, and carboxylic anhydride-modified both-end reactive silicone oils.
  • Commercially available products include, for example, the various silicone oils available as both-end reactive silicone oils manufactured by Shin-Etsu Chemical Co., Ltd.
  • single-end reactive silicone oils include single-end reactive modified type single-end reactive silicone oils, average single-end carboxyl modified type single-end reactive silicone oils, and more specifically, carbinol modified type single-end reactive silicone oils.
  • Commercially available products of these include, for example, the various silicone oils available as single-end reactive silicone oils manufactured by Shin-Etsu Chemical Co., Ltd.
  • side chain both-end reactive silicone oils examples include side chain both-end reactive silicone oils with amino and methoxy modified side chains, and epoxy modified side chain both-end reactive silicone oils.
  • Examples of commercially available products include various silicone oils sold as side chain both-end reactive silicone oils manufactured by Shin-Etsu Chemical Co., Ltd.
  • non-reactive silicone oils examples include side-chain non-reactive silicone oils in which organic groups are bonded as side chains to the Si atoms that contribute to siloxane bonds, and double-end non-reactive silicone oils in which organic groups are bonded to the Si atoms located at both ends of the structure.
  • Side-chain non-reactive silicone oils include, for example, polyether-modified side-chain non-reactive silicone oils, aralkyl-modified side-chain non-reactive silicone oils, fluoroalkyl-modified side-chain non-reactive silicone oils, long-chain alkyl-modified side-chain non-reactive silicone oils, higher fatty acid ester-modified side-chain non-reactive silicone oils, higher fatty acid-containing side-chain non-reactive silicone oils, and phenyl-modified side-chain non-reactive silicone oils.
  • Commercially available products include, for example, the various silicone oils available as side-chain non-reactive silicone oils manufactured by Shin-Etsu Chemical Co., Ltd.
  • a dual-end non-reactive silicone oil is a polyether-modified dual-end non-reactive silicone oil.
  • examples of commercially available products include various silicone oils sold as dual-end non-reactive silicone oils manufactured by Shin-Etsu Chemical Co., Ltd.
  • a preferred embodiment of the silicone-based compound (B) includes at least one selected from the group consisting of reactive silicone oils having at least one selected from the group consisting of polyether structures and carbinol structures, and non-reactive silicone oils having a polyether structure and an HLB value of 15 or less.
  • the silicone-based compound (B) can provide a surface protection film that adheres appropriately to an adherend and is easy to peel off, and that is inhibited from increasing in adhesion to the adherend over time, and that adheres appropriately to an adherend and is easy to peel off even after a long time has passed after it has been attached to the adherend.
  • An example of a reactive silicone oil having a polyether structure is a polyether-modified type reactive silicone oil at both ends.
  • polyether-modified, double-ended reactive silicone oils include, for example, “X-22-4952,” “X-22-4272,” and “KF-6123” manufactured by Shin-Etsu Chemical Co., Ltd.
  • reactive silicone oils having a carbinol structure examples include carbinol-modified side-chain reactive silicone oils, carbinol-modified both-end reactive silicone oils, and carbinol-modified one-end reactive silicone oils.
  • carbinol-modified side-chain reactive silicone oils include, for example, “X-22-4039” and “X-22-4015” manufactured by Shin-Etsu Chemical Co., Ltd.
  • carbinol-modified, double-ended reactive silicone oils include, for example, “KF-6000,” “KF-6001,” “KF-6002,” and “KF-6003” manufactured by Shin-Etsu Chemical Co., Ltd.
  • carbinol-modified single-terminated reactive silicone oils include, for example, “X-22-170BX” and “X-22-170DX” manufactured by Shin-Etsu Chemical Co., Ltd.
  • a non-reactive silicone oil having a polyether structure and an HLB value of 15 or less can be selected from non-reactive silicone oils having a polyether structure that have an HLB value of 15 or less.
  • non-reactive silicone oils with a polyether structure examples include polyether-modified side-chain non-reactive silicone oils and polyether-modified both-end non-reactive silicone oils.
  • polyether-modified side-chain non-reactive silicone oils include, for example, “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”, “KF-6011”, “KF-6012”, “KF-6015”, “KF-6017”, and “X-22-2516” manufactured by Shin-Etsu Chemical Co., Ltd.
  • the urethane-based adhesive composition may contain any other suitable components as long as they do not impair the effects of the present invention.
  • suitable components include ionic compounds, fatty acid esters, solvents, crosslinking accelerators, silane coupling agents, antioxidants, UV absorbers, light stabilizers, resin components, tackifiers, crosslinking retarders, inorganic fillers, organic fillers, metal powders, colorants (pigments, dyes, etc.), chain transfer agents, plasticizers, softeners, antioxidants, conductive agents, foil-like materials, surface lubricants, leveling agents, corrosion inhibitors, heat stabilizers, polymerization inhibitors, and lubricants.
  • the other components may be one type only, or two or more types.
  • the substrate may be a single layer or may be two or more layers.
  • the substrate may be a stretched substrate.
  • the thickness of the substrate is preferably 4 ⁇ m to 450 ⁇ m, more preferably 8 ⁇ m to 400 ⁇ m, even more preferably 12 ⁇ m to 350 ⁇ m, and particularly preferably 16 ⁇ m to 250 ⁇ m.
  • a release treatment can be performed by adding, for example, fatty acid amide, polyethyleneimine, long-chain alkyl additives, etc. to the substrate in order to form a roll that is easy to unwind, or a coating layer made of any suitable release agent, such as silicone-based, long-chain alkyl-based, or fluorine-based, can be provided.
  • any suitable material may be used as the material for the substrate depending on the application. Examples include plastic, paper, metal film, nonwoven fabric, etc. Plastic is preferable. That is, the substrate is preferably a plastic film.
  • the substrate may be made of one type of material, or may be made of two or more types of materials. For example, it may be made of two or more types of plastic.
  • polyester resins examples include polyester resins, polyamide resins, polyolefin resins, etc.
  • polyester resins examples include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, etc.
  • the substrate may contain any suitable additives as necessary.
  • additives that may be contained in the substrate include antioxidants, UV absorbers, light stabilizers, antistatic agents, fillers, and pigments.
  • the type, number, and amount of additives that may be contained in the substrate may be appropriately set depending on the purpose.
  • the substrate is made of plastic, it is preferable to contain some of the above additives for the purpose of preventing deterioration, etc.
  • particularly preferred additives include antioxidants, UV absorbers, light stabilizers, and fillers.
  • the surface protective film according to the embodiment of the present invention is typically attached to an exposed surface of an optical member or electronic member in the manufacturing process of the optical member or electronic member to prevent the surface of the optical member or electronic member from being scratched during processing, assembly, inspection, transportation, etc., and can be suitably used for surface protection of the optical member or electronic member.
  • the optical member of the present invention has the surface protective film of the present invention attached thereto.
  • the electronic member of the present invention has the surface protective film of the present invention attached thereto.
  • the conditions of the tensile test were an environment of 23°C and 50% RH, a peel angle of 180 degrees, and a peel speed (pulling speed) of 300 mm/min.
  • the peel force (load) when the surface protective film was peeled from the glass plate was measured, and the average peel force (average load) at that time was taken as the adhesive force (I) to the glass plate (sometimes simply referred to as adhesive force (I)).
  • adhesive force (I) 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.
  • the conditions of the tensile test were an environment of 23°C and 50% RH, a peel angle of 180 degrees, and a peel speed (pulling speed) of 300 mm/min.
  • the peel force (load) when the surface protective film was peeled from the glass plate was measured, and the average peel force (average load) at that time was taken as the adhesive force (II) to the glass plate (sometimes simply referred to as adhesive force (II)).
  • adhesive force (II) 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.
  • HM-150N Murakami Color Research Laboratory
  • ⁇ Anchor strength evaluation> The surface protection film was cut into a size of 50 mm x 50 mm to prepare an evaluation sample. After removing the release liner from the evaluation sample, the adhesive layer side was rubbed from the edge with a finger. If the adhesive layer peeled off from the substrate when rubbed hard, it was evaluated as ⁇ , if the adhesive layer peeled off from the substrate when rubbed hard, it was evaluated as ⁇ , and if the adhesive layer did not peel off from the substrate, it was evaluated as ⁇ .
  • the release liner was peeled off from the surface protection film (width 25 mm ⁇ length 140 mm), and the adhesive layer side of the film was cut by 1 cm at a 90 degree angle with a cutter blade.
  • G good
  • B better
  • hexamethylene diisocyanate product name "HDI", manufactured by Tosoh Corporation
  • polymerization was carried out by maintaining the temperature of the solution in the experimental apparatus at 90 ⁇ 2°C in a water bath for 4 hours to obtain a solution of urethane prepolymer A.
  • ethyl acetate was appropriately added dropwise to control the temperature during polymerization and to prevent a decrease in stirrability due to an increase in viscosity.
  • the total amount of ethyl acetate added was 300 g.
  • the solids concentration of the solution of urethane prepolymer A was 50% by weight.
  • hexamethylene diisocyanate product name "HDI", manufactured by Tosoh Corporation
  • HDI hexamethylene diisocyanate
  • toluene was appropriately added dropwise during the polymerization to control the temperature during polymerization and to prevent a decrease in stirrability due to an increase in viscosity.
  • the total amount of toluene added was 380 g.
  • the solid content concentration of the solution of urethane prepolymer B was 50% by weight.
  • a urethane-based pressure-sensitive adhesive composition (1) was obtained by blending 100 parts by weight of a urethane prepolymer A, 4.0 parts by weight of a polyfunctional isocyanate compound (Coronate HX (C/HX), manufactured by Nippon Polyurethane Co., Ltd.) as a crosslinking agent, 0.10 parts by weight of KF-354L (manufactured by Shin-Etsu Chemical Co., Ltd.) as a silicone-based compound, 0.50 parts by weight of Irganox 1010 (manufactured by BASF Co., Ltd.) as an antioxidant, and 0.20 parts by weight of Nikka Octix Zinc 18% (manufactured by Nippon Chemical Industry Co., Ltd.) as a catalyst, and diluting with ethyl acetate to a total solids content of 50% by weight.
  • a polyfunctional isocyanate compound (Coronate HX (C/HX), manufactured by Nippon Polyurethane Co.
  • the urethane-based adhesive composition (1) was applied to a substrate made of polyester resin (product name "T100-75S", thickness 75 ⁇ m, manufactured by Mitsubishi Chemical Corporation) so that the thickness after drying would be 75 ⁇ m, and cured and dried under conditions of a drying temperature of 150° C. and a drying time of 3 minutes to prepare an adhesive layer (1).
  • the silicone-treated surface of a release liner made of polyester resin having a thickness of 25 ⁇ m and one side of which was silicone-treated (product name "MRF25”, thickness 25 ⁇ m, manufactured by Mitsubishi Chemical Corporation) was laminated to the surface of the obtained adhesive layer (1) to obtain a surface protection film (1). Aging was carried out at room temperature for 5 days, and various evaluations were performed. The results are shown in Tables 1 and 2.
  • a urethane-based pressure-sensitive adhesive composition (2) was obtained by blending 100 parts by weight of urethane prepolymer A, 4.0 parts by weight of a polyfunctional isocyanate compound (Coronate HX (C/HX), manufactured by Nippon Polyurethane Co., Ltd.) as a crosslinking agent, 0.10 parts by weight of KF-640 (manufactured by Shin-Etsu Chemical Co., Ltd.) as a silicone-based compound, 0.50 parts by weight of Irganox 1010 (manufactured by BASF Co., Ltd.) as an antioxidant, and 0.20 parts by weight of Nikka Octix Zinc 18% (manufactured by Nippon Chemical Industry Co., Ltd.) as a catalyst, and diluting with ethyl acetate to a total solids content of 50% by weight.
  • a polyfunctional isocyanate compound (Coronate HX (C/HX), manufactured by Nippon Polyurethane Co., Ltd.
  • Example 2 Except for using the urethane-based pressure-sensitive adhesive composition (2) instead of the urethane-based pressure-sensitive adhesive composition (1), the same procedure as in Example 1 was carried out to obtain a pressure-sensitive adhesive layer (2) and a surface protective film (2). Aging was carried out at room temperature for 5 days, and various evaluations were carried out. The results are shown in Tables 1 and 2.
  • a urethane prepolymer A 100 parts by weight, a polyfunctional isocyanate compound (Coronate HX (C/HX), manufactured by Nippon Polyurethane Co., Ltd.) as a crosslinking agent: 4.0 parts by weight, a silicone-based compound: X-22-4515 (manufactured by Shin-Etsu Chemical Co., Ltd.): 0.10 parts by weight, an antioxidant: Irganox 1010 (manufactured by BASF Co., Ltd.): 0.50 parts by weight, and a catalyst: Nikka Octix Zinc 18% (manufactured by Nippon Chemical Industry Co., Ltd.): 0.20 parts by weight were mixed, and the mixture was diluted with ethyl acetate so that the total solid content was 50% by weight, to obtain a urethane-based pressure-sensitive adhesive composition (3).
  • a polyfunctional isocyanate compound (Coronate HX (C/HX), manufactured by Nippon Polyurethane Co
  • Example 2 Except for using the urethane-based pressure-sensitive adhesive composition (3) instead of the urethane-based pressure-sensitive adhesive composition (1), the same procedure as in Example 1 was carried out to obtain a pressure-sensitive adhesive layer (3) and a surface protective film (3). Aging was carried out at room temperature for 5 days, and various evaluations were carried out. The results are shown in Tables 1 and 2.
  • a urethane-based pressure-sensitive adhesive composition (4) was obtained by blending 100 parts by weight of a urethane prepolymer A, 4.0 parts by weight of a polyfunctional isocyanate compound (Coronate HX (C/HX), manufactured by Nippon Polyurethane Co., Ltd.) as a crosslinking agent, 0.10 parts by weight of KF-6001 (manufactured by Shin-Etsu Chemical Co., Ltd.) as a silicone-based compound, 0.50 parts by weight of Irganox 1010 (manufactured by BASF Co., Ltd.) as an antioxidant, and 0.20 parts by weight of Nikka Octix Zinc 18% (manufactured by Nippon Chemical Industry Co., Ltd.) as a catalyst, and diluting with ethyl acetate to a total solids content of 50% by weight.
  • a polyfunctional isocyanate compound (Coronate HX (C/HX), manufactured by Nippon Polyurethane Co.
  • Example 2 Except for using the urethane-based pressure-sensitive adhesive composition (4) instead of the urethane-based pressure-sensitive adhesive composition (1), the same procedure as in Example 1 was carried out to obtain a pressure-sensitive adhesive layer (4) and a surface protective film (4). Aging was carried out at room temperature for 5 days, and various evaluations were carried out. The results are shown in Tables 1 and 2.
  • a urethane-based pressure-sensitive adhesive composition (5) was obtained by blending 100 parts by weight of urethane prepolymer A, 4.0 parts by weight of a polyfunctional isocyanate compound (Coronate HX (C/HX), manufactured by Nippon Polyurethane Co., Ltd.) as a crosslinking agent, 0.10 parts by weight of KF-615A (manufactured by Shin-Etsu Chemical Co., Ltd.) as a silicone-based compound, 0.50 parts by weight of Irganox 1010 (manufactured by BASF Co., Ltd.) as an antioxidant, and 0.20 parts by weight of Nikka Octix Zinc 18% (manufactured by Nippon Chemical Industry Co., Ltd.) as a catalyst, and diluting with ethyl acetate to a total solids content of 50% by weight.
  • a polyfunctional isocyanate compound (Coronate HX (C/HX), manufactured by Nippon Polyurethane Co.,
  • Example 2 Except for using the urethane-based pressure-sensitive adhesive composition (5) instead of the urethane-based pressure-sensitive adhesive composition (1), the same procedure as in Example 1 was carried out to obtain a pressure-sensitive adhesive layer (5) and a surface protective film (5). Aging was carried out at room temperature for 5 days, and various evaluations were carried out. The results are shown in Tables 1 and 2.
  • a urethane-based pressure-sensitive adhesive composition (6) was obtained by blending 100 parts by weight of urethane prepolymer A, 4.0 parts by weight of a polyfunctional isocyanate compound (Coronate HX (C/HX), manufactured by Nippon Polyurethane Co., Ltd.) as a crosslinking agent, 0.10 parts by weight of KF-615A (manufactured by Shin-Etsu Chemical Co., Ltd.) as a silicone-based compound, 0.50 parts by weight of Irganox 1010 (manufactured by BASF Co., Ltd.) as an antioxidant, and 0.20 parts by weight of Orgatix TC-401 (titanium tetraacetylacetonate, manufactured by Matsumoto Fine Chemical Co., Ltd.) as a catalyst, and diluting with ethyl acetate to a total solid content of 50% by weight.
  • a polyfunctional isocyanate compound (Coronate HX (C/HX), manufactured by N
  • Example 2 Except for using the urethane-based pressure-sensitive adhesive composition (6) instead of the urethane-based pressure-sensitive adhesive composition (1), the same procedure as in Example 1 was carried out to obtain a pressure-sensitive adhesive layer (6) and a surface protective film (6). Aging was carried out at room temperature for 5 days, and various evaluations were carried out. The results are shown in Tables 1 and 2.
  • a urethane-based pressure-sensitive adhesive composition (7) was obtained by blending 100 parts by weight of urethane prepolymer A, 4.0 parts by weight of a polyfunctional isocyanate compound (Coronate HX (C/HX), manufactured by Nippon Polyurethane Co., Ltd.) as a crosslinking agent, 0.10 parts by weight of KF-615A (manufactured by Shin-Etsu Chemical Co., Ltd.) as a silicone-based compound, 0.50 parts by weight of Irganox 1010 (manufactured by BASF Co., Ltd.) as an antioxidant, and 0.20 parts by weight of Nursem Ferric (manufactured by Nippon Chemical Industry Co., Ltd.) as a catalyst, and diluting with ethyl acetate to a total solids content of 50% by weight.
  • a polyfunctional isocyanate compound (Coronate HX (C/HX), manufactured by Nippon Polyurethane Co., Ltd.) as
  • Example 2 Except for using the urethane-based pressure-sensitive adhesive composition (7) instead of the urethane-based pressure-sensitive adhesive composition (1), the same procedure as in Example 1 was carried out to obtain a pressure-sensitive adhesive layer (7) and a surface protective film (7). Aging was carried out at room temperature for 5 days, and various evaluations were carried out. The results are shown in Tables 1 and 2.
  • a urethane-based pressure-sensitive adhesive composition (8) was obtained by blending 100 parts by weight of urethane prepolymer A, 4.0 parts by weight of a polyfunctional isocyanate compound (Coronate HX (C/HX), manufactured by Nippon Polyurethane Co., Ltd.) as a crosslinking agent, 0.50 parts by weight of KF-615A (manufactured by Shin-Etsu Chemical Co., Ltd.) as a silicone-based compound, 0.50 parts by weight of Irganox 1010 (manufactured by BASF Co., Ltd.) as an antioxidant, and 0.20 parts by weight of Nikka Octix Zinc 18% (manufactured by Nippon Chemical Industry Co., Ltd.) as a catalyst, and diluting with ethyl acetate to a total solids content of 50% by weight.
  • a polyfunctional isocyanate compound (Coronate HX (C/HX), manufactured by Nippon Polyurethane Co.,
  • Example 2 Except for using the urethane-based pressure-sensitive adhesive composition (8) instead of the urethane-based pressure-sensitive adhesive composition (1), the same procedure as in Example 1 was carried out to obtain a pressure-sensitive adhesive layer (8) and a surface protective film (8). Aging was carried out at room temperature for 5 days, and various evaluations were carried out. The results are shown in Tables 1 and 2.
  • a urethane-based pressure-sensitive adhesive composition (C1) was obtained by blending 100 parts by weight of urethane prepolymer B, 4.0 parts by weight of a polyfunctional isocyanate compound (Coronate HX (C/HX), manufactured by Nippon Polyurethane Co., Ltd.) as a crosslinking agent, 0.10 parts by weight of KF-615A (manufactured by Shin-Etsu Chemical Co., Ltd.) as a silicone-based compound, 0.50 parts by weight of Irganox 1010 (manufactured by BASF Co., Ltd.) as an antioxidant, and 0.20 parts by weight of Nikka Octix Zinc 18% (manufactured by Nippon Chemical Industry Co., Ltd.) as a catalyst, and diluting with ethyl acetate to a total solids content of 50% by weight.
  • a polyfunctional isocyanate compound (Coronate HX (C/HX), manufactured by Nippon Polyurethane Co.
  • Example 1 Except for using the urethane-based pressure-sensitive adhesive composition (C1) instead of the urethane-based pressure-sensitive adhesive composition (1), the same procedure as in Example 1 was carried out to obtain a pressure-sensitive adhesive layer (C1) and a surface protective film (C1). Aging was carried out at room temperature for 5 days, and various evaluations were carried out. The results are shown in Tables 1 and 2.
  • a urethane-based pressure-sensitive adhesive composition (C2) was obtained by blending 100 parts by weight of urethane prepolymer C, 4.0 parts by weight of a polyfunctional isocyanate compound (Coronate HX (C/HX), manufactured by Nippon Polyurethane Co., Ltd.) as a crosslinking agent, 0.10 parts by weight of KF-615A (manufactured by Shin-Etsu Chemical Co., Ltd.) as a silicone-based compound, 0.50 parts by weight of Irganox 1010 (manufactured by BASF Co., Ltd.) as an antioxidant, and 0.20 parts by weight of Nikka Octix Zinc 18% (manufactured by Nippon Chemical Industry Co., Ltd.) as a catalyst, and diluting with ethyl acetate to a total solids content of 50% by weight.
  • a polyfunctional isocyanate compound (Coronate HX (C/HX), manufactured by Nippon Polyurethane Co.
  • Example 2 Except for using the urethane-based pressure-sensitive adhesive composition (C2) instead of the urethane-based pressure-sensitive adhesive composition (1), the same procedure as in Example 1 was carried out to obtain a pressure-sensitive adhesive layer (C2) and a surface protective film (C2). Aging was carried out at room temperature for 5 days, and various evaluations were carried out. The results are shown in Tables 1 and 2.
  • Example 9 to 16 For each of the surface protection films (1) to (8) obtained in Examples 1 to 8, the release liner was peeled off, and the pressure-sensitive adhesive layer side was attached to a polarizing plate (manufactured by Nitto Denko Corporation, product name "TEG1465DUHC”), which is an optical component, to obtain an optical component with a surface protection film attached thereto.
  • a polarizing plate manufactured by Nitto Denko Corporation, product name "TEG1465DUHC”
  • Example 17 to 24 For each of the surface protection films (1) to (8) obtained in Examples 1 to 8, the release liner was peeled off, and the pressure-sensitive adhesive layer side was attached to a conductive film (manufactured by Nitto Denko Corporation, product name "ELECRYSTA V270L-TFMP"), which is an electronic component, to obtain an electronic component having a surface protection film attached thereto.
  • a conductive film manufactured by Nitto Denko Corporation, product name "ELECRYSTA V270L-TFMP”
  • the surface protective film of the present invention can be used for any suitable application, and is preferably used in the fields of optical members and electronic members.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesive Tapes (AREA)
  • Laminated Bodies (AREA)
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JP2019218472A (ja) * 2018-06-20 2019-12-26 日東電工株式会社 表面保護フィルム
WO2022138179A1 (ja) * 2020-12-21 2022-06-30 日東電工株式会社 表面保護フィルム

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JP6368810B2 (ja) 2016-03-04 2018-08-01 日東電工株式会社 表面保護フィルム

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* Cited by examiner, † Cited by third party
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JP2019218472A (ja) * 2018-06-20 2019-12-26 日東電工株式会社 表面保護フィルム
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