JP6648168B2 - Surface protection film - Google Patents

Description

  The present invention relates to a surface protection film.

  In a manufacturing process of an optical member or an electronic member, a surface protective film is generally attached to an exposed surface to prevent the surface from being damaged during processing, assembly, inspection, transportation, and the like. Such a surface protection film is peeled off from the optical member or the electronic member when the surface protection is no longer necessary (Patent Document 1).

  In an optical member or an electronic member to which such a surface protective film is adhered, when the surface protective film is to be peeled as described above, only the interface between the surface protective film and the optical member or the electronic member is smooth. It is important that it can be peeled off.

  However, when the optical member or the electronic member includes a member that is easily damaged, such as thin glass or a barrier film, the conventional surface protective film having a light peeling property is used to remove the attached surface protective film. Even when it is used, the easily breakable member may be damaged by the peeling force.

  For this reason, a surface protection film having lighter releasability, that is, a super light releasability, is required as compared with a conventional surface protection film having light releasability.

  Here, when a large amount of a conventional release agent is contained in the pressure-sensitive adhesive layer of the surface protective film in order to reduce the release force, a certain degree of ultra-light release property may be exhibited. However, in such a method, after the surface protective film is peeled, the degree of contamination of the surface of the adherend by the release agent is large, and when the surface protective film is to be attached again, the surface protective film is contaminated by the surface of the adherend. However, there is a problem that sticking becomes difficult.

  Also, in the manufacturing process of optical and electronic components, the surface protection film attached to the exposed surface to prevent scratching of the surface during processing, assembly, inspection, transportation, etc., is kept as it is. Often. In this case, if the conventional surface protection film is stored with the film adhered thereto, the adhesive force will increase with time, causing a problem of heavy peeling.

  As described above, in the manufacturing process of the optical member and the electronic member, processing, assembly, inspection, in the surface protection film to be adhered to the exposed surface to prevent the surface scratches during transportation, etc., some There are points to be improved, that is, providing ultra-light peelability, lowering the contamination of the adherend surface, and suppressing heavy peeling over time.

JP-A-2006-17109

  It is an object of the present invention to provide a surface protective film provided with ultra-light peelability, to provide a surface protective film capable of reducing contamination on the surface of an adherend, and to provide a surface protection capable of suppressing heavy peeling over time. It is to provide a film.

The surface protective film of the present invention,
A surface protective film having an adhesive layer,
A 25 μm-thick polyethylene terephthalate film was bonded to the pressure-sensitive adhesive layer, and after 30 minutes at 23 ° C., the polyethylene terephthalate film had a peeling force of 0.08 N / sec when peeled at a peeling angle of 180 ° and a peeling speed of 6000 mm / min. It is 25 mm or less.

  In one embodiment, a 25 μm-thick polyethylene terephthalate film is attached to the pressure-sensitive adhesive layer, and after 30 minutes at 23 ° C., the polyethylene terephthalate film is peeled at a peel angle of 180 ° and a peel speed of 300 mm / min. The peeling force is 0.02 N / 25 mm or less.

The surface protective film of the present invention,
A surface protective film having an adhesive layer,
A 25 μm-thick polyethylene terephthalate film was attached to the pressure-sensitive adhesive layer, and after 7 days at 80 ° C., the polyethylene terephthalate film had a peeling force of 0.35 N / when peeled at a peeling angle of 180 ° and a peeling speed of 6000 mm / min. It is 25 mm or less.

  In one embodiment, a 25 μm-thick polyethylene terephthalate film is attached to the pressure-sensitive adhesive layer, and after 7 days at 80 ° C., the polyethylene terephthalate film is peeled at a peeling angle of 180 ° and a peeling speed of 300 mm / min. The peeling force is 0.07 N / 25 mm or less.

The surface protective film of the present invention,
A surface protective film having an adhesive layer,
A glass plate having a thickness of 1000 μm is attached to the pressure-sensitive adhesive layer, and after 30 minutes at 23 ° C., the peeling force when peeled from the glass plate at a peeling angle of 180 ° and a peeling speed of 6000 mm / min is 0.135 N / 25 mm or less. It is.

  In one embodiment, a 1000 μm-thick glass plate is attached to the pressure-sensitive adhesive layer, and after 30 minutes at 23 ° C., a peeling force when peeled from the glass plate at a peeling angle of 180 ° and a peeling speed of 300 mm / min. Is 0.023 N / 25 mm or less.

The surface protective film of the present invention,
A surface protective film having an adhesive layer,
A glass plate having a thickness of 1000 μm is stuck to the pressure-sensitive adhesive layer, and after 7 days at 80 ° C., the peeling force when peeled from the glass plate at a peeling angle of 180 ° and a peeling speed of 6000 mm / min is 0.35 N / 25 mm or less. It is.

  In one embodiment, a glass plate having a thickness of 1000 μm is attached to the pressure-sensitive adhesive layer, and after 7 days at 80 ° C., a peeling force when peeled from the glass plate at a peeling angle of 180 ° and a peeling speed of 300 mm / min. Is 0.05 N / 25 mm or less.

  In one embodiment, the surface protective film of the present invention has a residual adhesion of 50% or more.

  In one embodiment, the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer is formed from a pressure-sensitive adhesive composition, and the pressure-sensitive adhesive composition includes a base polymer and a silicone-based additive and / or a fluorine-based additive. .

  In one embodiment, the silicone-based additive is at least one selected from a siloxane bond-containing compound, a hydroxyl-containing silicone-based compound, and a crosslinkable functional group-containing silicone-based compound.

  In one embodiment, the fluorine-based additive is at least one selected from a fluorine-containing compound, a hydroxyl-containing fluorine-containing compound, and a crosslinkable functional group-containing fluorine-containing compound.

  In one embodiment, the base polymer is at least one selected from a urethane resin, an acrylic resin, a rubber resin, and a silicone resin.

  In one embodiment, the urethane-based resin is a urethane-based resin formed from a composition containing a polyol (A) and a polyfunctional isocyanate compound (B).

  In one embodiment, the urethane-based resin is a urethane-based resin formed from a composition containing a urethane prepolymer (C) and a polyfunctional isocyanate compound (B).

  In one embodiment, the pressure-sensitive adhesive composition contains a fatty acid ester.

  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.

  ADVANTAGE OF THE INVENTION According to this invention, the surface protection film which has super light peelability and has low contamination property of the adherend surface can be provided.

1 is a schematic sectional view of a surface protection film according to one embodiment of the present invention.

≪≪Surface protection film≫≫
The surface protective film of the present invention has a pressure-sensitive adhesive layer. The surface protective film of the present invention may be provided with any other appropriate member as long as it has a pressure-sensitive adhesive layer, as long as the effect of the present invention is not impaired. Typically, the surface protective film of the present invention has a base material layer and an adhesive layer.

  FIG. 1 is a schematic sectional view of a surface protection film according to one embodiment of the present invention. In FIG. 1, a surface protection film 10 includes a base material layer 1 and an adhesive layer 2. In FIG. 1, the base material layer 1 and the pressure-sensitive adhesive layer 2 are directly laminated.

  In FIG. 1, any appropriate release liner may be provided on the surface of the pressure-sensitive adhesive layer 2 on the side opposite to the base material layer 1 for protection or the like until use (not shown). As the release liner, for example, a release liner in which the surface of a base material (liner base material) such as paper or plastic film is silicone-treated, and the surface of a base material (liner base material) such as paper or plastic film is formed of a polyolefin resin A laminated release liner is exemplified. As a plastic film as a liner substrate, for example, polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate film, polybutylene terephthalate film, Examples include a polyurethane film and an ethylene-vinyl acetate copolymer film. The plastic film as the liner substrate is preferably a polyethylene film.

  The thickness of the release liner is preferably 1 μm to 500 μm, more preferably 3 μm to 450 μm, still more preferably 5 μm to 400 μm, and particularly preferably 10 μm to 300 μm.

  The thickness of the surface protective film is preferably 5 μm to 500 μm, more preferably 10 μm to 450 μm, still more preferably 15 μm to 400 μm, and particularly preferably 20 μm to 300 μm.

  In one embodiment of the surface protective film of the present invention, a 25 μm-thick polyethylene terephthalate film is laminated on the pressure-sensitive adhesive layer, and after 30 minutes at 23 ° C., the polyethylene terephthalate film is peeled at a peel angle of 180 ° and a peel speed of 6000 mm / min. Is preferably 0.08 N / 25 mm or less, more preferably 0.075 N / 25 mm or less, still more preferably 0.07 N / 25 mm or less, and still more preferably 0.065 N / 25 mm or less. / 25 mm or less, particularly preferably 0.06 N / 25 mm or less, and most preferably 0.055 N / 25 mm or less. The lower limit of the peeling force is actually 0.001 N / 25 mm or more. When the peeling force at a very high peeling speed of 6000 mm / min is within the above range, the surface protective film of the present invention can exhibit extremely excellent ultra-light peelability. The details of the measurement of the peeling force will be described later.

  In one embodiment of the surface protective film of the present invention, a 25 μm-thick polyethylene terephthalate film is bonded to the pressure-sensitive adhesive layer, and after 30 minutes at 23 ° C., the polyethylene terephthalate film is peeled at an angle of 180 ° and a peeling speed of 300 mm / min. Is preferably 0.02 N / 25 mm or less, more preferably 0.018 N / 25 mm or less, further preferably 0.015 N / 25 mm or less, and particularly preferably 0.012 N / 25 mm or less. / 25 mm or less, and most preferably 0.01 N / 25 mm or less. The lower limit of the peeling force is actually 0.001 N / 25 mm or more. When the peeling force is within the above range, the surface protective film of the present invention can exhibit ultra-light peelability. The details of the measurement of the peeling force will be described later.

  In one embodiment of the surface protective film of the present invention, a 25 μm-thick polyethylene terephthalate film is bonded to an adhesive layer, and after 7 days at 80 ° C., the polyethylene terephthalate film is peeled at a peel angle of 180 ° and a peel speed of 6000 mm / min. Is preferably 0.35 N / 25 mm or less, more preferably 0.33 N / 25 mm or less, still more preferably 0.3 N / 25 mm or less, and even more preferably 0.27 N or less. / 25 mm or less, particularly preferably 0.25 N / 25 mm or less, most preferably 0.23 N / 25 mm or less. The lower limit of the peeling force is actually 0.001 N / 25 mm or more. If the peeling force after 7 days at 80 ° C. is within the above range, the surface protective film of the present invention can sufficiently suppress heavy peeling over time. The details of the measurement of the peeling force will be described later.

  In one embodiment of the surface protective film of the present invention, a 25 μm-thick polyethylene terephthalate film is attached to an adhesive layer, and after 7 days at 80 ° C., the polyethylene terephthalate film is peeled at an angle of 180 ° and a peeling speed of 300 mm / min. Is preferably 0.07 N / 25 mm or less, more preferably 0.06 N / 25 mm or less, further preferably 0.05 N / 25 mm or less, and particularly preferably 0.045 N or less. / 25 mm or less, most preferably 0.04 N / 25 mm or less. The lower limit of the peeling force is actually 0.001 N / 25 mm or more. When the release force is within the above range, the surface protective film of the present invention can suppress heavy release over time. The details of the measurement of the peeling force will be described later.

  In one embodiment of the surface protective film of the present invention, a glass plate having a thickness of 1000 μm is attached to the pressure-sensitive adhesive layer, and after 30 minutes at 23 ° C., the glass plate is peeled off at a peeling angle of 180 ° and a peeling speed of 6000 mm / min. Is preferably 0.135 N / 25 mm or less, more preferably 0.1 N / 25 mm or less, further preferably 0.07 N / 25 mm or less, and still more preferably 0.065 N / 25 mm. Or less, particularly preferably 0.06 N / 25 mm or less, and most preferably 0.055 N / 25 mm or less. The lower limit of the peeling force is actually 0.001 N / 25 mm or more. When the peeling force at a very high peeling speed of 6000 mm / min is within the above range, the surface protective film of the present invention can exhibit extremely excellent ultra-light peelability. The details of the measurement of the peeling force will be described later.

  In one embodiment of the surface protection film of the present invention, a glass plate having a thickness of 1000 μm is bonded to the pressure-sensitive adhesive layer, and after 30 minutes at 23 ° C., the glass plate is peeled off at a peeling angle of 180 ° and a peeling speed of 300 mm / min. Is preferably 0.023 N / 25 mm or less, more preferably 0.022 N / 25 mm or less, further preferably 0.02 N / 25 mm or less, and particularly preferably 0.015 N / 25 mm. Or less, and most preferably 0.013 N / 25 mm or less. The lower limit of the peeling force is actually 0.001 N / 25 mm or more. When the peeling force is within the above range, the surface protective film of the present invention can exhibit ultra-light peelability. The details of the measurement of the peeling force will be described later.

  In one embodiment of the surface protective film of the present invention, a glass plate having a thickness of 1000 μm is bonded to the pressure-sensitive adhesive layer, and after 7 days at 80 ° C., the glass plate is peeled off at a peeling angle of 180 ° and a peeling speed of 6000 mm / min. Is preferably 0.35 N / 25 mm or less, more preferably 0.3 N / 25 mm or less, further preferably 0.25 N / 25 mm or less, and still more preferably 0.2 N / 25 mm. Or less, particularly preferably 0.15 N / 25 mm or less, and most preferably 0.1 N / 25 mm or less. The lower limit of the peeling force is actually 0.001 N / 25 mm or more. If the peeling force after 7 days at 80 ° C. is within the above range, the surface protective film of the present invention can sufficiently suppress heavy peeling over time. The details of the measurement of the peeling force will be described later.

  In one embodiment of the surface protective film of the present invention, a glass plate having a thickness of 1000 μm is attached to the pressure-sensitive adhesive layer, and after 7 days at 80 ° C., the glass plate is peeled off at a peeling angle of 180 ° and a peeling speed of 300 mm / min. Is preferably 0.05 N / 25 mm or less, more preferably 0.045 N / 25 mm or less, further preferably 0.04 N / 25 mm or less, and particularly preferably 0.035 N / 25 mm. Or less, and most preferably 0.03 N / 25 mm or less. The lower limit of the peeling force is actually 0.001 N / 25 mm or more. When the release force is within the above range, the surface protective film of the present invention can suppress heavy release over time. The details of the measurement of the peeling force will be described later.

  The surface protective film of the present invention has a residual adhesion rate of preferably 50% or more, more preferably 55% to 100%, further preferably 60% to 100%, and particularly preferably 65% to 100%. %, And most preferably 70% to 100%. When the residual adhesion ratio is within the above range, the surface protective film of the present invention can exhibit an effect that contamination on the adherend surface is low. The details of the measurement of the residual adhesion rate will be described later.

The surface protective film of the present invention can be manufactured by any appropriate method. Examples of such a manufacturing method include, for example,
(1) a method of applying a solution or a hot melt of a material for forming an adhesive layer on a base material layer,
(2) a method in which a solution or a hot melt of a material for forming the pressure-sensitive adhesive layer is applied to the separator, and the pressure-sensitive adhesive layer formed is transferred to the base material layer;
(3) a method of extruding a forming material for the pressure-sensitive adhesive layer onto the base material layer and forming and applying the material;
(4) a method of extruding the base material layer and the pressure-sensitive adhesive layer in two or multiple layers,
(5) a method of laminating the pressure-sensitive adhesive layer on the base material layer in a single layer or a method of laminating two pressure-sensitive adhesive layers together with the laminate layer;
(6) a method of laminating two or multiple layers of the pressure-sensitive adhesive layer and a base layer forming material such as a film or a laminate layer,
And the like, according to any appropriate manufacturing method.

  As a 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, or the like can be used.

≪Base layer≫
The base material layer may be only one layer, or may be two or more layers. The substrate layer may be stretched.

  The thickness of the base material layer is preferably 4 μm to 450 μm, more preferably 8 μm to 400 μm, still more preferably 12 μm to 350 μm, and particularly preferably 16 μm to 250 μm.

  For the purpose of forming a roll that can be easily unwound on the surface of the base material layer on which the pressure-sensitive adhesive layer is not attached, for example, a fatty acid amide, a polyethyleneimine, a long-chain alkyl-based additive may be added to the base material layer. Or the like, to perform a release treatment, or to provide a coat layer made of any appropriate release agent such as a silicone-based, long-chain alkyl-based, or fluorine-based release agent.

  Any appropriate material can be adopted as the material of the base material layer depending on the application. For example, plastic, paper, metal film, nonwoven fabric and the like can be mentioned. Preferably, it is plastic. That is, the substrate layer is preferably a plastic film. The base material layer may be composed of one type of material, or may be composed of two or more types of materials. For example, it may be composed of two or more plastics.

  Examples of the plastic include a polyester resin, a polyamide resin, and a polyolefin resin. Examples of the polyester-based resin include polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate. Examples of the polyolefin resin include a homopolymer of an olefin monomer and a copolymer of an olefin monomer. Specific examples of the polyolefin-based resin include, for example, homopolypropylene; propylene-based copolymers such as block-based, random-based, and graft-based copolymers having an ethylene component as a copolymer component; reactor TPO; Low-density, ultra-low-density ethylene polymers; ethylene / propylene copolymer, ethylene / vinyl acetate copolymer, ethylene / methyl acrylate copolymer, ethylene / ethyl acrylate copolymer, ethylene / acrylic acid Ethylene-based copolymers such as butyl copolymer, ethylene-methacrylic acid copolymer, ethylene-methyl methacrylate copolymer; and the like.

  The base material layer may contain any appropriate additive as needed. Examples of the additives that can be contained in the base material layer include an antioxidant, an ultraviolet absorber, a light stabilizer, an antistatic agent, a filler, and a pigment. 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 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 the weather resistance and the like, particularly preferably, the additives include an antioxidant, an ultraviolet absorber, a light stabilizer, and a filler.

  Any appropriate antioxidant can be employed as the antioxidant. Examples of such antioxidants include phenolic antioxidants, phosphorus-based processing heat stabilizers, lactone-based processing heat stabilizers, sulfur-based heat-resistant stabilizers, and phenol / phosphorus-based antioxidants. The content ratio of the antioxidant is preferably 1% by weight or less, more preferably 1% by weight, based on the base resin of the base material layer (when the base material layer is a blend, the blend 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 employed as the ultraviolet absorber. 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, the blend is the base resin). It is preferably at most 1% by weight, more preferably from 0.01% by weight to 0.5% by weight.

  Any appropriate light stabilizer can be employed as the light stabilizer. Examples of such a light stabilizer include a hindered amine light stabilizer and a benzoate light stabilizer. The content ratio of the light stabilizer is preferably 2% by weight or less based on the base resin forming the base material layer (when the base material layer is a blend, the blend is the base resin). It is preferably at most 1% by weight, more preferably from 0.01% by weight to 0.5% by weight.

  Any appropriate filler can be adopted as the filler. Examples of such a filler include an inorganic filler. Specific examples of the inorganic filler include, for example, 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, based on the base resin forming the base material layer (when the base material layer is a blend, the blend is the base resin). Is 10% by weight or less, and more preferably 0.01% by weight to 10% by weight.

  Further, as additives, surfactants, inorganic salts, polyhydric alcohols, metal compounds, inorganic compounds such as carbon, and low-molecular-weight and high-molecular-weight antistatic agents are preferably exemplified for the purpose of imparting antistatic properties. In particular, a high molecular weight antistatic agent and carbon are preferable from the viewpoint of contamination and maintenance of tackiness.

≪Adhesive layer≫
The pressure-sensitive adhesive layer can be manufactured by any appropriate manufacturing method. Examples of such a production method include a method in which a composition that is a material for forming an adhesive layer is applied on a substrate layer, and an adhesive layer is formed on the substrate layer. Examples of such a coating method include roll coating, gravure coating, reverse coating, roll brushing, spray coating, air knife coating, and extrusion coating with a die coater.

  The thickness of the pressure-sensitive adhesive layer is preferably 1 μm to 150 μm, more preferably 2 μm to 140 μm, still more preferably 3 μm to 130 μm, further preferably 4 μm to 120 μm, and still more preferably 5 μm to 100 μm. More preferably, it is 10 μm to 90 μm, particularly preferably 20 μm to 85 μm, and most preferably 30 μm to 80 μm.

  The pressure-sensitive adhesive layer is composed of a pressure-sensitive adhesive. The adhesive is formed from an adhesive composition.

  The pressure-sensitive adhesive composition preferably contains a base polymer and a silicone-based additive and / or a fluorine-based additive.

  The content of the silicone-based additive and / or the fluorine-based additive in the pressure-sensitive adhesive composition is preferably 0.01 part by weight as the total amount of the silicone-based additive and the fluorine-based additive based on 100 parts by weight of the base polymer. To 50 parts by weight, more preferably 0.02 to 25 parts by weight, still more preferably 0.025 to 10 parts by weight, and particularly preferably 0.03 to 5 parts by weight. And most preferably 0.05 to 3 parts by weight. When the content of the silicone-based additive and / or the fluorine-based additive in the pressure-sensitive adhesive composition is within the above range, the surface protective film of the present invention can exhibit higher ultra-light peelability, Body surface contamination may be lower.

<Base polymer>
The base polymer is preferably at least one selected from urethane resins, acrylic resins, rubber resins, and silicone resins. The base polymer is more preferably a urethane resin or an acrylic resin in that the effects of the present invention can be more exhibited.

(Urethane resin)
As the urethane-based resin, any appropriate urethane-based resin can be adopted as long as the effects of the present invention are not impaired. As the urethane resin, preferably, a urethane resin formed from a composition containing a polyol (A) and a polyfunctional isocyanate compound (B), or a urethane prepolymer (C) and a polyfunctional isocyanate compound (B) Is a urethane-based resin formed from a composition containing Since the wettability of the pressure-sensitive adhesive layer can be improved by employing the above-described urethane-based resin, the surface protective film of the present invention can be adhered without involving air bubbles.

  The urethane-based resin may contain any appropriate component as long as the effects of the present invention are not impaired. Examples of such components include resin components other than urethane-based resins, tackifiers, inorganic fillers, organic fillers, metal powders, pigments, foils, softeners, antioxidants, conductive agents, and ultraviolet absorbers. Agents, antioxidants, light stabilizers, surface lubricants, leveling agents, corrosion inhibitors, heat stabilizers, polymerization inhibitors, lubricants, solvents, catalysts and the like.

  The urethane-based resin preferably contains a deterioration inhibitor such as an antioxidant, an ultraviolet absorber, and a light stabilizer. When the urethane-based resin contains the deterioration inhibitor, even if it is stored in a heated state after being adhered to the adherend, the adherent can hardly be left on the adherend. The deterioration inhibitor may be only one kind or two or more kinds. As the deterioration inhibitor, an antioxidant is particularly preferred.

  Examples of the antioxidant include a radical chain inhibitor, a peroxide decomposer, and the like.

  Examples of the radical chain inhibitor include a phenolic antioxidant and an amine antioxidant.

  Examples of the peroxide decomposing agent include a sulfur-based antioxidant and a phosphorus-based antioxidant.

  Examples of the phenol-based antioxidant include a monophenol-based antioxidant, a bisphenol-based antioxidant, and a polymer-type phenol-based antioxidant.

  Examples of the monophenol-based 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 and the like.

  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- ( 3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl] 2,4,8,10-tetraoxaspiro [5,5] undecane.

  Examples of the polymeric 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 and the like.

  Examples of the sulfur-based antioxidant include dilauryl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate, distearyl 3,3'-thiodipropionate, and the like.

  Examples of the phosphorus-based antioxidant include triphenyl phosphite, diphenyl isodecyl phosphite, phenyl diisodecyl phosphite, and the like.

  Examples of the ultraviolet absorber include a benzophenone-based ultraviolet absorber, a benzotriazole-based ultraviolet absorber, a salicylic acid-based ultraviolet absorber, an oxalic anilide-based ultraviolet absorber, a cyanoacrylate-based ultraviolet absorber, and a triazine-based ultraviolet absorber. Can be

  Examples of the benzophenone-based ultraviolet absorber include, for example, 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 and the like.

  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'-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' ',-tetrahydrophthalimidomethyl) -5'-methylphenyl] benzotriazole, 2,2'methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol], 2- (2'-hydroxy-5'-methacryloxyphenyl) -2H-benzotriazole, and the like.

  Examples of the salicylic acid-based ultraviolet absorber include phenyl salicylate, p-tert-butylphenyl salicylate, p-octylphenyl salicylate and the like.

  Examples of the cyanoacrylate-based ultraviolet absorber include 2-ethylhexyl-2-cyano-3,3'-diphenyl acrylate, ethyl-2-cyano-3,3'-diphenyl acrylate, and the like.

  Examples of the light stabilizer include a hindered amine light stabilizer and an ultraviolet light stabilizer.

  Examples of the hindered amine light stabilizer include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, methyl -1,2,2,6,6-pentamethyl-4-piperidyl sebacate and the like.

  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-. Butyl-4-hydroxybenzyl-phosphate monoethylate, nickel-dibutyldithiocarbamate, benzoate-type quencher, nickel-dibutyldithiocarbamate and the like.

(Urethane resin formed from a composition containing a polyol (A) and a polyfunctional isocyanate compound (B))
The urethane resin formed from the composition containing the polyol (A) and the polyfunctional isocyanate compound (B) is preferably a composition containing the polyol (A) and the polyfunctional isocyanate compound (B). It is a urethane resin obtained by curing an object.

  The polyol (A) may be only one kind or two or more kinds.

  The polyfunctional isocyanate compound (B) may be only one kind or two or more kinds.

  As the polyol (A), preferably, for example, polyester polyol, polyether polyol, polycaprolactone polyol, polycarbonate polyol, and castor oil-based polyol are preferably used. The polyol (A) is more preferably a polyether polyol.

  The polyester polyol can be obtained, for example, by an esterification reaction between a polyol component and an acid component.

  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 -1,8-octanediol, 1,8-decanediol, octadecanediol, glycerin, trimethylolpropane, pentaerythritol, hexanetriol, polypropylene glycol and the like. Examples of the acid component include succinic acid, methylsuccinic acid, adipic acid, pimelic acid, azelaic acid, sebacic acid, 1,12-dodecandioic acid, 1,14-tetradecandioic 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′-biphenyldicarboxylic acid And their acid anhydrides.

  Examples of polyether polyols include water, low molecular weight polyols (such as propylene glycol, ethylene glycol, glycerin, trimethylolpropane, and pentaerythritol), bisphenols (such as bisphenol A), and dihydroxybenzenes (such as catechol, resorcinol, and hydroquinone). And a polyether polyol obtained by addition-polymerizing an alkylene oxide such as ethylene oxide, propylene oxide or butylene oxide. Specific examples include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and the like.

  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.

  As the polycarbonate polyol, for example, a polycarbonate polyol obtained by performing a polycondensation reaction of the above polyol component and phosgene; the above polyol component, dimethyl carbonate, diethyl carbonate, diprovyl carbonate, diisopropyl carbonate, dibutyl carbonate, ethylbutyl carbonate, ethylene carbonate, Polycarbonate polyol obtained by transesterification condensation of carbonic acid diesters such as propylene carbonate, diphenyl carbonate, dibenzyl carbonate, etc .; Copolymerized polycarbonate polyol obtained by using two or more of the above polyol components; A polycarbonate polyol obtained by subjecting a compound to an esterification reaction; A polycarbonate polyol obtained by a transesterification reaction; a polycarbonate polyol obtained by a transesterification reaction between the above-mentioned various polycarbonate polyols and an ester compound; a polycarbonate polyol obtained by a transesterification reaction between the above-mentioned various polycarbonate polyols and a hydroxyl group-containing compound; Polyester-based polycarbonate polyols obtained by polycondensation reaction of the above-mentioned various polycarbonate polyols and dicarboxylic acid compounds; copolymerized polyether-based polycarbonate polyols obtained by copolymerizing the above-mentioned various polycarbonate polyols with alkylene oxide; and the like.

  Examples of castor oil-based polyols include castor oil-based polyols obtained by reacting castor oil fatty acids with the above-mentioned polyol components. Specific examples include castor oil-based polyols obtained by reacting castor oil fatty acids with polypropylene glycol.

  The number average molecular weight Mn of the polyol (A) is preferably from 300 to 100,000, more preferably from 400 to 75,000, further preferably from 450 to 50,000, and particularly preferably from 500 to 30,000. By adjusting the number average molecular weight Mn of the polyol (A) within the above range, the wettability of the pressure-sensitive adhesive layer can be improved, so that the surface protective film of the present invention can be adhered without involving air bubbles. .

  The polyol (A) preferably contains a polyol (A1) having three OH groups and a number average molecular weight Mn of 300 to 100,000. The polyol (A1) may be only one kind or two or more kinds.

  The content ratio of the polyol (A1) in the polyol (A) is preferably 5% by weight or more, more preferably 25% by weight to 100% by weight, and further preferably 50% by weight to 100% by weight. By adjusting the content of the polyol (A1) in the polyol (A) within the above range, the wettability of the pressure-sensitive adhesive layer can be improved. Therefore, the surface protective film of the present invention can be adhered without involving air bubbles. Becomes possible.

  The number average molecular weight Mn of the polyol (A1) is preferably 1,000 to 100,000, more preferably 1200 to 80,000, further preferably 1500 to 70,000, further preferably 1750 to 50,000, and particularly preferably 1500 ４０40000, most preferably 2,000 to 30,000. By adjusting the number average molecular weight Mn of the polyol (A1) within the above range, the wettability of the pressure-sensitive adhesive layer can be improved, so that the surface protective film of the present invention can be adhered without involving air bubbles. .

  The polyol (A) may contain a polyol (A2) having three or more OH groups and a number average molecular weight Mn of 20,000 or less. The polyol (A2) may be only one kind, or two or more kinds. The number average molecular weight Mn of the polyol (A2) is preferably from 100 to 20,000, more preferably from 150 to 10000, further preferably from 200 to 7,500, particularly preferably from 300 to 6000, and most preferably from 300 to 6000. ~ 5000. When the number average molecular weight Mn of the polyol (A2) is out of the above range, in particular, the adhesive strength may increase with time, and excellent reworkability may not be exhibited. The polyol (A2) is preferably a polyol having three OH groups (triol), a polyol having four OH groups (tetraol), a polyol having five OH groups (pentaol), and having six OH groups. Having a polyol (hexaol).

  As the polyol (A2), the total amount of at least one of a polyol having four OH groups (tetraol), a polyol having five OH groups (pentaol), and a polyol having six OH groups (hexaol) is as follows: The content in the polyol (A) is preferably at most 70% by weight, more preferably at most 60% by weight, further preferably at most 40% by weight, particularly preferably at most 30% by weight. In the polyol (A), as the polyol (A2), at least a polyol having four OH groups (tetraol), a polyol having five OH groups (pentaol), and a polyol having six OH groups (hexaol) are used. By adjusting one kind to the above range, a urethane-based resin having excellent transparency can be provided, and the wettability of the pressure-sensitive adhesive layer can be improved. Sticking is possible without getting involved.

  The content ratio of the polyol (A2) in the polyol (A) is preferably 95% by weight or less, and more preferably 0% to 75% by weight. By adjusting the content of the polyol (A2) in the polyol (A) within the above range, the wettability of the pressure-sensitive adhesive layer can be improved, and thus the surface protective film of the present invention can be adhered without involving air bubbles. Becomes possible.

  In the polyol (A2), the content ratio of a polyol having four or more OH groups and a number average molecular weight Mn of 20,000 or less is preferably less than 70% by weight based on the whole polyol (A), and more preferably. Is at most 60% by weight, more preferably at most 50% by weight, particularly preferably at most 40% by weight, most preferably at most 30% by weight. By adjusting the content ratio of the polyol having a number average molecular weight Mn having 4 or more OH groups in the polyol (A2) of 20,000 or less to the above range, it is possible to provide a urethane resin excellent in transparency, Since the wettability of the pressure-sensitive adhesive layer can be improved, the surface protective film of the present invention can be stuck without involving air bubbles.

  The polyfunctional isocyanate compound (B) may be only one kind or two or more kinds.

  As the polyfunctional isocyanate compound (B), any appropriate polyfunctional isocyanate compound that can be used for a urethanization reaction can be employed. Examples of such a polyfunctional isocyanate compound (B) include a polyfunctional aliphatic isocyanate compound, a polyfunctional alicyclic isocyanate, and a polyfunctional aromatic isocyanate compound.

  Examples of the polyfunctional aliphatic isocyanate compound include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, 4-trimethylhexamethylene diisocyanate and the like.

  Examples of the polyfunctional alicyclic isocyanate compound include, for example, 1,3-cyclopentene diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, Hydrogenated tolylene diisocyanate, hydrogenated tetramethylxylylene diisocyanate and the like can be mentioned.

  Examples of the polyfunctional aromatic diisocyanate compound include phenylene diisocyanate, 2,4-tolylene diisosonate, 2,6-tolylene diisocyanate, 2,2′-diphenylmethane diisocyanate, 4,4′-diphenylmethane diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalenediisocyanate, xylylene diisocyanate, and the like.

  Examples of the polyfunctional isocyanate compound (B) include a trimethylolpropane adduct of the above-mentioned various polyfunctional isocyanate compounds, a buret body reacted with water, a trimer having an isocyanurate ring, and the like. These may be used in combination.

  The equivalent ratio of the NCO group to the OH group in the polyol (A) and the polyfunctional isocyanate compound (B) is preferably 5.0 or less as NCO group / OH group, and more preferably 0.1 to 3.0. , More preferably 0.2 to 2.5, particularly preferably 0.3 to 2.25, and most preferably 0.5 to 2.0. By adjusting the equivalent ratio of NCO group / OH group within the above range, the wettability of the pressure-sensitive adhesive layer can be improved, so that the surface protective film of the present invention can be adhered without involving air bubbles.

  As for the content ratio of the polyfunctional isocyanate compound (B), the polyfunctional isocyanate compound (B) is preferably from 1.0% by weight to 30% by weight, more preferably 1.5% by weight, based on the polyol (A). % To 27% by weight, more preferably 2.0% to 25% by weight, particularly preferably 2.3% to 23% by weight, most preferably 2.5% to 20% by weight. It is. By adjusting the content of the polyfunctional isocyanate compound (B) within the above range, the wettability of the pressure-sensitive adhesive layer can be improved. Therefore, the surface protective film of the present invention can be stuck without involving air bubbles. Become.

  Specifically, the polyurethane resin is preferably formed by curing a composition containing the polyol (A) and the polyfunctional isocyanate compound (B).

  Examples of a method for curing a composition containing a polyol (A) and a polyfunctional isocyanate compound (B) to form a urethane resin include the effects of the present invention, such as a urethanization reaction method using bulk polymerization or solution polymerization. Any appropriate method can be adopted as long as the method does not impair.

  To cure the composition containing the polyol (A) and the polyfunctional isocyanate compound (B), a catalyst is preferably used. Examples of such a catalyst include an organometallic compound, a tertiary amine compound, and the like.

  Examples of the organometallic compound include an iron compound, a tin compound, a titanium compound, a zirconium compound, a lead compound, a cobalt compound, and a zinc compound. Among these, iron-based compounds and tin-based compounds are preferred in terms of reaction rate and pot life of the pressure-sensitive adhesive layer.

  Examples of the iron-based compound include iron acetylacetonate, iron 2-ethylhexanoate, and the like.

  As the tin-based compound, for example, dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin maleate, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin sulfide, tributyltin methoxide, tributyltin acetate, triethyltin ethoxide, Examples include tributyltin ethoxide, dioctyltin oxide, dioctyltin dilaurate, tributyltin chloride, tributyltin trichloroacetate, and tin 2-ethylhexanoate.

  Examples of the titanium-based compound include dibutyl titanium dichloride, tetrabutyl titanate, butoxy titanium trichloride and the like.

  Examples of the zirconium-based compound include zirconium naphthenate and zirconium acetylacetonate.

  Examples of the lead compound include lead oleate, lead 2-ethylhexanoate, lead benzoate, lead naphthenate, and the like.

  Examples of the cobalt-based compound include cobalt 2-ethylhexanoate, cobalt benzoate, and the like.

  Examples of the zinc-based compound include zinc naphthenate and zinc 2-ethylhexanoate.

  Examples of the tertiary amine compound include triethylamine, triethylenediamine, 1,8-diazabicyclo- (5,4,0) -undecene-7, and the like.

  The catalyst may be only one kind or two or more kinds. Further, a catalyst and a crosslinking retarder may be used in combination. The amount of the catalyst is preferably 0.005% by weight to 1.00% by weight, more preferably 0.01% by weight to 0.75% by weight, and still more preferably 0% by weight, based on the polyol (A). 0.01% to 0.50% by weight, particularly preferably 0.01% to 0.20% by weight. By adjusting the amount of the catalyst within the above range, the wettability of the pressure-sensitive adhesive layer can be improved, so that the surface protective film of the present invention can be adhered without involving air bubbles.

  The composition containing the polyol (A) and the polyfunctional isocyanate compound (B) may contain any appropriate other components as long as the effects of the present invention are not impaired. As such other components, for example, a resin component other than the polyurethane resin, a tackifier, an inorganic filler, an organic filler, a metal powder, a pigment, a foil, a softener, an antioxidant, a conductive agent, Examples include ultraviolet absorbers, antioxidants, light stabilizers, surface lubricants, leveling agents, corrosion inhibitors, heat stabilizers, polymerization inhibitors, lubricants, solvents, and catalysts.

(Urethane-based resin formed from a composition containing a urethane prepolymer (C) and a polyfunctional isocyanate compound (B))
The urethane resin formed from the composition containing the urethane prepolymer (C) and the polyfunctional isocyanate compound (B) may be any urethane resin obtained using a so-called “urethane prepolymer” as a raw material. An appropriate urethane-based resin can be employed.

  The urethane resin formed from the composition containing the urethane prepolymer (C) and the polyfunctional isocyanate compound (B) includes, for example, a polyurethane polyol as the urethane prepolymer (C) and the polyfunctional isocyanate compound (B). Urethane-based resin formed from the composition. The urethane prepolymer (C) may be only one kind or two or more kinds. The polyfunctional isocyanate compound (B) may be only one kind or two or more kinds.

  The polyurethane polyol as the urethane prepolymer (C) is preferably a polyester polyol (a1) or a polyether polyol (a2) alone or in a mixture of (a1) and (a2) in the presence of a catalyst or It is obtained by reacting with an organic polyisocyanate compound (a3) in the absence of a catalyst.

  As the polyester polyol (a1), any appropriate polyester polyol can be used. Examples of such a polyester polyol (a1) include a polyester polyol obtained by reacting an acid component and a glycol component. Examples of the acid component include terephthalic acid, adipic acid, azelaic acid, sebacic acid, phthalic anhydride, isophthalic acid, trimellitic acid, and the like. 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′-dimethylolheptane, polyoxyethylene glycol, Polyoxypropylene glycol, 1,4-butanediol, neopentyl glycol, butylethylpentanediol, glycerin, trimethylolpropane, pentaerythritol and the like as polyol components are exemplified. Other examples of the polyester polyol (a1) include polyester polyols obtained by ring-opening polymerization of lactones such as polycaprolactone, poly (β-methyl-γ-valerolactone), and polyvalerolactone.

  The molecular weight of the polyester polyol (a1) can be used from a low molecular weight to a high molecular weight. As the molecular weight of the polyester polyol (a1), the number average molecular weight is preferably 100 to 100,000. If the number average molecular weight is less than 100, the reactivity may be high and gelation may be easily caused. When the number average molecular weight exceeds 100,000, the reactivity may be low, and the cohesive force of the polyurethane polyol itself may be low. The amount of the polyester polyol (a1) used is preferably 0 mol% to 90 mol% in the polyol constituting the polyurethane polyol.

  As the polyether polyol (a2), any appropriate polyether polyol can be used. As such a polyether polyol (a2), for example, water, a low molecular weight polyol such as propylene glycol, ethylene glycol, glycerin, and trimethylolpropane is used as an initiator, and ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, and the like are used. A polyether polyol obtained by polymerizing an oxirane compound is exemplified. Specific examples of such a polyether polyol (a2) include polyether polyols having two or more functional groups, such as polypropylene glycol, polyethylene glycol, and polytetramethylene glycol.

  The molecular weight of the polyether polyol (a2) can be used from a low molecular weight to a high molecular weight. The number average molecular weight of the polyether polyol (a2) is preferably 100 to 100,000. If the number average molecular weight is less than 100, the reactivity may be high and gelation may be easily caused. When the number average molecular weight exceeds 100,000, the reactivity may be low, and the cohesive force of the polyurethane polyol itself may be low. The amount of the polyether polyol (a2) used is preferably 0 mol% to 90 mol% in the polyol constituting the polyurethane polyol.

  If necessary, the polyether polyol (a2) partially includes glycols such as ethylene glycol, 1,4-butanediol, neopentyl glycol, butylethylpentanediol, glycerin, trimethylolpropane, and pentaerythritol; Polyamines such as ethylenediamine, N-aminoethylethanolamine, isophoronediamine, xylylenediamine and the like can be used in combination.

  As the polyether polyol (a2), only a bifunctional polyether polyol may be used, or a polyether having a number average molecular weight of 100 to 100,000 and having at least three or more hydroxyl groups in one molecule. A part or all of the polyol may be used. When the polyether polyol (a2) has a number average molecular weight of 100 to 100,000 and uses a part or all of a polyether polyol having at least three or more hydroxyl groups in one molecule, the adhesive strength and the removability are improved. The balance can be good. If such a polyether polyol has a number average molecular weight of less than 100, the reactivity may be high and gelation may be easily caused. Further, in such a polyether polyol, if the number average molecular weight exceeds 100,000, the reactivity becomes low, and the cohesive force of the polyurethane polyol itself may be reduced. The number average molecular weight of such a polyether polyol is more preferably from 100 to 10,000.

  Any appropriate organic polyisocyanate compound can be used as the organic polyisocyanate compound (a3). Examples of such an organic polyisocyanate compound (a3) include aromatic polyisocyanate, aliphatic polyisocyanate, araliphatic polyisocyanate, and alicyclic polyisocyanate.

  Examples of the aromatic polyisocyanate include 1,3-phenylene diisocyanate, 4,4′-diphenyl diisocyanate, 1,4-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6 -Tolylene diisocyanate, 4,4'-toluidine diisocyanate, 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate benzene, dianisidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4 ', 4 "-triphenylmethane triisocyanate and the like.

  Examples of the aliphatic polyisocyanate include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate.

  As the araliphatic polyisocyanate, for example, ω, ω′-diisocyanate-1,3-dimethylbenzene, ω, ω′-diisocyanate-1,4-dimethylbenzene, ω, ω′-diisocyanate-1,4-diethylbenzene , 1,4-tetramethylxylylene diisocyanate, 1,3-tetramethyl xylylene diisocyanate, and the like.

  Examples of the alicyclic polyisocyanate include 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate, 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, and methyl-2. , 4-cyclohexanediisocyanate, methyl-2,6-cyclohexanediisocyanate, 4,4'-methylenebis (cyclohexylisocyanate), 1,4-bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanatomethyl) cyclohexane and the like. Can be

  As the organic polyisocyanate compound (a3), a trimethylolpropane adduct, a burette having reacted with water, a trimer having an isocyanurate ring, and the like can also be used in combination.

  Any appropriate catalyst can be used as a catalyst that can be used for obtaining the polyurethane polyol. Examples of such a catalyst include a tertiary amine compound and an organometallic compound.

  Examples of the tertiary amine compound include triethylamine, triethylenediamine, 1,8-diazabicyclo (5,4,0) -undecene-7 (DBU), and the like.

  Examples of the organometallic compound include a tin compound and a non-tin compound.

  Examples of the tin compound include dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin dimaleate, dibutyltin dilaurate (DBTDL), dibutyltin diacetate, dibutyltin sulfide, tributyltin sulfide, tributyltin oxide, and tributyltin. Examples include tin acetate, triethyltin ethoxide, tributyltin ethoxide, dioctyltin oxide, tributyltin chloride, tributyltin trichloroacetate, and tin 2-ethylhexanoate.

  Examples of the non-tin compounds include titanium compounds such as dibutyl titanium dichloride, tetrabutyl titanate and butoxy titanium trichloride; lead compounds such as lead oleate, lead 2-ethylhexanoate, lead benzoate and lead naphthenate. Iron compounds such as iron 2-ethylhexanoate and iron acetylacetonate; cobalt compounds such as cobalt benzoate and cobalt 2-ethylhexanoate; zinc compounds such as zinc naphthenate and zinc 2-ethylhexanoate; Zirconium compounds such as zirconium naphthenate; and the like.

  When a catalyst is used to obtain a polyurethane polyol, in a system in which two types of polyols, a polyester polyol and a polyether polyol, are present, due to a difference in reactivity, a single catalyst system causes gelation or a reaction solution. The problem of cloudiness is likely to occur. Therefore, by using two types of catalysts when obtaining a 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 such a combination of two types of catalysts include tertiary amine / organic metal, tin / non-tin, and tin / tin, and are preferably tin / tin, and more preferably tin / tin. Is a combination of dibutyltin dilaurate and tin 2-ethylhexanoate. As for the compounding ratio, tin 2-ethylhexanoate / dibutyltin dilaurate is preferably less than 1 and more preferably 0.2 to 0.6 by weight. If the compounding ratio is 1 or more, gelation may be easily caused due to the balance of the catalytic activities.

  When a catalyst is used for obtaining the polyurethane polyol, the amount of the catalyst is preferably 0.01 to the total amount of the polyester polyol (a1), the polyether polyol (a2) and the organic polyisocyanate compound (a3). ~ 1.0% by weight.

  When a catalyst is used in obtaining the polyurethane polyol, the reaction temperature is preferably lower than 100C, more preferably 85C to 95C. When 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 polyurethane polyol having a predetermined molecular weight.

  When obtaining a polyurethane polyol, a catalyst may not be used. In that case, the reaction temperature is preferably 100 ° C. or higher, more preferably 110 ° C. or higher. When a polyurethane polyol is obtained in the absence of a catalyst, the reaction is preferably performed for 3 hours or more.

  As a method for obtaining a polyurethane polyol, for example, 1) a method in which a polyester polyol, a polyether polyol, a catalyst, and an organic polyisocyanate are charged in a total volume flask; 2) a method in which a polyester polyol, a polyether polyol, and a catalyst are charged in a flask, and an organic polyisocyanate Is added dropwise. As a method for obtaining a polyurethane polyol, the method 2) is preferable for controlling the reaction.

  In obtaining the polyurethane polyol, any appropriate solvent can be used. Examples of such a solvent include methyl ethyl ketone, ethyl acetate, toluene, xylene, acetone and the like. Among these solvents, toluene is preferable.

  As the polyfunctional isocyanate compound (B), those described above can be used.

  The composition containing the urethane prepolymer (C) and the polyfunctional isocyanate compound (B) may contain any appropriate other components as long as the effects of the present invention are not impaired. As such other components, for example, a resin component other than the polyurethane resin, a tackifier, an inorganic filler, an organic filler, a metal powder, a pigment, a foil, a softener, an antioxidant, a conductive agent, Examples include ultraviolet absorbers, antioxidants, light stabilizers, surface lubricants, leveling agents, corrosion inhibitors, heat stabilizers, polymerization inhibitors, lubricants, solvents, and catalysts.

  As a method for producing a polyurethane resin formed from a composition containing a urethane prepolymer (C) and a polyfunctional isocyanate compound (B), a polyurethane resin is produced using a so-called “urethane prepolymer” as a raw material. If it is a method, any appropriate manufacturing method can be adopted.

  The number average molecular weight Mn of the urethane prepolymer (C) is preferably 3,000 to 1,000,000.

  The equivalent ratio of NCO groups to OH groups in the urethane prepolymer (C) and the polyfunctional isocyanate compound (B) is preferably 5.0 or less as NCO groups / OH groups, more preferably 0.01 to 3 as NCO groups / OH groups. 0.0, more preferably 0.02 to 2.5, particularly preferably 0.03 to 2.25, and most preferably 0.05 to 2.0. By adjusting the equivalent ratio of NCO group / OH group within the above range, the wettability of the pressure-sensitive adhesive layer can be improved, so that the surface protective film of the present invention can be adhered without involving air bubbles.

  The content ratio of the polyfunctional isocyanate compound (B) is preferably 0.01% by weight to 30% by weight, more preferably 0.1% by weight, based on the urethane prepolymer (C). 03% to 20% by weight, more preferably 0.05% to 15% by weight, particularly preferably 0.075% to 10% by weight, and most preferably 0.1% to 8% by weight. % By weight. By adjusting the content of the polyfunctional isocyanate compound (B) within the above range, the wettability of the pressure-sensitive adhesive layer can be improved. Therefore, the surface protective film of the present invention can be stuck without involving air bubbles. Become.

(Acrylic resin)
As the acrylic resin, any appropriate acrylic pressure-sensitive adhesive such as a known acrylic pressure-sensitive adhesive described in, for example, JP-A-2013-241606 can be employed as long as the effects of the present invention are not impaired.

  The acrylic resin may contain any appropriate component as long as the effects of the present invention are not impaired. Such components include, for example, resin components other than acrylic resins, tackifiers, inorganic fillers, organic fillers, metal powders, pigments, foils, softeners, antioxidants, conductive agents, and ultraviolet absorbers. Agents, antioxidants, light stabilizers, surface lubricants, leveling agents, corrosion inhibitors, heat stabilizers, polymerization inhibitors, lubricants, solvents, catalysts and the like.

(Rubber resin)
As the rubber-based resin, any appropriate rubber-based pressure-sensitive adhesive such as a known rubber-based pressure-sensitive adhesive described in JP-A-2015-074711, for example, may be employed as long as the effects of the present invention are not impaired. These may be only one kind or two or more kinds.

  The rubber-based resin may contain any appropriate component as long as the effects of the present invention are not impaired. Such components include, for example, resin components other than rubber-based resins, tackifiers, inorganic fillers, organic fillers, metal powders, pigments, foils, softeners, antioxidants, conductive agents, and ultraviolet absorbers. Agents, antioxidants, light stabilizers, surface lubricants, leveling agents, corrosion inhibitors, heat stabilizers, polymerization inhibitors, lubricants, solvents, catalysts and the like.

(Silicone resin)
As the silicone-based pressure-sensitive adhesive, any appropriate silicone-based pressure-sensitive adhesive, such as a known silicone-based pressure-sensitive adhesive described in JP-A-2014-047280, for example, may be employed as long as the effects of the present invention are not impaired. . These may be only one kind or two or more kinds.

  The silicone resin may contain any appropriate component as long as the effects of the present invention are not impaired. Such components include, for example, resin components other than silicone resins, tackifiers, inorganic fillers, organic fillers, metal powders, pigments, foils, softeners, antioxidants, conductive agents, and ultraviolet absorbers. Agents, antioxidants, light stabilizers, surface lubricants, leveling agents, corrosion inhibitors, heat stabilizers, polymerization inhibitors, lubricants, solvents, catalysts and the like.

<Silicone-based additive>
As the silicone-based additive, any appropriate silicone-based additive can be adopted as long as the effect of the present invention is not impaired. Such a silicone-based additive preferably includes at least one selected from a siloxane bond-containing compound, a hydroxyl-containing silicone-based compound, and a crosslinkable functional group-containing silicone-based compound.

  The silicone-based additive may be only one kind or two or more kinds.

  Examples of the siloxane bond-containing compound include a polyether-modified polyorganosiloxane in which a polyether group is introduced into a main chain or a side chain of a polyorganosiloxane skeleton (such as polydimethylsiloxane); Polyester-modified polyorganosiloxane having a polyester group introduced therein, organic compound-introduced polyorganosiloxane having an organic compound introduced into the main chain or side chain of the polyorganosiloxane skeleton, silicone modified (poly) siloxane having been introduced into a (meth) acrylic resin ( Examples include (meth) acrylic resins, silicone-modified organic compounds in which a polyorganosiloxane is introduced into an organic compound, and silicone-containing organic compounds obtained by copolymerizing an organic compound and a silicone compound. As such a siloxane bond-containing polymer, commercially available products include, for example, trade name “LE-302” (manufactured by Kyoeisha Chemical Co., Ltd.) and a BYK series leveling agent (“BYK-300” manufactured by BYK Japan KK). "," 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- 77, BYK-378, BYK-UV3500, BYK-UV3510, BYK-UV3570, BYK-3550, BYK-SILCLEAN3700, BYK-SILCLEAN3720, etc.), Algin Chemie Leveling agents of the AC series ("AC FS180", "AC FS360", "AC S20", etc.) 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., and a leveling agent of KP series manufactured by Shin-Etsu Chemical Co., Ltd. (" KP- 323 "," KP-326 "," KP-34 " 1), "KP-104", "KP-110", "KP-112", X22 series and KF series manufactured by Shin-Etsu Chemical Co., Ltd., and leveling agents manufactured by Toray Dow Corning Co., Ltd. ("LP −7001 ”,“ LP-7002 ”,“ 8032ADDITIVE ”,“ 57ADDITIVE ”,“ L-7604 ”,“ FZ-2110 ”,“ FZ-2105 ”,“ 67ADDITIVE ”,“ 8618ADDITIVE ”,“ 3ADDITIVE ”,“ 56ADDITIVE ” And the like).

  Examples of the hydroxyl group-containing silicone compound include a polyether-modified polyorganosiloxane in which a polyether group is introduced into a main chain or a side chain of a polyorganosiloxane skeleton (such as polydimethylsiloxane), and a main chain or a side chain of a polyorganosiloxane skeleton. Polyester-modified polyorganosiloxane with a polyester group introduced into the polymer, organic compound-introduced polyorganosiloxane with an organic compound introduced into the main or side chain of the polyorganosiloxane skeleton, or silicone-modified with a (meth) acrylic resin into which a polyorganosiloxane is introduced Examples include (meth) acrylic resins, silicone-modified organic compounds obtained by introducing a polyorganosiloxane into an organic compound, and silicone-containing organic compounds obtained by copolymerizing an organic compound and a silicone compound. In these, the hydroxyl group may be possessed by a polyorganosiloxane skeleton, and may be possessed by a polyether group, a polyester group, a (meth) acryloyl group, or an organic compound. As such hydroxyl group-containing silicone, commercially available products include, for example, trade names “X-22-4015”, “X-22-4039”, “KF6000”, “KF6001”, “KF6002”, “KF6003”, “X-22-170BX”, “X-22-170DX”, “X-22-176DX”, “X-22-176F” (manufactured by Shin-Etsu Chemical Co., Ltd.), “BYK” manufactured by BYK Japan KK -370 "," BYK-SILCLEAN 3700 "," BYK-SILCLEAN 3720 "and the like.

  Examples of the crosslinkable functional group-containing silicone compound include polyether-modified polyorganosiloxane in which a polyether group is introduced into a main chain or a side chain of a polyorganosiloxane skeleton (such as polydimethylsiloxane), and a polyorganosiloxane skeleton. Polyester-modified polyorganosiloxane with a polyester group introduced into the chain or side chain, organic compound-introduced polyorganosiloxane with an organic compound introduced into the main or side chain of the polyorganosiloxane skeleton, polyorganosiloxane in the (meth) acrylic resin Examples thereof include a silicone-modified (meth) acrylic resin introduced, a silicone-modified organic compound in which a polyorganosiloxane is introduced into an organic compound, and a silicone-containing organic compound obtained by copolymerizing an organic compound and a silicone compound. In these, the crosslinkable functional group may have a polyorganosiloxane skeleton, and may have a polyether group, a polyester group, a (meth) acryloyl group, or an organic compound. Examples of the crosslinkable functional group include an amino group, an epoxy group, a mercapto group, a carboxyl group, an isocyanate group, and a methacrylate group. Examples of commercially available isocyanate group-containing silicones include “BY16-855”, “SF8413”, “BY16-839”, “SF8421”, and “BY16-750” manufactured by Dow Corning Toray Co., Ltd. ", BY16-880", "BY16-152C", "KF-868", "KF-865", "KF-864", "KF-859", "KF-393" manufactured by Shin-Etsu Chemical Co., Ltd. , "KF-860", "KF-880", "KF-8004", "KF-8002", "KF-8005", "KF-867", "KF-8021", "KF-869", " “KF-861”, “X-22-343”, “KF-101”, “X-22-2000”, “X-22-4741”, “KF-1002”, “KF-2001”, “ -22-3701E "," X-22-164 "," X-22-164A "," X-22-164B "," X-22-164AS ", and the like" X-22-2445 ".

<Fluorine additive>
As the fluorine-based additive, any appropriate fluorine-based additive can be adopted as long as the effects of the present invention are not impaired. Such a fluorine-based additive preferably includes at least one selected from a fluorine-containing compound, a hydroxyl-containing fluorine-containing compound, and a crosslinkable functional group-containing fluorine-containing compound.

  The fluorine-based additive may be only one kind or two or more kinds.

  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 compound, and a fluorine-containing compound containing an organic compound. Examples of the fluoroaliphatic hydrocarbon skeleton include fluoro C1-C10 alkanes such as fluoromethane, fluoroethane, fluoropropane, fluoroisopropane, fluorobutane, fluoroisobutane, fluorot-butane, fluoropentane, and fluorohexane. Can be As such fluorine-containing compounds, commercially available products include, for example, leveling agents (“S-242”, “S-243”, “S-420”, “S-420”, “S-242”, manufactured by AGC Seimi Chemical Co., Ltd.) S-611 "," S-651 "," S-386 ", etc.) BYK series leveling agent (" BYK-340 ", etc.) manufactured by BYK Japan KK, and AC series leveling manufactured by Algin Chemie. (“AC 110a”, “AC 100a”, etc.), leveling agents of MegaFac series manufactured by DIC Corporation (“MegaFac F-114”, “MegaFac F-410”, “MegaFac F-444”) , “MegaFac EXP TP-2066”, “MegaFac F-430”, “MegaFac F-472SF”, “MegaFac -577 "," MegaFac F-552 "," MegaFac F-553 "," MegaFac F-554 "," MegaFac F-555 "," MegaFac R-94 "," MegaFac RS-72 " -K "," MegaFac RS-75 "," MegaFac F-556 "," MegaFac EXP TF-1367 "," MegaFac EXP TF-1437 "," MegaFac F-558 "," MegaFac EXP " TF-1537 "), FC series leveling agents (" FC-4430 "," FC-4432 ", etc.) manufactured by Sumitomo 3M Co., Ltd., and Futergent series leveling agents (" Fergent "manufactured by Neos Corporation). 100, "Fargent 100C", "Fargent 110", "Fargent 150", "Fargent 1" 50CH "," Fergent AK "," Fergent 501 "," Fergent 250 "," Fergent 251 "," Fergent 222F "," Fergent 208G "," Fergent 300 "," Fergent " 310 "," Fugent 400SW ", etc.), a leveling agent of the PF series manufactured by Kitamura Chemical Industry Co., Ltd. (" PF-136A "," PF-156A "," PF-151N "," PF-636 "," PF-636 " PF-6320 "," PF-656 "," PF-6520 "," PF-651 "," PF-652 "," PF-3320 ", etc.).

  As the hydroxyl group-containing fluorine-based compound, for example, conventionally known resins can be used. For example, WO94 / 06870, JP-A-8-12921, JP-A-10-72569, and JP-A-4-275379. And hydroxyl-containing fluororesins described in WO 97/11130, WO 96/26254, and the like. Other hydroxyl group-containing fluororesins include, for example, fluoroolefin copolymers described in JP-A-8-231919, JP-A-10-265731, JP-A-10-204374, JP-A-8-12922 and the like. Polymers. Other examples include a copolymer of a compound having a fluorinated alkyl group with a hydroxyl group-containing compound, a fluorine-containing organic compound obtained by copolymerizing a hydroxyl-containing compound with a fluorine-containing compound, and a fluorine-containing compound containing a hydroxyl group-containing organic compound. Commercially available examples of such a hydroxyl group-containing fluorine-based compound include "Lumiflon" (trade name, manufactured by Asahi Glass Co., Ltd.), "Sefural Coat" (trade name, manufactured by Central Glass Co., Ltd.), and "Zaflon" trade name. (Manufactured by Toa Gosei Co., Ltd.), trade name “Zeffle” (manufactured by Daikin Industries, Ltd.), trade name “MegaFac F-571”, and “Fluonate” (manufactured by DIC Corporation).

  Examples of the crosslinkable functional group-containing fluorine compound 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 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. As such a crosslinkable functional group-containing fluorine-based compound, commercially available products include, for example, trade names “MegaFac F-570”, “MegaFac RS-55”, “MegaFac RS-56”, and “MegaFac RS-56”. RS-72-K "," MegaFac RS-75 "," MegaFac RS-76-E "," MegaFac RS-76-NS "," MegaFac RS-78 "," MegaFac RS-90 " (Manufactured by DIC Corporation).

<Other components>
The pressure-sensitive adhesive composition may contain any appropriate other components as long as the effects of the present invention are not impaired. Such other components include, for example, other resin components, tackifiers, inorganic fillers, organic fillers, metal powders, pigments, foils, softeners, antioxidants, conductive agents, ultraviolet absorbers , Antioxidants, light stabilizers, surface lubricants, leveling agents, corrosion inhibitors, heat stabilizers, polymerization inhibitors, lubricants, solvents, catalysts and the like.

  The pressure-sensitive adhesive composition may contain a fatty acid ester. 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 from 100 to 800, more preferably from 150 to 500, further preferably from 200 to 480, particularly preferably from 200 to 400, and most preferably from 250 to 350. It is. By adjusting the number average molecular weight Mn of the fatty acid ester within the above range, the wettability of the pressure-sensitive adhesive layer can be improved.

  As the fatty acid ester, any appropriate fatty acid ester can be adopted as long as the effects of the present invention are not impaired. Examples of such fatty acid esters include polyoxyethylene bisphenol A laurate, butyl stearate, 2-ethylhexyl palmitate, 2-ethylhexyl stearate, monoglyceride behenate, cetyl 2-ethylhexanoate, and myristate. Isopropyl, isopropyl palmitate, cholesteryl isostearate, lauryl methacrylate, methyl cocoate, methyl laurate, methyl oleate, methyl stearate, myristyl myristate, octyl dodecyl myristate, pentaerythritol monooleate, pentaerythritol monostearate , Pentaerythritol tetrapalmitate, stearyl stearate, isotridecyl stearate, triglycera 2-ethylhexanoate De, butyl laurate, and the like octyl oleate.

  When the pressure-sensitive adhesive composition contains a fatty acid ester, the content ratio of the fatty acid ester is preferably 1 to 50 parts by weight, more preferably 1.5 to 45 parts by weight, based on 100 parts by weight of the base polymer. Parts by weight, more preferably 2 to 40 parts by weight, particularly preferably 2.5 to 35 parts by weight, and most preferably 3 to 30 parts by weight.

  The pressure-sensitive adhesive composition may include an ionic liquid containing a fluoroorganic anion. When the pressure-sensitive adhesive composition contains an ionic liquid containing a fluoroorganic anion, a pressure-sensitive adhesive composition having extremely excellent antistatic properties can be provided. Such an ionic liquid may be only one kind or two or more kinds.

  In the present invention, the ionic liquid means a molten salt (ionic compound) that is in a liquid state at 25 ° C.

  As the ionic liquid, any appropriate ionic liquid can be adopted as long as the effect of the present invention is not impaired, as long as the ionic liquid contains a fluoroorganic anion. Such an ionic liquid is preferably an ionic liquid composed of a fluoroorganic anion and an onium cation. By employing an ionic liquid composed of a fluoroorganic anion and an onium cation as the ionic liquid, a pressure-sensitive adhesive composition having extremely excellent antistatic properties can be provided.

  As the onium cation that can constitute the ionic liquid, any appropriate onium cation can be adopted as long as the effects of the present invention are not impaired. Such an onium cation is preferably at least one selected from a nitrogen-containing onium cation, a sulfur-containing onium cation, and a phosphorus-containing onium cation. By selecting these onium cations, a pressure-sensitive adhesive composition having extremely excellent antistatic properties can be provided.

The onium cation that can constitute the ionic liquid is preferably at least one selected from cations having structures represented by general formulas (1) to (5).

  In the general formula (1), Ra represents a hydrocarbon group having 4 to 20 carbon atoms and may include a hetero atom, and Rb and Rc are the same or different and are hydrogen or a hydrocarbon group having 1 to 16 carbon atoms. Represents a hydrogen group and may contain a hetero atom. However, when the nitrogen atom contains a double bond, there is no Rc.

  In the general formula (2), Rd represents a hydrocarbon group having 2 to 20 carbon atoms and may contain a hetero atom, and Re, Rf, and Rg are the same or different and each have a hydrogen atom or 1 to 20 carbon atoms. Represents 16 hydrocarbon groups and may contain heteroatoms.

  In the general formula (3), Rh represents a hydrocarbon group having 2 to 20 carbon atoms and may include a hetero atom, and Ri, Rj, and Rk are the same or different and each have a hydrogen atom or a carbon number of 1 to 20. Represents 16 hydrocarbon groups and may contain heteroatoms.

  In the general formula (4), Z represents a nitrogen atom, a sulfur atom, or a phosphorus atom; Rl, Rm, Rn, and Ro represent the same or different and represent a hydrocarbon group having 1 to 20 carbon atoms, It may contain atoms. However, when Z is a sulfur atom, there is no Ro.

  In the general formula (5), X represents a Li atom, a Na atom, or a K atom.

  Examples of the cation represented by the general formula (1) include a pyridinium cation, a pyrrolidinium cation, a piperidinium cation, a cation having a pyrroline skeleton, a cation having a pyrrole skeleton, and the like.

  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 cation; 1-ethyl-1-methylpyrrolidinium cation, 1-methyl-1-propylpyrrolidinium cation, 1-methyl-1-butylpyrrolidinium cation, 1-methyl-1-pentylpyrrolidini Cation, 1-methyl-1-hexylpyrrolidinium cation, 1-methyl-1-heptylpyrrolidinium cation, 1-ethyl-1-propylpyrrolidinium cation, 1-ethyl-1-butylpyrrolidinium cation 1-ethyl-1-pentylpyrrolidinium cation, 1-ethyl-1-hexylpyrrolidinium cation, 1-ethyl-1-heptylpyrrolidinium cation, 1,1-dipropylpyrrolidinium cation, Pyrrolidinium cations such as 1-propyl-1-butylpyrrolidinium cation and 1,1-dibutylpyrrolidinium cation; 1-propylpiperidinium cation, 1-pentylpiperidinium cation, 1-methyl-1- Ethyl piperidinium cation, 1-methyl-1-propyl piperidinium cation A 1-methyl-1-butylpiperidinium cation, a 1-methyl-1-pentylpiperidinium cation, a 1-methyl-1-hexylpiperidinium cation, a 1-methyl-1-heptylpiperidinium cation, 1-ethyl-1-propylpiperidinium cation, 1-ethyl-1-butylpiperidinium cation, 1-ethyl-1-pentylpiperidinium cation, 1-ethyl-1-hexylpiperidinium cation, 1- Ethyl-1-heptylpiperidinium cation, 1-propyl-1-butylpiperidinium cation, 1,1-dimethylpiperidinium cation, 1,1-dipropylpiperidinium cation, 1,1-dibutylpi Piperidinium cation such as peridinium cation; 2-methyl-1-pyrroline cation; A tyl-2-phenylindole cation; a 1,2-dimethylindole cation; a 1-ethylcarbazole cation;

  Of these, 1-ethylpyridinium cation, 1-butylpyridinium cation, 1-hexylpyridinium cation, 1-ethyl-3-methylpyridinium cation and 1-ethylpyridinium cation are preferable in that the effects 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- Methylpyrrolidinium cation, 1-methyl-1-propylpyrrolidinium cation, 1-methyl-1-butylpyrrolidinium cation, 1-methyl-1-pentylpyrrolidinium cation, 1-methyl-1-hexyl Pyrrolidinium cation, 1-methyl-1-f Tylpyrrolidinium cation, 1-ethyl-1-propylpyrrolidinium cation, 1-ethyl-1-butylpyrrolidinium cation, 1-ethyl-1-pentylpyrrolidinium cation, 1-ethyl-1-hexyl Pyrrolidinium cations such as pyrrolidinium cation and 1-ethyl-1-heptylpyrrolidinium cation; 1-methyl-1-ethylpiperidinium cation, 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-propyl piperidinium cation, 1-ethyl-1-butyl piperidinium click 1-ethyl-1-pentylpiperidinium cation, 1-ethyl-1-hexylpiperidinium cation, 1-ethyl-1-heptylpiperidinium cation, 1-propyl-1-butylpiperidinium cation And more preferably 1-hexylpyridinium cation, 1-ethyl-3-methylpyridinium cation, 1-butyl-3-methylpyridinium cation, 1-octyl-4-methyl A pyridinium cation, a 1-methyl-1-propylpyrrolidinium cation, and a 1-methyl-1-propylpiperidinium cation.

  Examples of the cation represented by the general formula (2) include an imidazolium cation, a tetrahydropyrimidinium cation, and a dihydropyrimidinium cation.

  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, 1-butyl -3-methylimidazolium cation, 1-hexyl-3-methylimidazolium cation, 1-octyl-3-methylimidazolium cation, 1-decyl-3-methylimidazolium cation, 1-dodecyl-3-methylimidazo Lium cation, 1-tetradecyl-3-methylimidazolium cation, 1,2-dimethyl-3-propylimidazolium cation, 1-ethyl-2,3-dimethylimidazolium cation, 1-butyl-2,3-dimethylimidazo Lithium cation, 1-hexyl-2,3-dimethylimidazo Imidazolium cations such as cations; 1,3-dimethyl-1,4,5,6-tetrahydropyrimidinium cation; 1,2,3-trimethyl-1,4,5,6-tetrahydropyrimidinium cation; , 2,3,4-tetramethyl-1,4,5,6-tetrahydropyrimidinium cation and 1,2,3,5-tetramethyl-1,4,5,6-tetrahydropyrimidinium cation 1,3-dimethyl-1,4-dihydropyrimidinium cation, 1,3-dimethyl-1,6-dihydropyrimidinium cation, 1,2,3-trimethyl-1,4-tetrahydropyrimidinium cation Dihydropyrimidinium cation, 1,2,3-trimethyl-1,6-dihydropyrimidinium cation, 1,2,3,4-tetramethyl-1 4-dihydropyrimidinium cation, 1,2,3,4-tetramethyl-1,6-dihydropyrimidinium dihydropyrimidinium cation, such as cations; and the like.

  Among these, 1,3-dimethylimidazolium cation, 1,3-diethylimidazolium cation, 1-ethyl-3-methylimidazolium cation, and 1-dimethylimidazolium cation are preferable in that the effects 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, imidazolium cations such as 1-tetradecyl-3-methyl imidazolium cation, more preferably 1-ethyl-3-methyl imidazolium cation, 1-hexyl-3-methyl imidazolium cation is there.

  Examples of the cation represented by the general formula (3) include a pyrazolium cation and a pyrazolinium cation.

  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; Pyra such as 1-ethyl-2,3,5-trimethylpyrazolinium cation, 1-propyl-2,3,5-trimethylpyrazolinium cation, 1-butyl-2,3,5-trimethylpyrazolinium cation A zolinium cation;

  Examples of the cation represented by the general formula (4) include a tetraalkylammonium cation, a trialkylsulfonium cation, and a tetraalkylphosphonium cation, and a part of the alkyl group is substituted with an alkenyl group or an alkoxyl group, and further, an epoxy group. And the like.

  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, triethylmethylammonium Cation, tributylethylammonium cation, trimethylpropylammonium cation, trimethyldecylammonium cation, N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium cation, glycidyltrimethylammonium cation, trimethylsulfonium cation, triethylsulfonium cation , Tributylsulfonium cation, trihexylsulfonium cation , Diethylmethylsulfonium cation, dibutylethylsulfonium cation, dimethyldecylsulfonium cation, tetramethylphosphonium cation, tetraethylphosphonium cation, tetrabutylphosphonium cation, tetrahexylphosphonium cation, tetraoctylphosphonium cation, triethylmethylphosphonium cation, tributylethylphosphonium cation, Trimethyldecylphosphonium cation, diallyldimethylammonium cation and the like.

  Among these, from the viewpoint that the effects of the present invention can be further exhibited, preferably, triethylmethylammonium cation, tributylethylammonium cation, trimethyldecylammonium cation, diethylmethylsulfonium cation, dibutylethylsulfonium cation, dimethyldecylsulfonium cation, Asymmetric tetraalkylammonium cations such as triethylmethylphosphonium cation, tributylethylphosphonium cation, and trimethyldecylphosphonium cation, trialkylsulfonium cations, tetraalkylphosphonium cations, and N, N-diethyl-N-methyl-N- (2-methoxy Ethyl) ammonium cation, glycidyl trimethyl ammonium cation, diallyl dimethyl ammonium 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-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- -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, triethylheptyl ammonium cation, N, N-dipropyl-N-methyl-N-ethylammonium cation, N, N-dipropyl-N-methyl-N-pentylammonium cation, N, N-dipropyl-N-butyl-N -Hexyl ammonium 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-pentylammonium cation, and the like, and more preferably trimethylpropylammonium cation.

  As the fluoroorganic anion that can constitute the ionic liquid, any appropriate fluoroorganic anion can be adopted as long as the effects of the present invention are not impaired. Such a fluoroorganic anion may be completely fluorinated (perfluorinated) or partially fluorinated.

  Such fluoroorganic anions include, for example, fluorinated arylsulfonates, perfluoroalkanesulfonates, bis (fluorosulfonyl) imides, bis (perfluoroalkanesulfonyl) imides, cyanoperfluoroalkanesulfonylamides, bis (cyano) Perfluoroalkanesulfonyl methide, cyano-bis- (perfluoroalkanesulfonyl) methide, tris (perfluoroalkanesulfonyl) methide, trifluoroacetate, perfluoroalkylate, tris (perfluoroalkanesulfonyl) methide, (perfluoroalkane Sulfonyl) trifluoroacetamide and the like.

  Among these fluoroorganic anions, more preferred are perfluoroalkylsulfonate, bis (fluorosulfonyl) imide, and bis (perfluoroalkanesulfonyl) imide. More specifically, for example, trifluoromethanesulfonate, pentafluoroethane Sulfonate, heptafluoropropanesulfonate, nonafluorobutanesulfonate, bis (fluorosulfonyl) imide and bis (trifluoromethanesulfonyl) imide.

Specific examples of the ionic liquid can be appropriately selected from the combination of the cation component and the anion component and used. Specific examples of such an ionic liquid include, for example, 1-hexylpyridinium bis (fluorosulfonyl) imide, 1-ethyl-3-methylpyridinium trifluoromethanesulfonate, 1-ethyl-3-methylpyridinium pentafluoroethanesulfonate, 1-ethyl-3-methylpyridinium heptafluoropropanesulfonate, 1-ethyl-3-methylpyridinium nonafluorobutanesulfonate, 1-butyl-3-methylpyridinium trifluoromethanesulfonate, 1-butyl-3-methylpyridiniumbis (trifluoromethane Sulfonyl) imide, 1-butyl-3-methylpyridinium bis (pentafluoroethanesulfonyl) imide, 1-octyl-4-methylpyridinium bis (fluorosulfonyl) imid 1,1-dimethylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-ethylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-propylpyrrolidinium bis (trifluoromethanesulfonyl) ) Imide, 1-methyl-1-propylpyrrolidinium bis (fluorosulfonyl) imide, 1-methyl-1-butylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-pentylpyrrolidinium bis ( Trifluoromethanesulfonyl) imide, 1-methyl-1-hexylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-heptylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-ethyl-1- Propyl pyro Dinium bis (trifluoromethanesulfonyl) imide, 1-ethyl-1-butylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-ethyl-1-pentylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-ethyl-1- Hexylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-ethyl-1-heptylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1,1-dipropylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1 -Propyl-1-butylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1,1-dibutylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-propylpiperidinium bis (trifluoromethanesulfonyl) Nil) imide, 1-pentylpiperidinium bis (trifluoromethanesulfonyl) imide, 1,1-dimethylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-ethylpiperidinium bis (trifluoromethanesulfonyl) Imide, 1-methyl-1-propylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-propylpiperidinium bis (fluorosulfonyl) imide, 1-methyl-1-butylpiperidinium bis (trifluoro) 1-methyl-1-pentylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-hexylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-heptylpiperide Dinium bis (trifluoromethanesulfonyl) imide, 1-ethyl-1-propylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-ethyl-1-butylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-ethyl-1- Pentylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-ethyl-1-hexylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-ethyl-1-heptylpiperidinium bis (trifluoromethanesulfonyl) imide, 1,1-dipropylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-propyl-1-butylpiperidinium bis (trifluoromethanesulfonyl) imide, 1,1-dibutylpiperidinium bis (trifluoro Tansulfonyl) imide, 1,1-dimethylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-ethylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-propylpyrrolidide Ammonium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-butylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-pentylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, Methyl-1-hexylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-heptylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-propylpyrrolidinium bis ( Pentafluoroethane Rufonyl) imide, 1-ethyl-1-butylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-pentylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-hexyl Pyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-heptylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1,1-dipropylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-propyl-1-butylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1,1-dibutylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-propylpiperidinium bis (pentafluoroethanesulfonyl) imide , 1- Pentylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1,1-dimethylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-ethylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1 -Methyl-1-propylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-butylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-pentylpiperidinium bis (penta Fluoroethanesulfonyl) imide, 1-methyl-1-hexylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-heptylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl- 1-prop Piperidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-butylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-pentylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-hexylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-heptylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1,1-dipropylpiperidinium bis (Pentafluoroethanesulfonyl) imide, 1-propyl-1-butylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1,1-dibutylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-3- Methyl imidazoli Trifluoroacetate, 1-ethyl-3-methylimidazolium heptafluorobutyrate, 1-ethyl-3-methylimidazolium trifluoromethanesulfonate, 1-ethyl-3-methylimidazolium heptafluoropropanesulfonate, 1-ethyl-3 -Methylimidazolium nonafluorobutanesulfonate, 1-ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide, 1-ethyl-3-methylimidazolium bis (fluorosulfonyl) imide, 1-ethyl-3-methylimidazo Lithium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-3-methylimidazolium tris (trifluoromethanesulfonyl) methide, 1-butyl-3-methylimidazolium trifluoroacetate 1-butyl-3-methylimidazolium heptafluorobutyrate, 1-butyl-3-methylimidazolium trifluoromethanesulfonate, 1-butyl-3-methylimidazolium perfluorobutanesulfonate, 1-butyl-3-methyl Imidazolium bis (trifluoromethanesulfonyl) imide, 1-hexyl-3-methylimidazolium trifluoromethanesulfonate, 1-hexyl-3-methylimidazolium bis (fluorosulfonyl) imide, 1,2-dimethyl-3-propylimidazo Lithium bis (trifluoromethanesulfonyl) imide, 1-ethyl-2,3,5-trimethylpyrazolium bis (trifluoromethanesulfonyl) imide, 1-propyl-2,3,5-trimethylpyrazolium bis (trifluoro Methanesulfonyl) imide, 1-butyl-2,3,5-trimethylpyrazolium bis (trifluoromethanesulfonyl) imide, 1-ethyl-2,3,5-trimethylpyrazolium bis (pentafluoroethanesulfonyl) imide, 1-propyl-2,3,5-trimethylpyrazolium bis (pentafluoroethanesulfonyl) imide, 1-butyl-2,3,5-trimethylpyrazoliumbis (pentafluoroethanesulfonyl) imide, 1-ethyl- 2,3,5-trimethylpyrazolium (trifluoromethanesulfonyl) trifluoroacetamide, 1-propyl-2,3,5-trimethylpyrazolium (trifluoromethanesulfonyl) trifluoroacetamide, 1-butyl-2,3 5-trimethylpyrazolium (trifluoro Tansulfonyl) trifluoroacetamide, trimethylpropylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-ethyl-N-propylammoniumbis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-ethyl- N-butylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-ethyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-ethyl-N-hexylammoniumbis ( Trifluoromethanesulfonyl) imide, N, N-dimethyl-N-ethyl-N-heptylammoniumbis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-ethyl-N-nonylammoniumbis (trifluoromethanesulfonyl) imide Fluoromethanesulfonyl) imide, N, N-dimethyl-N, N-dipropylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-propyl-N-butylammoniumbis (trifluoromethanesulfonyl) imide, N N, N-dimethyl-N-propyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-propyl-N-hexylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N -Propyl-N-heptylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-butyl-N-hexylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-butyl-N-heptylethyl Monium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-pentyl-N-hexylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N, N-dihexylammonium bis (trifluoromethanesulfonyl) imide, Trimethylheptyl ammonium bis (trifluoromethanesulfonyl) imide, N, N-diethyl-N-methyl-N-propylammonium bis (trifluoromethanesulfonyl) imide, N, N-diethyl-N-methyl-N-pentylammonium bis (trifluoro Romethansulfonyl) imide, N, N-diethyl-N-methyl-N, N-heptylammonium bis (trifluoromethanesulfonyl) imide, N, N-diethyl-N-propyl-N-pentylan Numium bis (trifluoromethanesulfonyl) imide, triethylpropylammonium bis (trifluoromethanesulfonyl) imide, triethylpentylammonium bis (trifluoromethanesulfonyl) imide, triethylheptylammonium bis (trifluoromethanesulfonyl) imide, N, N-dipropyl-N-methyl -N-ethylammoniumbis (trifluoromethanesulfonyl) imide, N, N-dipropyl-N-methyl-N-pentylammoniumbis (trifluoromethanesulfonyl) imide, N, N-dipropyl-N-butyl-N-hexylammoniumbis (Trifluoromethanesulfonyl) imide, N, N-dipropyl-N, N-dihexylammonium bis (trifluoromethanesulfonyl) imide, N N, N-dibutyl-N-methyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, N, N-dibutyl-N-methyl-N-hexylammonium bis (trifluoromethanesulfonyl) imide, trioctylmethylammonium bis ( Trifluoromethanesulfonyl) imide, N-methyl-N-ethyl-N-propyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, 1-butylpyridinium (trifluoromethanesulfonyl) trifluoroacetamide, 1-butyl-3-methyl Pyridinium (trifluoromethanesulfonyl) trifluoroacetamide, 1-ethyl-3-methylimidazolium (trifluoromethanesulfonyl) trifluoroacetamide, tetrahexylammonium (Trifluoromethanesulfonyl) imide, diallyldimethylammonium trifluoromethanesulfonate, diallyldimethylammoniumbis (trifluoromethanesulfonyl) imide, diallyldimethylammoniumbis (pentafluoroethanesulfonyl) imide, N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium trifluoromethanesulfonate, N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium bis (trifluoromethanesulfonyl) imide, N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium bis (pentafluoroethanesulfonyl) imide, glycidyltrimethylammonium trifluoromethanesulfonate, glycidyltrimethylammonium Umbis (trifluoromethanesulfonyl) imide, glycidyltrimethylammonium bis (pentafluoroethanesulfonyl) imide, diallyldimethylammonium bis (trifluoromethanesulfonyl) imide, diallyldimethylbis (pentafluoroethanetansulfonyl) imide, lithium bis (trifluoromethanesulfonyl) Imide, lithium bis (fluorosulfonyl) imide and the like.

  Among these ionic liquids, more preferably, 1-hexylpyridinium bis (fluorosulfonyl) imide, 1-ethyl-3-methylpyridinium trifluoromethanesulfonate, 1-ethyl-3-methylpyridinium pentafluoroethanesulfonate, Ethyl-3-methylpyridinium heptafluoropropanesulfonate, 1-ethyl-3-methylpyridinium nonafluorobutanesulfonate, 1-butyl-3-methylpyridinium trifluoromethanesulfonate, 1-butyl-3-methylpyridiniumbis (trifluoromethanesulfonyl) Imide, 1-octyl-4-methylpyridinium bis (fluorosulfonyl) imide, 1-methyl-1-propylpyrrolidinium bis (trifluoromethanesulfonyl) imid , 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, trimethylpropylammonium bis (trifluoromethanesulfonyl) imide, Chiumubisu (trifluoromethanesulfonyl) imide, lithium bis (fluorosulfonyl) imide.

  As the ionic liquid, a commercially available ionic liquid may be used, but the ionic liquid can also be synthesized as described below. The method for synthesizing the ionic liquid is not particularly limited as long as the desired ionic liquid is obtained. In general, however, the literature “Ionic liquids—the forefront of development and the future—” (CMC Publishing Co., Ltd.) The halide method, the hydroxide method, the acid ester method, the complex formation method, the neutralization method, and the like as described in the publication are used.

  The synthesis method of the halide method, hydroxide method, acid ester method, complex formation method, and neutralization method will be described below using a nitrogen-containing onium salt as an example. Other sulfur-containing onium salts and phosphorus-containing onium salts And other ionic liquids can be obtained by the same method.

  The halide method is a method performed by a reaction as shown in reaction formulas (1) to (3). First, a tertiary amine is reacted with an alkyl halide to obtain a halide (reaction formula (1), and chlorine, bromine, and iodine are used as halogen).

Acid (HA) or salt having an anionic structure (A ⁻ ) of an ionic liquid intended for the obtained halide (MA, M is a cation that forms a salt with the desired anion such as ammonium, lithium, sodium, potassium, etc.) ) To obtain the desired ionic liquid (R ₄ NA).

The hydroxide method is a method performed by a reaction as shown in reaction formulas (4) to (8). First, halide (R ₄ NX) is subjected to ion exchange membrane electrolysis (reaction formula (4)), OH-type ion exchange resin method (reaction formula (5)) or reaction with silver oxide (Ag ₂ O) (reaction formula ( 6)) to obtain a hydroxide (R ₄ NOH) (chlorine, bromine and iodine are used as halogen).

The target ionic liquid (R ₄ NA) can be obtained by using the reactions of reaction formulas (7) and (8) in the same manner as in the above-mentioned halogenation method, for the obtained hydroxide.

The acid ester method is a method performed by a reaction as shown in reaction formulas (9) to (11). First, a tertiary amine (R ₃ N) is reacted with an acid ester to obtain an acid ester product (reaction formula (9). Examples of the acid ester include inorganic acids such as sulfuric acid, sulfurous acid, phosphoric acid, phosphorous acid, and carbonic acid). Esters and esters of organic acids such as methanesulfonic acid, methylphosphonic acid, and formic acid are used).

The target ionic liquid (R ₄ NA) can be obtained by using the reactions of Reaction Formulas (10) to (11) in the same manner as in the above-mentioned halogenation method for the obtained acid ester. Further, by using methyl trifluoromethanesulfonate, methyl trifluoroacetate or the like as an acid ester, an ionic liquid can be directly obtained.

The neutralization method is a method performed by a reaction as shown in the reaction formula (12). A tertiary amine is reacted with an organic acid such as CF ₃ COOH, CF ₃ SO ₃ H, (CF ₃ SO ₂ ) ₂ NH, (CF ₃ SO ₂ ) ₃ CH, and (C ₂ F ₅ SO ₂ ) ₂ NH. Can be obtained.

  R in the above reaction formulas (1) to (12) represents hydrogen or a hydrocarbon group having 1 to 20 carbon atoms, and may contain a hetero atom.

  The blending amount of the ionic liquid cannot be unconditionally defined because it varies depending on the compatibility of the polymer to be used and the ionic liquid, but generally, it is preferably 0.001 to 100 parts by weight of the base polymer. Parts by weight to 50 parts by weight, more preferably 0.01 to 40 parts by weight, still more preferably 0.01 to 30 parts by weight, particularly preferably 0.01 to 20 parts by weight. Parts, most preferably 0.01 to 10 parts by weight. By adjusting the blending amount of the ionic liquid within the above range, a pressure-sensitive adhesive composition having extremely excellent antistatic properties can be provided. If the amount of the ionic liquid is less than 0.01 part by weight, sufficient antistatic properties may not be obtained. When the amount of the ionic liquid is more than 50 parts by weight, contamination of the adherend tends to increase.

  The pressure-sensitive adhesive composition may contain a modified silicone oil as long as the effects of the present invention are not impaired. When the pressure-sensitive adhesive composition contains the modified silicone oil, the effect of antistatic properties can be exhibited. In particular, when used in combination with an ionic liquid, the effect of antistatic properties can be more effectively exhibited.

  When the pressure-sensitive adhesive composition contains a modified silicone oil, the content is preferably 0.001 to 50 parts by weight, more preferably 0.005 to 40 parts by weight, based on 100 parts by weight of the base polymer. Parts by weight, more preferably 0.007 to 30 parts by weight, particularly preferably 0.008 to 20 parts by weight, and most preferably 0.01 to 10 parts by weight. By adjusting the content of the modified silicone oil within the above range, the effect of the antistatic property can be more effectively exhibited.

  As the modified silicone oil, any appropriate modified silicone oil can be adopted as long as the effects of the present invention are not impaired. Examples of such a modified silicone oil include a modified silicone oil available from Shin-Etsu Chemical Co., Ltd.

  The modified silicone oil is preferably a polyether-modified silicone oil. By using a polyether-modified silicone oil, the effect of antistatic properties can be more effectively exerted.

  Examples of the polyether-modified silicone oil include a side-chain type polyether-modified silicone oil and a double-ended polyether-modified silicone oil. Among these, a double-ended polyether-modified silicone oil is preferable in that the effect of antistatic properties can be sufficiently and more effectively exhibited.

≪≪Application≫≫
The surface protective film of the present invention has super light peelability and low contamination on the adherend surface. Therefore, it can be suitably used for protecting the surface of optical members and electronic members. 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.

  Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples. In addition, the test and evaluation method in an Example etc. are as follows. In addition, when described as “parts”, it means “parts by weight” unless otherwise specified, and when described as “%”, it means “% by weight” unless otherwise specified.

<PET peeling force at a peeling speed of 6000 mm / min (peeling force after 23 ° C. × 30 minutes and peeling force after 80 ° C. × 7 days)>
A 25 μm-thick polyethylene terephthalate film was bonded to the pressure-sensitive adhesive layer, and the peeling force when the polyethylene terephthalate film was peeled at 23 ° C., a peeling angle of 180 °, and a peeling speed of 6000 mm / min was measured as follows.
Through a double-sided adhesive tape (trade name “No. 531”, manufactured by Nitto Denko Corporation), on the entire surface of the surface protective film (width 50 mm × length 140 mm) from which the separator was peeled away from the pressure-sensitive adhesive layer. The SUS304 plate was stuck using a 2 kg hand roller.
Then, a polyethylene terephthalate film (trade name “Lumirror S-10”, manufactured by Toray Industries, Inc., thickness: 25 μm, width: 25 mm) was adhered to the surface of the adhesive layer (temperature: 23 ° C., humidity: 65%, 2kg roller 1 round trip).
The evaluation sample obtained as described above was measured by a tensile test. As a tensile tester, a product name “Autograph AG-Xplus HS 6000 mm / min high-speed model (AG-50NXplus)” manufactured by Shimadzu Corporation was used. After the evaluation sample was set on the tensile tester, the tensile test was started after leaving it at an environment temperature of 23 ° C. for 30 minutes or after leaving it at a temperature environment of 80 ° C. for 7 days. The conditions for the tensile test were a peel angle of 180 degrees and a peel speed (tensile speed) of 6000 mm / min. The load when the PET film was peeled from the surface protective film was measured, and the average load at that time was defined as the peeling force of the surface protective film.

<PET peeling force at a peeling speed of 300 mm / min (peeling force after 23 ° C. × 30 minutes and peeling force after 80 ° C. × 7 days)>
A 25 μm-thick polyethylene terephthalate film was bonded to the pressure-sensitive adhesive layer, and the peeling force when the polyethylene terephthalate film was peeled at 23 ° C., a peel angle of 180 °, and a peel speed of 300 mm / min was measured as follows.
Through a double-sided adhesive tape (trade name “No. 531”, manufactured by Nitto Denko Corporation), on the entire surface of the surface protective film (width 50 mm × length 140 mm) from which the separator was peeled away from the pressure-sensitive adhesive layer. The SUS304 plate was stuck using a 2 kg hand roller.
Then, a polyethylene terephthalate film (trade name “Lumirror S-10”, manufactured by Toray Industries, Inc., thickness: 25 μm, width: 25 mm) was adhered to the surface of the adhesive layer (temperature: 23 ° C., humidity: 65%, 2kg roller 1 round trip).
The evaluation sample obtained as described above was subjected to a tensile test. As a tensile tester, a product name “Autograph AG-Xplus HS 6000 mm / min high-speed model (AG-50NXplus)” manufactured by Shimadzu Corporation was used. After the evaluation sample was set on the tensile tester, the tensile test was started after leaving it at an environment temperature of 23 ° C. for 30 minutes or after leaving it at a temperature environment of 80 ° C. for 7 days. The conditions for the tensile test were a peel angle of 180 degrees and a peel speed (tension speed) of 300 mm / min. The load when the PET film was peeled from the surface protective film was measured, and the average load at that time was defined as the peeling force of the surface protective film.

<Remaining adhesion rate>
A surface protection film was stuck on the entire surface of a glass plate (manufactured by Matsunami Glass, 1.35 mm × 10 cm × 10 cm) with a hand roller, and stored for 24 hours in an atmosphere of a temperature of 23 ° C. and a humidity of 55% RH. The surface protective film was peeled off at a speed of 3 m / min, and cut to a length of 150 mm. A 31 kg tape (manufactured by Nitto Denko Corporation, base material thickness: 25 μm) was applied by a 2.0 kg roller with one reciprocation in an atmosphere of a temperature of 23 ° C. and a humidity of 55% RH. After curing in an atmosphere of a temperature of 23 ° C. and a humidity of 55% RH for 30 minutes, a tensile tester (trade name “Autograph AG-Xplus HS 6000 mm / min high-speed model (AG-50NXplus)” manufactured by Shimadzu Corporation) Was peeled at a peel angle of 180 ° and a pulling speed of 300 mm / min, and the adhesive strength was measured.
Separately, a 19 mm wide No. 1 glass sheet is also similarly treated with a glass plate not subjected to the above-described treatment. The adhesive strength of the 31B tape was measured, and the residual adhesion was calculated by the following equation.
Residual adhesion rate (%) = (No. 31B adhesion to glass plate after peeling off surface protective film / No. 31B adhesion to glass plate) × 100
This residual adhesion ratio is an index of how much the pressure-sensitive adhesive component of the surface protective film is transferred to the adherend and contaminated. It can be said that the higher the value of the residual adhesion rate, the better the surface protection film without contaminating the adherend, and the lower the value of the residual adhesion rate, the more contaminating the surface of the adherend with the adhesive component or the like. .

<Peel force against glass at a peel speed of 6000 mm / min (peel force after 23 ° C. × 30 minutes and peel force after 80 ° C. × 7 days)>
The surface protection film (width 25 mm x length 140 mm) from which the separator was peeled off was adhered to glass (soda lime glass, manufactured by Matsunami Glass Industry Co., Ltd.) with one reciprocation of a 2 kg hand roller.
The evaluation sample obtained as described above was measured with a tensile tester. As a tensile tester, a product name “Autograph AG-Xplus HS 6000 mm / min high-speed model (AG-50NXplus)” manufactured by Shimadzu Corporation was used. After the evaluation sample was set on the tensile tester, the tensile test was started after leaving it at an environment temperature of 23 ° C. for 30 minutes or after leaving it at a temperature environment of 80 ° C. for 7 days. The conditions for the tensile test were a peel angle of 180 degrees and a peel speed (tensile speed) of 6000 mm / min. The load when the surface protection film was peeled from the glass was measured, and the average load at that time was defined as the peeling force of the surface protection film.

<Peel force against glass at a peel speed of 300 mm / min (peel force after 23 ° C. × 30 minutes and peel force after 80 ° C. × 7 days)>
The surface protection film (width 25 mm x length 140 mm) from which the separator was peeled off was adhered to glass (soda lime glass, manufactured by Matsunami Glass Industry Co., Ltd.) with one reciprocation of a 2 kg hand roller.
The evaluation sample obtained as described above was measured with a tensile tester. As a tensile tester, a product name “Autograph AG-Xplus HS 6000 mm / min high-speed model (AG-50NXplus)” manufactured by Shimadzu Corporation was used. After the evaluation sample was set on the tensile tester, the tensile test was started after leaving it at an environment temperature of 23 ° C. for 30 minutes or after leaving it at a temperature environment of 80 ° C. for 7 days. The conditions for the tensile test were a peel angle of 180 degrees and a peel speed (tension speed) of 300 mm / min. The load when the surface protection film was peeled from the glass was measured, and the average load at that time was defined as the peeling force of the surface protection film.

[Example 7]
"Cyabain SH-109" (solid content 54%, containing fatty acid ester, manufactured by Toyo Ink Co.) as urethane prepolymer (C): 100 parts by weight, polyfunctional isocyanate compound (B) as polyfunctional alicyclic isocyanate compound Certain coronate HX (manufactured by Nippon Polyurethane Industry Co., Ltd.): 7.05 parts by weight, fluorine-containing polymer (manufactured by DIC, trade name: F-571): 1.00 part by weight, and toluene: 208 parts by weight as a diluting solvent are blended. Then, the mixture was stirred with a disper to prepare a pressure-sensitive adhesive composition (7).
The obtained pressure-sensitive adhesive composition (7) was applied to a polyester resin base material “Lumirror S10” (thickness: 38 μm, manufactured by Toray Industries Co., Ltd.) so that the thickness after drying with a fountain roll was 10 μm, and the drying temperature was reduced. It was cured and dried at 130 ° C. for a drying time of 30 seconds. Thus, an adhesive layer was formed on the substrate. Next, the silicone-treated surface of a base material (separator) made of a polyester resin having a thickness of 25 μm and having one surface subjected to silicone treatment was bonded to the surface of the pressure-sensitive adhesive layer to obtain a surface protection film (7) with a separator. .
The results are shown in Table 1 .

Example 8
An adhesive composition (8) was produced in the same manner as in Example 7, except that the amount of the fluorine-containing polymer (manufactured by DIC, trade name: F-571) was changed to 2.00 parts by weight. A surface protective film (8) was obtained.
The results are shown in Table 1 .

[Example 9]
An adhesive composition (9) was produced in the same manner as in Example 7, except that the amount of the fluorine-containing polymer (manufactured by DIC, trade name: F-571) was changed to 3.00 parts by weight, and a pressure-sensitive adhesive composition (9) was prepared. A surface protective film (9) was obtained.
The results are shown in Table 1 .

[Example 10]
"Cyabain SH-109" (solid content 54%, containing fatty acid ester, manufactured by Toyo Ink Co.) as urethane prepolymer (C): 100 parts by weight, polyfunctional isocyanate compound (B) as polyfunctional alicyclic isocyanate compound Certain coronate HX (manufactured by Nippon Polyurethane Industry Co., Ltd.): 3.6 parts by weight, fluorinated polymer (manufactured by DIC, trade name: F-571): 1.00 part by weight, and toluene: 208 parts by weight as a diluting solvent. Then, the mixture was stirred with a disper to produce a pressure-sensitive adhesive composition (10).
The obtained pressure-sensitive adhesive composition (10) was applied to a substrate “Lumirror S10” (thickness: 38 μm, manufactured by Toray Industries, Inc.) made of a polyester resin so that the thickness after drying with a fountain roll was 50 μm, and the drying temperature was reduced. It was cured and dried at 130 ° C. for a drying time of 30 seconds. Thus, an adhesive layer was formed on the substrate. Next, the silicone-treated surface of a 25 μm-thick polyester resin-based substrate (separator) having one surface subjected to silicone treatment was bonded to the surface of the pressure-sensitive adhesive layer to obtain a surface protective film (10) with a separator. .
The results are shown in Tables 2 and 3 .

[Example 11]
An adhesive composition (11) was produced in the same manner as in Example 10, except that the amount of the fluorine-containing polymer (manufactured by DIC, trade name: F-571) was changed to 3.00 parts by weight, and a pressure-sensitive adhesive composition (11) was produced. A surface protective film (11) was obtained.
The results are shown in Tables 2 and 3 .

[Example 12]
An adhesive composition (12) was produced in the same manner as in Example 10 except that the amount of the fluorine-containing polymer (manufactured by DIC, trade name: F-571) was changed to 5.00 parts by weight, and a pressure-sensitive adhesive composition (12) was produced. A surface protection film (12) was obtained.
The results are shown in Tables 2 and 3 .

[Comparative Example 8]
Except not using a fluorine-containing polymer (manufactured by DIC, trade name: F-571), the same procedure as in Example 10 was carried out to produce a pressure-sensitive adhesive composition (C8) and obtain a surface protective film with a separator (C8). Was.
The results are shown in Tables 2 and 3 .

[Comparative Example 9]
Performed in the same manner as in Example 10 except that the amount of Coronate HX (manufactured by Nippon Polyurethane Industry Co., Ltd.) was changed to 7.05 parts by weight and a fluorine-containing polymer (manufactured by DIC, trade name: F-571) was not used. To prepare a pressure-sensitive adhesive composition (C9) to obtain a surface protective film with a separator (C9).
The results are shown in Tables 2 and 3 .

[Example 13]
"Cyabain SH-109" (solid content 54%, containing fatty acid ester, manufactured by Toyo Ink Co.) as urethane prepolymer (C): 100 parts by weight, polyfunctional isocyanate compound (B) as polyfunctional alicyclic isocyanate compound Certain coronate HX (manufactured by Nippon Polyurethane Industry Co., Ltd.): 7.05 parts by weight, fluorine-containing polymer (manufactured by DIC, trade name: F-571): 1.00 part by weight, and toluene: 208 parts by weight as a diluting solvent are blended. Then, the mixture was stirred with a disper to produce a pressure-sensitive adhesive composition (13).
The obtained pressure-sensitive adhesive composition (13) was applied to a substrate “Lumirror S10” (thickness: 38 μm, manufactured by Toray Industries, Inc.) made of a polyester resin so that the thickness after drying with a fountain roll was 50 μm, and the drying temperature was reduced. It was cured and dried at 130 ° C. for a drying time of 30 seconds. Thus, an adhesive layer was formed on the substrate. Next, the silicone-treated surface of a substrate (separator) made of a polyester resin having a thickness of 25 μm and having one surface subjected to silicone treatment was bonded to the surface of the pressure-sensitive adhesive layer to obtain a surface protective film (13) with a separator. .
The results are shown in Tables 2 and 3 .

[Example 14]
An adhesive composition (14) was produced in the same manner as in Example 13, except that the amount of the fluorine-containing polymer (manufactured by DIC, trade name: F-571) was changed to 3.00 parts by weight. A surface protective film (14) was obtained.
The results are shown in Tables 2 and 3 .

[Example 15]
An adhesive composition (15) was produced in the same manner as in Example 13 except that the amount of the fluorine-containing polymer (manufactured by DIC, trade name: F-571) was changed to 5.00 parts by weight, and a pressure-sensitive adhesive composition (15) was produced. A surface protection film (15) was obtained.
The results are shown in Tables 2 and 3 .

[Comparative Example 10]
Example 13 was repeated except that a fluorine-containing polymer (manufactured by DIC, trade name: F-571) was not used, and a silicone release agent (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KS-776A): 1 part by weight was used. In the same manner, a pressure-sensitive adhesive composition (C10) was produced, and a surface protective film with a separator (C10) was obtained.
The results are shown in Tables 2 and 3 .

[Comparative Example 11]
Example 13 was repeated except that a fluorine-containing polymer (manufactured by DIC, trade name: F-571) was not used and a silicone release agent (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KS-776A): 3 parts by weight was used. In the same manner, a pressure-sensitive adhesive composition (C11) was produced, and a surface protective film with a separator (C11) was obtained.
The results are shown in Tables 2 and 3 .

[Comparative Example 12]
The amount of Coronate HX (manufactured by Nippon Polyurethane Industry Co., Ltd.) was changed to 17.7 parts by weight, the fluorine-containing polymer (manufactured by DIC, trade name: F-571) was not used, and the thickness of the pressure-sensitive adhesive layer was 10 μm. A pressure-sensitive adhesive composition (C12) was produced, and a surface protective film with a separator (C12) was obtained.
The results are shown in Tables 2 and 3 .

[Comparative Example 13]
The amount of Coronate HX (manufactured by Nippon Polyurethane Industry Co., Ltd.) was changed to 17.7 parts by weight, the fluorine-containing polymer (manufactured by DIC, trade name: F-571) was not used, and the thickness of the pressure-sensitive adhesive layer was 25 μm. A pressure-sensitive adhesive composition (C13) was produced, and a surface protective film with a separator (C13) was obtained.
The results are shown in Tables 2 and 3 .

[Example 32]
The separator of the surface protective film with separator (7) obtained in Example 7 was peeled off, and the pressure-sensitive adhesive layer side was attached to a polarizing plate (trade name “TEG1465DUHC” manufactured by Nitto Denko Corporation) as an optical member, An optical member to which the surface protective film was adhered was obtained.

(Example 33)
The separator of the surface protective film with separator (10) obtained in Example 10 was peeled off, and the pressure-sensitive adhesive layer side was adhered to a polarizing plate (trade name “TEG1465DUHC” manufactured by Nitto Denko Corporation) as an optical member. Thus, an optical member to which a surface protection film was adhered was obtained.

(Example 34)
The separator of the surface protective film with separator (13) obtained in Example 13 was peeled off, and the pressure-sensitive adhesive layer side was adhered to a polarizing plate (trade name “TEG1465DUHC” manufactured by Nitto Denko Corporation) as an optical member. Thus, an optical member to which a surface protection film was adhered was obtained.

[Example 37]
The separator of the surface protective film with separator (7) with separator obtained in Example 7 was peeled off, and the pressure-sensitive adhesive layer side was a conductive film as an electronic member (trade name “Elecrista V270L-TFMP” manufactured by Nitto Denko Corporation). To obtain an electronic member having a surface protective film attached thereto.

[Example 38]
The separator of the surface protection film with separator (10) with separator obtained in Example 10 was peeled off, and the adhesive layer side was a conductive film as an electronic member (trade name “Elecrista V270L-TFMP” manufactured by Nitto Denko Corporation). To obtain an electronic member having a surface protective film attached thereto.

(Example 39)
The separator of the surface protective film with separator (13) obtained in Example 13 was peeled off, and the pressure-sensitive adhesive layer side was a conductive film as an electronic member (trade name “Elecrista V270L-TFMP” manufactured by Nitto Denko Corporation). To obtain an electronic member having a surface protective film attached thereto.

  The surface protective film of the present invention can be used for any appropriate use. Preferably, the surface protective film of the present invention is preferably used in the field of optical members and electronic members.

DESCRIPTION OF SYMBOLS 1 Base material layer 2 Adhesive layer 10 Surface protective film

Claims (8)

A surface protective film having an adhesive layer,
A 25 μm-thick polyethylene terephthalate film was bonded to the pressure-sensitive adhesive layer, and after 30 minutes at 23 ° C., the polyethylene terephthalate film had a peeling force of 0.08 N / sec when peeled at a peeling angle of 180 ° and a peeling speed of 6000 mm / min. 25 mm or less,
A 25 μm-thick polyethylene terephthalate film was stuck to the pressure-sensitive adhesive layer, and after 30 minutes at 23 ° C., the polyethylene terephthalate film had a peeling force of 0.02 N / when peeled off at a peeling angle of 180 ° and a peeling speed of 300 mm / min. 25 mm or less,
The pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer is formed from a pressure-sensitive adhesive composition,
The pressure-sensitive adhesive composition comprises a base polymer, a silicone-based additive and / or a fluorine-based additive,
The base polymer is a urethane prepolymer,
The silicone-based additive is at least one selected from a hydroxyl-containing silicone-based compound and a crosslinkable functional group-containing silicone-based compound,
The fluorine-based additive is at least one selected from a compound having a fluoroaliphatic hydrocarbon skeleton, a fluorine-containing organic compound obtained by copolymerizing an organic compound and a fluorine compound, a hydroxyl-containing fluorine compound, and a crosslinkable functional group-containing fluorine-containing compound. And
When the content of the silicone-based additive and / or the fluorine-based additive in the pressure-sensitive adhesive composition is 0 as a total amount of the silicone-based additive and the fluorine-based additive relative to 100 parts by weight of the base polymer, 0.01 parts by weight to 50 parts by weight,
Surface protection film.
However, the above-mentioned pressure-sensitive adhesive composition contains 100 parts by weight of "CYAVINE SH-109H" (54% solid content, manufactured by Toyochem Corporation) as a urethane pressure-sensitive adhesive, and "CYAVINE BXX-6269" (manufactured by Toyochem Corporation) as a crosslinking agent. .9 parts by weight, leveling agent (Grandick PC4100 (Silicone), manufactured by DIC): 0.05 parts by weight or 0.01 parts by weight, diluted with toluene so that the solid content of the adhesive composition becomes 45% However, this does not include the case of a urethane-based pressure-sensitive adhesive composition obtained by stirring with a disper. A surface protective film having an adhesive layer,
A 25 μm-thick polyethylene terephthalate film was attached to the pressure-sensitive adhesive layer, and after 7 days at 80 ° C., the polyethylene terephthalate film had a peeling force of 0.35 N / when peeled at a peeling angle of 180 ° and a peeling speed of 6000 mm / min. 25 mm or less,
A 25 μm-thick polyethylene terephthalate film was attached to the pressure-sensitive adhesive layer, and after 7 days at 80 ° C., the polyethylene terephthalate film had a peeling force of 0.07 N / when peeled at a peeling angle of 180 ° and a peeling speed of 300 mm / min. 25 mm or less,
The pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer is formed from a pressure-sensitive adhesive composition,
The pressure-sensitive adhesive composition comprises a base polymer, a silicone-based additive and / or a fluorine-based additive,
The base polymer is a urethane prepolymer,
The silicone-based additive is at least one selected from a hydroxyl-containing silicone-based compound and a crosslinkable functional group-containing silicone-based compound,
The fluorine-based additive is at least one selected from a compound having a fluoroaliphatic hydrocarbon skeleton, a fluorine-containing organic compound obtained by copolymerizing an organic compound and a fluorine compound, a hydroxyl-containing fluorine compound, and a crosslinkable functional group-containing fluorine-containing compound. And
When the content of the silicone-based additive and / or the fluorine-based additive in the pressure-sensitive adhesive composition is 0 as a total amount of the silicone-based additive and the fluorine-based additive relative to 100 parts by weight of the base polymer, 0.01 parts by weight to 50 parts by weight,
Surface protection film.
However, the above-mentioned pressure-sensitive adhesive composition contains 100 parts by weight of "CYAVINE SH-109H" (54% solid content, manufactured by Toyochem Corporation) as a urethane pressure-sensitive adhesive, and "CYAVINE BXX-6269" (manufactured by Toyochem Corporation) as a crosslinking agent. .9 parts by weight, leveling agent (Grandick PC4100 (Silicone), manufactured by DIC): 0.05 parts by weight or 0.01 parts by weight, diluted with toluene so that the solid content of the adhesive composition becomes 45% However, this does not include the case of a urethane-based pressure-sensitive adhesive composition obtained by stirring with a disper. A surface protective film having an adhesive layer,
A glass plate having a thickness of 1000 μm is attached to the pressure-sensitive adhesive layer, and after 30 minutes at 23 ° C., the peeling force when peeled from the glass plate at a peeling angle of 180 ° and a peeling speed of 6000 mm / min is 0.135 N / 25 mm or less. And
A glass plate having a thickness of 1000 μm is bonded to the pressure-sensitive adhesive layer, and after 30 minutes at 23 ° C., the peeling force when peeled from the glass plate at a peeling angle of 180 ° and a peeling speed of 300 mm / min is 0.023 N / 25 mm or less. And
The pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer is formed from a pressure-sensitive adhesive composition,
The pressure-sensitive adhesive composition comprises a base polymer, a silicone-based additive and / or a fluorine-based additive,
The base polymer is a urethane prepolymer,
The silicone-based additive is at least one selected from a hydroxyl-containing silicone-based compound and a crosslinkable functional group-containing silicone-based compound,
The fluorine-based additive is at least one selected from a compound having a fluoroaliphatic hydrocarbon skeleton, a fluorine-containing organic compound obtained by copolymerizing an organic compound and a fluorine compound, a hydroxyl-containing fluorine compound, and a crosslinkable functional group-containing fluorine-containing compound. And
When the content of the silicone-based additive and / or the fluorine-based additive in the pressure-sensitive adhesive composition is 0 as a total amount of the silicone-based additive and the fluorine-based additive relative to 100 parts by weight of the base polymer, 0.01 parts by weight to 50 parts by weight,
Surface protection film.
However, the above-mentioned pressure-sensitive adhesive composition contains 100 parts by weight of "CYAVINE SH-109H" (54% solid content, manufactured by Toyochem Corporation) as a urethane pressure-sensitive adhesive, and "CYAVINE BXX-6269" (manufactured by Toyochem Corporation) as a crosslinking agent. .9 parts by weight, leveling agent (Grandick PC4100 (Silicone), manufactured by DIC): 0.05 parts by weight or 0.01 parts by weight, diluted with toluene so that the solid content of the adhesive composition becomes 45% However, this does not include the case of a urethane-based pressure-sensitive adhesive composition obtained by stirring with a disper. A surface protective film having an adhesive layer,
A glass plate having a thickness of 1000 μm is stuck to the pressure-sensitive adhesive layer, and after 7 days at 80 ° C., the peeling force when peeled from the glass plate at a peeling angle of 180 ° and a peeling speed of 6000 mm / min is 0.35 N / 25 mm or less. And
A glass plate having a thickness of 1000 μm is bonded to the pressure-sensitive adhesive layer, and after 7 days at 80 ° C., the peeling force when peeled off from the glass plate at a peeling angle of 180 ° and a peeling speed of 300 mm / min is 0.05 N / 25 mm or less. And
The pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer is formed from a pressure-sensitive adhesive composition,
The pressure-sensitive adhesive composition comprises a base polymer, a silicone-based additive and / or a fluorine-based additive,
The base polymer is a urethane prepolymer,
The silicone-based additive is at least one selected from a hydroxyl-containing silicone-based compound and a crosslinkable functional group-containing silicone-based compound,
The fluorine-based additive is at least one selected from a compound having a fluoroaliphatic hydrocarbon skeleton, a fluorine-containing organic compound obtained by copolymerizing an organic compound and a fluorine compound, a hydroxyl-containing fluorine compound, and a crosslinkable functional group-containing fluorine-containing compound. And
When the content of the silicone-based additive and / or the fluorine-based additive in the pressure-sensitive adhesive composition is 0 as a total amount of the silicone-based additive and the fluorine-based additive relative to 100 parts by weight of the base polymer, 0.01 parts by weight to 50 parts by weight,
Surface protection film.
However, the above-mentioned pressure-sensitive adhesive composition contains 100 parts by weight of "CYAVINE SH-109H" (54% solid content, manufactured by Toyochem Corporation) as a urethane pressure-sensitive adhesive, and "CYAVINE BXX-6269" (manufactured by Toyochem Corporation) as a crosslinking agent. .9 parts by weight, leveling agent (Grandick PC4100 (Silicone), manufactured by DIC): 0.05 parts by weight or 0.01 parts by weight, diluted with toluene so that the solid content of the adhesive composition becomes 45% However, this does not include the case of a urethane-based pressure-sensitive adhesive composition obtained by stirring with a disper. The surface protective film according to any one of claims 1 to 4 , wherein the residual adhesion ratio is 50% or more. The surface protective film according to any one of claims 1 to 5 , wherein the pressure-sensitive adhesive composition contains a fatty acid ester. An optical member to which the surface protective film according to any one of claims 1 to 6 is adhered. An electronic member to which the surface protection film according to any one of claims 1 to 6 is adhered.

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