KR101972729B1 - Surface protective film - Google Patents

Abstract

The present invention provides a surface protective film having a cemented carbide peeling property and a low staining property on the surface of an adherend. The surface protective film of the present invention is a surface protective film having a pressure-sensitive adhesive layer, and a polyethylene terephthalate film having a thickness of 25 占 퐉 is bonded to the pressure-sensitive adhesive layer. After 30 minutes at 23 占 폚, the polyethylene terephthalate film is peeled off at 180 占, The peeling force when peeling at a peeling speed of 6000 mm / min is 0.08 N / 25 mm or less.

Description

Surface protective film

The present invention relates to a surface protective film.

BACKGROUND ART [0002] In an optical member or an electronic member manufacturing process, a surface protective film is generally adhered to an exposed surface in order to prevent surface scratches during processing, assembly, inspection, and transportation. Such a surface protective film is peeled off from an optical member or an electronic member at a time when the need for surface protection is eliminated (Patent Document 1).

When an optical member or an electronic member to which such a surface protective film is adhered is to be peeled as described above, it is important that the surface protective film can be smoothly peeled off from the interface between the surface protective film and the optical member or the electron member.

However, in the case where the optical member or the electron member is provided with a fragile member such as a foil glass or a barrier film, even if a conventional surface protective film having a light yellowing property is used, There is a case where the member which is likely to be broken by the force is damaged.

For this reason, a surface protective film having lighter peelability, that is, a peelability in peelability, is required as compared with a conventional surface protective film having a light yellowing property.

Here, when a conventional release agent is contained in a large amount in the pressure-sensitive adhesive layer of the surface protective film in order to weaken the peeling force, there is a case where a certain degree of cement-based releasability can be exhibited. However, in such a method, when the surface protective film is peeled off, the degree of contamination of the surface of the adherend due to the peeling agent is large, and when the surface protective film is further adhered to the surface, the surface protective film is difficult to adhere due to contamination of the surface of the adherend there is a problem.

In addition, in the manufacturing process of the optical member and the electronic member, the surface protective film adhered to the exposed surface is frequently adhered and kept bonded to prevent scratches on the surface during processing, assembly, inspection, and transport. In this case, when the conventional surface protective film is stored while being adhered, the adhesive strength is increased over time, which results in a serious problem.

As described above, the surface protective film to be adhered to the exposed surface in order to prevent scratches on the surface during processing, assembling, inspecting, transportation, and the like in the manufacturing process of the optical member and the electron member, That is, it is necessary to improve cemented carbide peelability, to reduce the stain on the surface of the adherend, to suppress heavy fading in time, and the like.

Japanese Patent Application Laid-Open No. 2016-17109

Disclosure of the Invention Problems to be Solved by the Invention A problem to be solved by the present invention is to provide a surface protective film imparted with cementedia peelability and providing a surface protective film capable of lowering the staining property of the surface of an adherend and to provide a surface protective film capable of suppressing heavy- .

In the surface protective film of the present invention,

A surface protective film having a pressure-sensitive adhesive layer,

A polyethylene terephthalate film having a thickness of 25 占 퐉 was bonded to the pressure-sensitive adhesive layer, and after peeling the polyethylene terephthalate film at 23 占 폚 for 30 minutes at a peeling angle of 180 degrees and a peeling speed of 6000 mm / min, the peeling force was 0.08 N / 25mm or less.

In one embodiment, a polyethylene terephthalate film having a thickness of 25 占 퐉 was bonded to the pressure-sensitive adhesive layer, and after 30 minutes at 23 占 폚, the polyethylene terephthalate film was peeled off at a peeling angle of 180 degrees and a peeling rate of 300 mm / The peel force is 0.02 N / 25 mm or less.

In the surface protective film of the present invention,

A surface protective film having a pressure-sensitive adhesive layer,

A polyethylene terephthalate film having a thickness of 25 占 퐉 was bonded to the pressure-sensitive adhesive layer, and after peeling the polyethylene terephthalate film at 80 占 폚 for 7 days at a peeling angle of 180 degrees and a peeling rate of 6000 mm / min, the peeling force was 0.35 N / 25mm or less.

In one embodiment, a polyethylene terephthalate film having a thickness of 25 占 퐉 was bonded to the pressure-sensitive adhesive layer, and after 7 days at 80 占 폚, the polyethylene terephthalate film was peeled off at a peeling angle of 180 degrees and a peeling rate of 300 mm / The peel force is 0.07 N / 25 mm or less.

In the surface protective film of the present invention,

A surface protective film having a pressure-sensitive adhesive layer,

A releasing force of 0.135 N / 25 mm or less when peeled off from the glass plate at 23 deg. C at a peeling angle of 180 deg. And a peeling rate of 6000 mm / min after joining a glass plate having a thickness of 1000 mu m to the pressure sensitive adhesive layer.

In one embodiment, a glass plate having a thickness of 1000 占 퐉 is bonded to the pressure-sensitive adhesive layer, and after 30 minutes at 23 占 폚, the releasing force from the glass plate at a peeling angle of 180 degrees and a peeling rate of 300 mm / N / 25mm or less.

In the surface protective film of the present invention,

A surface protective film having a pressure-sensitive adhesive layer,

A releasing force of 0.35 N / 25 mm or less is obtained when the glass plate having a thickness of 1000 占 퐉 is bonded to the pressure-sensitive adhesive layer and peeled from the glass plate at 80 占 폚 at a peeling angle of 180 degrees and a peeling rate of 6000 mm / min.

In one embodiment, a glass plate having a thickness of 1000 占 퐉 is bonded to the pressure-sensitive adhesive layer, and after 7 days at 80 占 폚, the releasing force when peeled off from the glass plate at a peeling angle of 180 degrees and a peeling rate of 300 mm / N / 25mm or less.

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

In one embodiment, the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer is formed of 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 additive is at least one selected from a siloxane bond-containing compound, a hydroxyl group-containing silicone compound, and a crosslinkable functional group-containing silicone compound.

In one embodiment, the fluorine-based additive is at least one selected from the group consisting of a fluorine-containing compound, a hydroxyl group-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 resin is a urethane 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 includes a fatty acid ester.

The optical member of the present invention is one to which the surface protective film of the present invention is adhered.

The electronic member of the present invention is one to which the surface protective film of the present invention is adhered.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a surface protective film having a cemented carbide peeling property and a low staining property on the surface of an adherend.

1 is a schematic sectional view of a surface protective film according to an 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 suitable other member as long as it does not impair the effect of the present invention, provided that it has a pressure sensitive adhesive layer. Typically, the surface protective film of the present invention has a base layer and a pressure-sensitive adhesive layer.

1 is a schematic sectional view of a surface protective film according to an embodiment of the present invention. 1, the surface protective film 10 comprises a base layer 1 and a pressure-sensitive adhesive layer 2. The surface- In Fig. 1, the base layer 1 and the pressure-sensitive adhesive layer 2 are directly laminated.

In Fig. 1, the surface of the pressure-sensitive adhesive layer 2 on the opposite side of the base layer 1 may be provided with any suitable release liner (not shown) for protection until use. As the release liner, for example, a release liner in which the surface of a substrate (liner base) such as paper or plastic film is subjected to silicone treatment, a release liner in which the surface of a substrate (liner base) such as paper or plastic film is laminated with a polyolefin- And the like. Examples of the plastic film as the liner substrate include a polyethylene film, a polypropylene film, a polybutene film, a polybutadiene film, a polymethylpentene film, a polyvinyl chloride film, a vinyl chloride copolymer film, a polyethylene terephthalate film, A phthalate film, 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 占 퐉 to 500 占 퐉, more preferably 3 占 퐉 to 450 占 퐉, still more preferably 5 占 퐉 to 400 占 퐉, and particularly preferably 10 占 퐉 to 300 占 퐉.

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

In one embodiment of the surface protective film of the present invention, a polyethylene terephthalate film having a thickness of 25 占 퐉 is bonded to a pressure-sensitive adhesive layer, and after 30 minutes at 23 占 폚, the polyethylene terephthalate film is peeled off at a peeling angle of 180 degrees, Min or less, 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, 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 practically 0.001 N / 25 mm or more. When the peeling force at a very high peeling rate of 6000 mm / min is within the above range, the surface protective film of the present invention can exhibit very excellent peelability. 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 polyethylene terephthalate film having a thickness of 25 占 퐉 is bonded to a pressure-sensitive adhesive layer, and after 30 minutes at 23 占 폚, the polyethylene terephthalate film is peeled off at a peeling angle of 180 degrees, Min or less, preferably 0.02 N / 25 mm or less, more preferably 0.018 N / 25 mm or less, still more preferably 0.015 N / 25 mm or less, and particularly preferably 0.012 N / 25 mm or less, and most preferably 0.01 N / 25 mm or less. The lower limit of the peeling force is practically 0.001 N / 25 mm or more. When the peel force is within the above range, the surface protective film of the present invention can exhibit the peelability of the peel. Details of the measurement of the peeling force will be described later.

In one embodiment of the surface protective film of the present invention, the polyethylene terephthalate film having a thickness of 25 占 퐉 is bonded to the pressure-sensitive adhesive layer, and after 7 days at 80 占 폚, the polyethylene terephthalate film is peeled off at a peeling angle of 180 degrees, Min or less, preferably 0.35 N / 25 mm or less, more preferably 0.33 N / 25 mm or less, more preferably 0.3 N / 25 mm or less, still more preferably 0.27 N / / 25 mm or less, particularly preferably 0.25 N / 25 mm or less, and most preferably 0.23 N / 25 mm or less. The lower limit of the peeling force is practically 0.001 N / 25 mm or more. When the peeling force after 7 days at 80 占 폚 is within the above range, the surface protective film of the present invention can sufficiently suppress the occurrence of serious deterioration with time. Details of the measurement of the peeling force will be described later.

In one embodiment of the surface protective film of the present invention, the polyethylene terephthalate film having a thickness of 25 占 퐉 is bonded to the pressure-sensitive adhesive layer, and after 7 days at 80 占 폚, the polyethylene terephthalate film is peeled off at a peeling angle of 180 deg. Min or less, preferably 0.07 N / 25 mm or less, more preferably 0.06 N / 25 mm or less, still more preferably 0.05 N / 25 mm or less, and particularly preferably 0.045 N / 25 mm or less, and most preferably 0.04 N / 25 mm or less. The lower limit of the peeling force is practically 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 suppress the occurrence of heavy sticking with time. Details of the measurement of the peeling force will be described later.

In one embodiment of the surface protective film of the present invention, when a glass plate having a thickness of 1000 占 퐉 is bonded to the pressure-sensitive adhesive layer and peeled from the glass plate at 23 占 폚 for 30 minutes at a peeling angle of 180 degrees and a peeling rate of 6000 mm / Is preferably 0.135 N / 25 mm or less, more preferably 0.1 N / 25 mm or less, still more preferably 0.07 N / 25 mm or less, still more preferably 0.065 N / 25 mm or less 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 practically 0.001 N / 25 mm or more. When the peeling force at a very high peeling rate of 6000 mm / min is within the above range, the surface protective film of the present invention can exhibit very excellent peelability. Details of the measurement of the peeling force will be described later.

In one embodiment of the surface protective film of the present invention, when a glass plate having a thickness of 1000 占 퐉 is bonded to the pressure-sensitive adhesive layer and peeled from the glass plate at 23 占 폚 for 30 minutes at a peeling angle of 180 degrees and a peeling rate of 300 mm / Is preferably 0.023 N / 25 mm or less, more preferably 0.022 N / 25 mm or less, still more preferably 0.02 N / 25 mm or less, particularly preferably 0.015 N / 25 mm or less, 0.013 N / 25 mm or less. The lower limit of the peeling force is practically 0.001 N / 25 mm or more. When the peel force is within the above range, the surface protective film of the present invention can exhibit the peelability of the peel. Details of the measurement of the peeling force will be described later.

In one embodiment of the surface protective film of the present invention, when a 1,000 mu m thick glass plate is bonded to the pressure-sensitive adhesive layer and peeled from the glass plate at 80 DEG C for 7 days at a peeling angle of 180 DEG and a peeling rate of 6000 mm / Is preferably not more than 0.35 N / 25 mm, more preferably not more than 0.3 N / 25 mm, more preferably not more than 0.25 N / 25 mm, even more preferably not more than 0.2 N / 25 mm, 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 practically 0.001 N / 25 mm or more. When the peeling force after 7 days at 80 占 폚 is within the above range, the surface protective film of the present invention can sufficiently suppress the serious deterioration with time. Details of the measurement of the peeling force will be described later.

In one embodiment of the surface protective film of the present invention, when a glass plate having a thickness of 1000 占 퐉 is bonded to the pressure-sensitive adhesive layer and peeled from the glass plate at 80 占 폚 for 7 days at a peeling angle of 180 degrees and a peeling rate of 300 mm / Is preferably 0.05 N / 25 mm or less, more preferably 0.045 N / 25 mm or less, still more preferably 0.04 N / 25 mm or less, particularly preferably 0.035 N / 25 mm or less, 0.03 N / 25 mm or less. The lower limit of the peeling force is practically 0.001 N / 25 mm or more. When the peeling force is in the above range, the surface protective film of the present invention can suppress the occurrence of heavy sticking with time. Details of the measurement of the peeling force will be described later.

The surface protective film of the present invention preferably has a residual adhesion rate of 50% or more, more preferably 55% to 100%, further preferably 60% to 100%, particularly preferably 65% 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 the surface stain on the adherend is low. Details of the measurement of the residual adhesion rate will be described later.

The surface protective film of the present invention can be produced by any suitable method. As such a manufacturing method, for example,

(1) Method of forming a pressure-sensitive adhesive layer A method of applying a solution or heat melt of a material on a substrate layer,

(2) Method of forming a pressure-sensitive adhesive layer A method of adhering a pressure-sensitive adhesive layer formed by applying a solution of a material or a hot melt onto a separator,

(3) a method of extruding and forming a pressure-sensitive adhesive layer forming material on a base layer,

(4) a method of extruding the base layer and the pressure-sensitive adhesive layer into two layers or multiple layers,

(5) a method in which the pressure-sensitive adhesive layer is laminated on the base layer or a method in which the pressure-sensitive adhesive layer is laminated on the two layers together with the laminate layer,

(6) a method of laminating a pressure-sensitive adhesive layer and a base layer forming material such as a film or a laminate layer in a two-layer or multilayer manner

, And the like.

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 and the like can be used.

&Quot; Base layer "

The base layer may be a single layer or two or more layers. The base layer may be stretched.

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

The surface of the base layer not to be provided with the pressure-sensitive adhesive layer may be prepared by adding a fatty acid amide, a polyethyleneimine, a long-chain alkyl-based additive, or the like to the base layer, for example, for the purpose of forming a winding- Or a coat layer containing any suitable releasing agent such as a silicone system, a long chain alkyl system, or a fluorine system may be formed.

As the material of the base layer, any suitable material may be employed depending on the application. Examples thereof include plastics, paper, metal films, and nonwoven fabrics. It is preferably a plastic. That is, the substrate layer is preferably a plastic film. The substrate layer may be composed of one kind of material, or may be composed of two or more kinds of materials. For example, it may be composed of two or more kinds of 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-based resin include a homopolymer of an olefin monomer, a copolymer of an olefin monomer, and the like. Specific examples of the polyolefin-based resin include homopolypropylene; Propylene-based copolymers such as a block system, a random system and a graft system having an ethylene component as a copolymerization component; Reactor TPO; Ethylene polymers such as low density, high density, linear low density and ultra low density; Ethylene / vinyl acetate copolymers, ethylene / vinyl acetate copolymers, ethylene / vinyl acetate copolymers, ethylene / acrylate copolymers, ethylene / acrylate copolymers, ethylene / And the like; And the like.

The base layer may contain any suitable additives as required. Examples of additives that can be contained in the base layer include antioxidants, ultraviolet absorbers, light stabilizers, antistatic agents, fillers, pigments and the like. The kind, quantity, and amount of the additive that may be contained in the base layer may be appropriately set according to the purpose. Particularly, 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 or the like. From the viewpoint of improving weatherability and the like, additives such as an antioxidant, an ultraviolet absorber, a light stabilizer and a filler are particularly preferable.

As the antioxidant, any suitable antioxidant may be employed. Examples of such an antioxidant include a phenol-based antioxidant, a phosphorus-based heat stabilizer, a lactone-based heat stabilizer, a sulfur-based heat stabilizer, and a phenol-phosphorus antioxidant. The content of the antioxidant is preferably 1% by weight or less, more preferably 0.5% by weight or less based on the base resin of the base layer (when the base layer is a blend, the blend is the base resin) More preferably 0.01% by weight to 0.2% by weight.

As the ultraviolet absorber, any appropriate ultraviolet absorber can be employed. Examples of such ultraviolet absorbers include benzotriazole ultraviolet absorbers, triazine ultraviolet absorbers, benzophenone ultraviolet absorbers, and the like. The content of the ultraviolet absorber is preferably at most 2% by weight, more preferably at most 1% by weight, based on the base resin forming the base layer (when the base layer is a blend, the blend is the base resin) By weight, and more preferably 0.01% by weight to 0.5% by weight.

As the light stabilizer, any suitable light stabilizer can be employed. Examples of such light stabilizers include hindered amine light stabilizers, benzoate light stabilizers, and the like. The content of the light stabilizer is preferably 2% by weight or less, more preferably 1% by weight or less, based on the base resin forming the base layer (when the base layer is a blend, the blend is the base resin) By weight, and more preferably 0.01% by weight to 0.5% by weight.

As the filler, any suitable filler can be employed. Examples of such fillers include inorganic fillers. Specific examples of the inorganic filler include carbon black, titanium oxide, zinc oxide and the like. The content of the filler is preferably 20% by weight or less, more preferably 10% by weight or less, based on the base resin forming the base layer (when the base layer is a blend, the blend is the base resin) By weight, more preferably 0.01% by weight to 10% by weight.

As the additive, inorganic, low molecular weight and high molecular weight antistatic agents such as surfactants, inorganic salts, polyhydric alcohols, metal compounds and carbon are preferably used for the purpose of imparting antistatic properties. Particularly, from the viewpoints of keeping contamination and tackiness, high molecular weight antistatic agents and carbon are preferable.

«Pressure-sensitive adhesive layer»

The pressure-sensitive adhesive layer can be produced by any suitable manufacturing method. Such a production method includes, for example, a method of applying a composition, which is a material for forming a pressure-sensitive adhesive layer, on a base layer and forming a pressure-sensitive adhesive layer on the base layer. Examples of such coating methods include roll coats, gravure coats, reverse coats, roll brushes, spray coats, air knife coats, extrusion coats with die coaters, and the like.

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

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

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

The content of the silicone additive and / or the fluorine-based additive in the pressure-sensitive adhesive composition is preferably 0.01 to 50 parts by weight, more preferably 0.02 parts by weight, per 100 parts by weight of the base polymer, To 25 parts by weight, more preferably 0.025 parts by weight to 10 parts by weight, particularly preferably 0.03 parts by weight to 5 parts by weight, and most preferably 0.05 parts by weight 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 hardness peelability and further reduce stain on the surface of the adherend.

<Base polymer>

The base polymer is preferably at least one selected from a urethane-based resin, an acrylic resin, a rubber-based resin, and a silicone-based resin. The base polymer is more preferably a urethane-based resin or an acrylic-based resin in that the effect of the present invention can be further exerted.

[Urethane resin]

As the urethane-based resin, any suitable urethane-based resin can be employed as long as the effect of the present invention is not impaired. The urethane resin is preferably a urethane resin formed from a composition containing a polyol (A) and a polyfunctional isocyanate compound (B), or a urethane resin formed from a composition containing a urethane prepolymer (C) and a polyfunctional isocyanate compound (B) Based resin. Since the wettability of the pressure-sensitive adhesive layer can be improved by adopting the same as the urethane resin, the surface protective film of the present invention can be bonded without bubbling the bubbles.

The urethane-based resin may contain any suitable components as long as the effect of the present invention is not impaired. Examples of such components include a resin component other than the urethane resin, a tackifier, an inorganic filler, an organic filler, a metal powder, a pigment, a foil, a softener, an antioxidant, a conductive agent, an ultraviolet absorber, an antioxidant, , A leveling agent, a corrosion inhibitor, a heat stabilizer, a polymerization inhibitor, a lubricant, a solvent, a catalyst and the like.

The urethane-based resin preferably includes an antioxidant such as an antioxidant, an ultraviolet absorber, or a light stabilizer. Since the urethane-based resin contains a deterioration inhibitor, it is possible to obtain excellent adhesive residue retention property, for example, it is difficult for the adhesive to remain on the adherend even after being adhered to the adherend and preserved in a heated state. The deterioration inhibitor may be one kind or two or more kinds. As the deterioration inhibitor, it is particularly preferably an antioxidant.

Examples of the antioxidant include a radical chain inhibitor and a peroxide dissolution inhibitor.

Examples of the radical chain inhibitor include phenol-based antioxidants and amine-based antioxidants.

Examples of the releasing of peroxide 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 antioxidant include 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di- (3,5-di-t-butyl-4-hydroxyphenyl) propionate.

Examples of the bisphenol-based antioxidant include 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2,2'-methylenebis , 3'-thiobis (3-methyl-6-t-butylphenol), 4,4'-butylidenebis Propyloxy] ethyl] 2,4,8,10-tetraoxaspiro [5,5] undecane, and the like, in the presence of a base such as triethylamine, .

Examples of the polymer type phenolic antioxidant include 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 1,3,5-trimethyl- Tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, tetrakis- [methylene- (3'-hydroxy-3'-t-butylphenyl) butanoic acid] glycol ester, 1,3,5-tris (3 ', 5'-di -t-butyl-4'-hydroxybenzyl) -S-triazine-2,4,6- (1H, 3H, 5H) trione and tocophenol.

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 antioxidant include triphenyl phosphite, diphenyl isodecyl phosphite, phenyl diisodecyl phosphite and the like.

Examples of the ultraviolet absorber include benzophenone ultraviolet absorbers, benzotriazole ultraviolet absorbers, salicylic acid ultraviolet absorbers, oxalanilide ultraviolet absorbers, cyanoacrylate ultraviolet absorbers, triazine-based ultraviolet absorbers, and the like.

Examples of the benzophenone ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2- -Dodecyloxybenzophenone, 2,2'-dihydroxy-4-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4- 5-sulfobenzophenone, bis (2-methoxy-4-hydroxy-5-benzoylphenyl) methane and the like.

Examples of the benzotriazole ultraviolet absorber include 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-5'- Butylphenyl) benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) Benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) 3'- (3 &quot;, 4 &quot;, 5 &quot; -tetramethylphenyl) benzotriazole, 2- (2'- , 6 ", -tetrahydrophthalimidomethyl) -5'-methylphenyl] benzotriazole, 2,2'methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- Triazol-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, and p-octylphenyl salicylate.

Examples of the cyanoacrylate ultraviolet absorber include 2-ethylhexyl-2-cyano-3,3'-diphenylacrylate, ethyl-2-cyano- .

Examples of the light stabilizer include hindered amine light stabilizers and ultraviolet light stabilizers.

Examples of hindered amine light stabilizers include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl- 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-octylphenolato)] n-butylamine nickel, nickel complex- tert-butyl-4-hydroxybenzyl-phosphoric acid monoethylate, nickel-dibutyldithiocarbamate, benzoate type, and nickel-dibutyldithiocarbamate.

(A urethane-based resin formed of 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 resin obtained by curing a composition containing the polyol (A) and the polyfunctional isocyanate compound (B) Based resin.

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

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

The polyol (A) is preferably a polyester polyol, a polyether polyol, a polycaprolactone polyol, a polycarbonate polyol or a castor oil-based polyol, for example. The polyol (A) is more preferably a polyether polyol.

The polyester polyol can be obtained, for example, by an esterification reaction of 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, , 3-propanediol, 2,4-diethyl-1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 1,8-octanediol, 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-dodecanedioic acid, 1,14-tetradecanedioic acid, Cyclohexane dicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, isophthalic acid, terephthalic acid, 1,4-naphthalene dicarboxylic acid, 4,4'- -Biphenyl dicarboxylic acid, and their acid anhydrides.

Examples of the polyether polyols include water, low molecular polyols (propylene glycol, ethylene glycol, glycerin, trimethylol propane, pentaerythritol, etc.), bisphenols (such as bisphenol A), dihydroxybenzenes (catechol, resorcin, Hydroquinone, etc.) as an initiator and addition polymerization of an alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide and the like. Specific examples thereof include polyethylene glycol, polypropylene glycol, and polytetramethylene glycol.

Examples of the polycaprolactone polyols include caprolactone-based polyester diols obtained by ring-opening polymerization of cyclic ester monomers such as? -Caprolactone and? -Valerolactone.

Examples of the polycarbonate polyol include a polycarbonate polyol obtained by a polycondensation reaction of the polyol component and phosgene; The above-mentioned polyol component is mixed with the carbonic acid di (methane) carbonate such as dimethyl carbonate, diethyl carbonate, dipropyl carbonate, diisopropyl carbonate, dibutyl carbonate, ethylbutyl carbonate, ethylene carbonate, propylene carbonate, diphenyl carbonate, Polycarbonate polyols obtained by ester exchange condensation of esters; A copolymerized polycarbonate polyol obtained by using two or more of the above polyol components in combination; A polycarbonate polyol obtained by esterifying the various polycarbonate polyols and a carboxyl group-containing compound; A polycarbonate polyol obtained by etherifying the various polycarbonate polyols and a hydroxyl group-containing compound; A polycarbonate polyol obtained by transesterifying various polycarbonate polyols and an ester compound; A polycarbonate polyol obtained by an ester exchange reaction between the various polycarbonate polyols and a hydroxyl group-containing compound; A polyester polycarbonate polyol obtained by polycondensation reaction of the various polycarbonate polyols and a dicarboxylic acid compound; A copolymerized polyether polycarbonate polyol obtained by copolymerizing the various polycarbonate polyols and an alkylene oxide; And the like.

Examples of the castor oil-based polyol include a castor oil-based polyol obtained by reacting a castor oil fatty acid with the polyol component. Specifically, there can be mentioned, for example, castor oil-based polyols obtained by reacting castor oil fatty acid with polypropylene glycol.

The number average molecular weight Mn of the polyol (A) is preferably 300 to 100000, more preferably 400 to 75000, still more preferably 450 to 50000, and particularly preferably 500 to 30000. Since the wettability of the pressure-sensitive adhesive layer can be improved by adjusting the number-average molecular weight Mn of the polyol (A) within the above range, the surface protective film of the present invention can be bonded without bubbling the 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 one kind alone, or two or more kinds.

The content 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 still more preferably 50% by weight to 100% by weight. Since the wettability of the pressure-sensitive adhesive layer can be improved by adjusting the content of the polyol (A1) in the polyol (A) within the above range, the surface protective film of the present invention can be bonded without bubbling the bubbles.

The number average molecular weight Mn of the polyol (A1) is preferably from 1000 to 100000, more preferably from 1200 to 80000, still more preferably from 1500 to 70000, even more preferably from 1750 to 50000, Is from 1500 to 40000, and most preferably from 2,000 to 30,000. Since the wettability of the pressure-sensitive adhesive layer can be improved by adjusting the number-average molecular weight Mn of the polyol (A1) within the above range, the surface protective film of the present invention can be bonded without bubbling the bubbles.

The polyol (A) may contain a polyol (A2) having 3 or more OH groups and a number average molecular weight Mn of 20,000 or less. The polyol (A2) may be one kind alone, or two or more kinds. The number average molecular weight Mn of the polyol (A2) is preferably 100 to 20,000, more preferably 150 to 10000, still more preferably 200 to 7500, particularly preferably 300 to 6000, and most preferably, 300 to 5000. If the number-average molecular weight Mn of the polyol (A2) deviates from the above-mentioned range, there is a possibility that the riseability of the adhesive strength with time may be increased, and the excellent reworkability may not be exhibited. The polyol (A2) is preferably a polyol (triol) having three OH groups, a polyol (tetraol) having four OH groups, a polyol (pentanol) having five OH groups, a polyol having six OH groups Come).

The total amount of at least one of the polyol (tetraol) having 4 OH groups, the polyol (pentanol) having 5 OH groups and the polyol (hexaol) having 6 OH groups as the polyol (A2) Is preferably 70% by weight or less, more preferably 60% by weight or less, still more preferably 40% by weight or less, and particularly preferably 30% by weight or less. At least one of a polyol (tetraol) having 4 OH groups, a polyol (pentanol) having 5 OH groups and a polyol (hexaol) having 6 OH groups in the polyol (A) It is possible to provide a urethane resin having excellent transparency and further improve the wettability of the pressure-sensitive adhesive layer, so that the surface protective film of the present invention can be bonded without bubbling the bubbles.

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

The content of the polyol having a number average molecular weight Mn of not more than 20,000 and not less than 4 OH groups in the polyol (A2) is preferably less than 70% by weight, Preferably 60 wt% or less, more preferably 50 wt% or less, particularly preferably 40 wt% or less, and most preferably 30 wt% or less. By adjusting the content ratio of the polyol having four or more OH groups in the polyol (A2) and having a number average molecular weight Mn of 20,000 or less within the above range, it is possible to provide a urethane resin having excellent transparency and to improve the wettability of the pressure- The surface protective film of the present invention can be bonded without bubbling the bubbles.

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

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

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

Examples of the polyfunctional alicyclic isocyanate compound include 1,3-cyclopentene diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate , Hydrogenated xylylene diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated tetramethyl xylylene diisocyanate, and the like.

Examples of the polyfunctional aromatic diisocyanate compound include phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,2'-diphenylmethane diisocyanate, 4,4'-diphenyl Methane diisocyanate, 4,4'-toluidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate and xylylene diisocyanate. have.

Examples of the polyfunctional isocyanate compound (B) include trimethylolpropane adducts of various polyfunctional isocyanate compounds as described above, burettes obtained by reacting with water, trimer having an isocyanurate ring, and the like. These may be used in combination.

The equivalent ratio of the NCO group and the OH group in the polyol (A) and the polyfunctional isocyanate compound (B) is preferably 5.0 or less, more preferably 0.1 to 3.0, as NCO group / OH group, Is from 0.2 to 2.5, particularly preferably from 0.3 to 2.25, and most preferably from 0.5 to 2.0. By adjusting the equivalent ratio of the 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 bonded without bubbling the bubbles.

The content of the polyfunctional isocyanate compound (B) is preferably 1.0% by weight to 30% by weight, more preferably 1.5% by weight to 27% by weight, based on the polyol (A) %, More preferably from 2.0 wt% to 25 wt%, particularly preferably from 2.3 wt% to 23 wt%, and most preferably from 2.5 wt% to 20 wt%. Since the wettability of the pressure-sensitive adhesive layer can be improved by adjusting the content of the polyfunctional isocyanate compound (B) within the above range, the surface protective film of the present invention can be bonded without bubbling the bubbles.

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

As a method of curing a composition containing a polyol (A) and a polyfunctional isocyanate compound (B) to form a urethane-based resin, a method such as a urethane-forming reaction method using bulk polymerization or solution polymerization, Any suitable method may be employed.

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

Examples of the organometallic compounds include iron compounds, tin compounds, titanium compounds, zirconium compounds, lead compounds, cobalt compounds, zinc compounds and the like. Of these, iron-based compounds and tin-based compounds are preferable from the viewpoints of the reaction rate and the time of use of the pressure-sensitive adhesive layer.

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

Examples of the tin compound include dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin maleate, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin sulfide, Tributyltin dichloride, tributyltin dichloride, tributyltin dichloride, tributyltin dichloride, tributyltin dichloride, tributyltin dichloride, tributyltin dichloride, tributyltin dichloride, tributyltin dichloride, tributyltin dichloride, - ethylhexanoate tin, and the like.

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

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

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

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

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 of only one type, or two or more types. In addition, 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 0.01% by weight to 0.50% by weight, relative to the polyol (A) And preferably 0.01% by weight 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 bonded without bubbling the bubbles.

The composition containing the polyol (A) and the polyfunctional isocyanate compound (B) may contain any suitable other components as long as the effect of the present invention is not impaired. Examples of such other components include a resin component other than a polyurethane resin, a tackifier, an inorganic filler, an organic filler, a metal powder, a pigment, a foil, a softener, an antioxidant, a conductive agent, an ultraviolet absorber, Surface lubricants, leveling agents, corrosion inhibitors, heat stabilizers, polymerization inhibitors, lubricants, solvents, catalysts and the like.

(A urethane-based resin formed from a composition containing a urethane prepolymer (C) and a polyfunctional isocyanate compound (B)

The urethane-based resin formed from the composition containing the urethane prepolymer (C) and the polyfunctional isocyanate compound (B) may be any suitable urethane-based resin as long as it is a urethane-based resin obtained by using so-called "urethane prepolymer" as a raw material.

The urethane resin formed from the composition containing the urethane prepolymer (C) and the polyfunctional isocyanate compound (B) is formed by, for example, a composition containing a polyurethane polyol as the urethane prepolymer (C) and a polyfunctional isocyanate compound (B) Based resin. The urethane prepolymer (C) may be one kind or two or more kinds. The polyfunctional isocyanate compound (B) may be either 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), either individually or as a mixture of (a1) and (a2) With the organic polyisocyanate compound (a3).

As the polyester polyol (a1), any suitable polyester polyol can be used. As such polyester polyol (a1), for example, polyester polyol obtained by reacting an acid component with a glycol component can be given. Examples of the acid component include terephthalic acid, adipic acid, azelaic acid, sebacic acid, phthalic anhydride, isophthalic acid and trimellitic acid. Examples of the glycol component include ethylene glycol, propylene glycol, diethylene glycol, butylene glycol, 1,6-hexane glycol, 3-methyl-1,5-pentanediol, 3,3'-dimethylolheptane, Ethylene glycol, polyoxypropylene glycol, 1,4-butanediol, neopentyl glycol, butyl ethyl pentane diol, and polyol components such as glycerin, trimethylol propane and pentaerythritol. Examples of the polyester polyol (a1) include polyester polyols obtained by ring-opening polymerization of lactones such as polycaprolactone, poly (beta -methyl- -valerolactone) and polyvalerolactone.

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

As the polyether polyol (a2), any suitable polyether polyol can be used. Examples of the polyether polyol (a2) include low molecular weight polyols such as water, propylene glycol, ethylene glycol, glycerin, trimethylol propane, etc., as initiators, and ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran And a polyether polyol obtained by polymerizing an oxirane compound such as furan. Specific examples of the polyether polyol (a2) include a polyether polyol having two or more functional groups such as polypropylene glycol, polyethylene glycol, and polytetramethylene glycol.

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

The polyether polyol (a2) can be obtained by partially replacing the polyether polyol (a2) with a glycol such as ethylene glycol, 1,4-butanediol, neopentyl glycol, butyl ethyl pentanediol, glycerin, trimethylol propane, pentaerythritol, Aminomethylethanolamine, N-aminoethylethanolamine, isophoronediamine, xylylenediamine, and the like.

As the polyether polyol (a2), only a bifunctional polyether polyol may be used, or a polyether polyol having a number average molecular weight of 100 to 100,000 and at least three hydroxyl groups in one molecule may be partially or wholly used. When a polyether polyol (a2) having a number average molecular weight of 100 to 100,000 and a part or all of a polyether polyol having at least three hydroxyl groups in one molecule is used, the balance between adhesive strength and re-releasability can be improved. In such a polyether polyol, if the number average molecular weight is less than 100, the reactivity becomes high and gelation tends to occur. Further, in such a polyether polyol, when the number average molecular weight exceeds 100000, the reactivity is lowered, and further, the cohesive force of the polyurethane polyol itself may be reduced. The number average molecular weight of such a polyether polyol is more preferably 100 to 10,000.

As the organic polyisocyanate compound (a3), any suitable organic polyisocyanate compound can be used. Examples of the organic polyisocyanate compound (a3) include aromatic polyisocyanates, aliphatic polyisocyanates, aromatic aliphatic polyisocyanates, alicyclic polyisocyanates, and the like.

Examples of the aromatic polyisocyanate include 1,3-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,4-phenylenediisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4- 2,6-tolylene diisocyanate, 4,4'-toluidine diisocyanate, 2,4,6-triisocyanatotoluene, 1,3,5-triisocyanatobenzene, dianisidine diisocyanate, 4 , 4'-diphenyl ether diisocyanate, 4,4 ', 4 "-triphenyl methane 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, Isocyanate, dodecamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, and the like.

Examples of the aromatic aliphatic polyisocyanate include ω, ω'-diisocyanato-1,3-dimethylbenzene, ω'-diisocyanato-1,4-dimethylbenzene, ω, 1,4-diethyl benzene, 1,4-tetramethyl xylylene 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, methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4'-methylene bis (cyclohexyl isocyanate), 1,4- Methyl) cyclohexane, 1,4-bis (isocyanatomethyl) cyclohexane, and the like.

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

Any suitable catalyst may be used as the catalyst that can be used to obtain the polyurethane polyol. Examples of such catalysts include tertiary amine compounds and organometallic compounds.

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 compounds include tin compounds and non-saponified compounds.

As the tin compound, for example, dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin dimaleate, dibutyltin dilaurate (DBTDL), dibutyltin diacetate, dibutyl Tributyl tin oxide, tributyl tin acetate, triethyl tin ethoxide, tributyl tin ethoxide, dioctyl tin oxide, tributyl tin chloride, tributyl tin trichloroacetate , 2-ethylhexanoate tin, and the like.

Examples of non-saponified compounds include titanium-based compounds such as dibutyltitanium dichloride, tetrabutyl titanate, and butoxy titanium trichloride; Lead compounds such as lead oleate, lead 2-ethylhexanoate, lead benzoate and lead naphthene; Iron-based compounds such as 2-ethylhexanoate and iron acetylacetonate; Cobalt compounds such as cobalt benzoate and cobalt 2-ethylhexanoate; Zinc-based compounds such as zinc naphthenate, and zinc 2-ethylhexanoate; Zirconium compounds such as zirconium naphthenate; And the like.

In the case where a catalyst is used to obtain a polyurethane polyol and two types of polyols such as a polyester polyol and a polyether polyol are present, due to the difference in reactivity thereof, in a system of a single catalyst, It is easy to cause the problem that it is caused. Thus, by using two kinds of catalysts for obtaining polyurethane polyol, it becomes easy to control the reaction rate, catalyst selectivity, etc., and these problems can be solved. Examples of combinations of these two types of catalysts include tertiary amines / organometallic compounds, tin compounds / non-petroleum compounds and tin compounds / tin compounds, preferably tin compounds / tin compounds, Butyl tin dilaurate and 2-ethylhexanoic acid tin. The compounding ratio thereof is preferably 2-ethylhexanoate / dibutyltin dilaurate in a weight ratio of preferably less than 1, more preferably 0.2 to 0.6. When the compounding ratio is 1 or more, gelation tends to occur due to the balance of the catalytic activity.

When a catalyst is used to obtain the polyurethane polyol, the amount of the catalyst to be used is preferably 0.01 to 1.0 wt.% (Based on the total amount of the polyester polyol (a1), the polyether polyol (a2) and the organic polyisocyanate compound %to be.

When a catalyst is used to obtain the polyurethane polyol, the reaction temperature is preferably less than 100 占 폚, more preferably 85 占 폚 to 95 占 폚. When the temperature is higher than 100 ° C, there is a possibility that the reaction rate and control of the crosslinking structure become difficult, and it is difficult to obtain a polyurethane polyol having a predetermined molecular weight.

When a polyurethane polyol is obtained, a catalyst may not be used. In that case, the reaction temperature is preferably 100 占 폚 or higher, and more preferably 110 占 폚 or higher. When the polyurethane polyol is obtained in the absence of a catalyst, the reaction is preferably carried out for 3 hours or more.

Examples of the method for obtaining the polyurethane polyol include: 1) a method in which all of the polyester polyol, the polyether polyol, the catalyst and the organic polyisocyanate are put into a flask; 2) a polyester polyol, a polyether polyol and a catalyst are put in a flask And a method of dropping and adding an organic polyisocyanate. As a method for obtaining a polyurethane polyol, the method 2) is preferred in terms of controlling the reaction.

When a polyurethane polyol is obtained, any appropriate solvent may 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), the above-mentioned compounds can be used.

The composition containing the urethane prepolymer (C) and the polyfunctional isocyanate compound (B) may contain any suitable other components as long as the effect of the present invention is not impaired. Examples of such other components include a resin component other than a polyurethane resin, a tackifier, an inorganic filler, an organic filler, a metal powder, a pigment, a foil, a softener, an antioxidant, a conductive agent, an ultraviolet absorber, Surface lubricants, leveling agents, corrosion inhibitors, heat stabilizers, polymerization inhibitors, lubricants, solvents, catalysts and the like.

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

The number average molecular weight Mn of the urethane prepolymer (C) is preferably 3000 to 1000000.

The equivalent ratio of the NCO group and the OH group in the urethane prepolymer (C) and the polyfunctional isocyanate compound (B) is preferably 5.0 or less, more preferably 0.01 to 3.0, and still more preferably 1.0 or less, 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 the 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 bonded without bubbling the bubbles.

The content of the polyfunctional isocyanate compound (B) is preferably 0.01% by weight to 30% by weight, more preferably 0.03% by weight to 20% by weight, relative to the urethane prepolymer (C) By weight, more preferably 0.05% by weight to 15% by weight, particularly preferably 0.075% by weight to 10% by weight, and most preferably 0.1% by weight to 8% by weight. Since the wettability of the pressure-sensitive adhesive layer can be improved by adjusting the content of the polyfunctional isocyanate compound (B) within the above range, the surface protective film of the present invention can be bonded without bubbling the bubbles.

[Acrylic resin]

As the acrylic resin, any suitable acrylic pressure-sensitive adhesive, such as a known acrylic pressure-sensitive adhesive described in, for example, Japanese Laid-Open Patent Application No. 2013-241606 or the like can be employed as long as the effect of the present invention is not impaired.

The acrylic resin may contain any suitable component as long as the effect of the present invention is not impaired. Examples of such components include a resin component other than an acrylic resin, a tackifier, an inorganic filler, an organic filler, a metal powder, a pigment, a foil, a softener, an antioxidant, a conductive agent, an ultraviolet absorber, an antioxidant, , A leveling agent, a corrosion inhibitor, a heat stabilizer, a polymerization inhibitor, a lubricant, a solvent, a catalyst and the like.

[Rubber-based resin]

As the rubber-based resin, any appropriate rubber-based pressure-sensitive adhesive, such as a known rubber-based pressure-sensitive adhesive described in, for example, Japanese Patent Laid-Open Publication No. 2015-074771, etc. may be employed as long as the effect of the present invention is not impaired. These may be one kind or two or more kinds.

The rubber-based resin may contain any suitable component as long as the effect of the present invention is not impaired. Examples of such components include, but are not limited to, a resin component other than the rubber-based resin, a tackifier, an inorganic filler, an organic filler, a metal powder, a pigment, a foil, a softener, an anti-aging agent, a conductive agent, an ultraviolet absorber, , A leveling agent, a corrosion inhibitor, a heat stabilizer, a polymerization inhibitor, a lubricant, a solvent, a catalyst and the like.

[Silicone resin]

As the silicone adhesive, arbitrary suitable silicone adhesive can be employed as long as the effect of the present invention is not impaired, such as a known silicone adhesive described in, for example, Japanese Patent Laid-Open Publication No. 2014-047280. These may be one kind or two or more kinds.

The silicone resin may contain any suitable component as long as the effect of the present invention is not impaired. Examples of such components include a resin component other than a silicone resin, a tackifier, an inorganic filler, an organic filler, a metal powder, a pigment, a foil, a softener, an antioxidant, a conductive agent, an ultraviolet absorber, an antioxidant, , A leveling agent, a corrosion inhibitor, a heat stabilizer, a polymerization inhibitor, a lubricant, a solvent, a catalyst and the like.

&Lt; Silicon Additive >

Any suitable silicone-based additive can be employed as long as the effect of the present invention is not impaired. As such a silicone additive, at least one selected from a siloxane bond-containing compound, a hydroxyl group-containing silicone compound and a crosslinkable functional group-containing silicone compound is preferable.

The silicon-based additive may be of only one type, or may be two or more types.

Examples of the siloxane bond-containing compound include a polyether-modified polyorganosiloxane having a polyether group introduced into the main chain or side chain of a polyorganosiloxane skeleton (such as polydimethylsiloxane), a polyester having a polyorganosiloxane skeleton Modified polyorganosiloxane having a polyorganosiloxane introduced therein, an organic compound-introduced polyorganosiloxane having an organic compound introduced into the main chain or side chain of the polyorganosiloxane skeleton, a silicone-modified (meth) Methacrylic resin, a silicone-modified organic compound in which a polyorganosiloxane is introduced into an organic compound, and a silicon-containing organic compound in which an organic compound and a silicone compound are copolymerized. Examples of commercially available products of such siloxane bond-containing polymers include BYK-300 ("BYK-300", trade name, manufactured by Kyoeisha Kagaku Kogyo Co., 314 "," BYK-320 "," BYK-322 "," BYK-310 "," BYK- BYK-323, BYK-325, BYK-330, BYK-331, BYK-333, BYK-337, BYK- BYK-375 "," BYK-378 "," BYK-348 "," BYK- BYK-UV3500, BYK-UV3510, BYK-UV3570, BYK-3550, BYK-SILCLEAN3700 and BYK-SILCLEAN3720), a leveling agent of AC series manufactured by Algin Chemie ("POLY FLOW KL-400X", "POLYFLOW KL-400HF", "POLY FLOW KL-400HF", "POLY FLOW KL-400HF" Flow KL-401 &quot;, &quot; Reflow KL-402 "," Polyflow KL-403 "and" Polyflow KL-404 ") and leveling agents of KP series manufactured by Shinetsu Kagaku Kogyo Co., Ltd. (" KP-323 " Manufactured by Dow Corning Incorporated) such as X22 series and KF series manufactured by Shin-Etsu Chemical Co., Ltd., KP-341, KP-104, KP-110 and KP- ("LP-7001", "LP-7002", "8032ADDITIVE", "57ADDITIVE", "L-7604", "FZ-2110", "FZ-2105", "67ADDITIVE", "8618ADDITIVE" 3ADDITIVE &quot;, &quot; 56ADDITIVE &quot;, etc.).

Examples of the hydroxyl group-containing silicone compound include a polyether-modified polyorganosiloxane having a polyether group introduced into the main chain or side chain of a polyorganosiloxane skeleton (such as polydimethylsiloxane), a polyester having a polyorganosiloxane skeleton Modified polyorganosiloxane having a polyorganosiloxane introduced therein, an organic compound-introduced polyorganosiloxane having an organic compound introduced into the main chain or side chain of the polyorganosiloxane skeleton, a silicone-modified (meth) Methacrylic resin, a silicone-modified organic compound in which a polyorganosiloxane is introduced into an organic compound, and a silicon-containing organic compound in which an organic compound and a silicone compound are copolymerized. In these, the hydroxyl group may have a polyorganosiloxane skeleton, or may have a polyether group, a polyester group, a (meth) acryloyl group, or an organic compound. Examples of such a hydroxyl group-containing silicone include commercially available products such as X-22-4015, X-22-4039, KF6000, KF6001, KF6002, KF6003, BYK-370 (manufactured by Shin-Etsu Chemical Co., Ltd.), "X-22-170DX", "X-22-176DX" BYK-SILCLEAN 3700 &quot;, and &quot; BYK-SILCLEAN 3720 &quot;.

Examples of the crosslinkable functional group-containing silicone compound include a polyether-modified polyorganosiloxane having a polyether group introduced into the main chain or side chain of a polyorganosiloxane skeleton (e.g., polydimethylsiloxane), a polyether-modified polyorganosiloxane having a polyorganosiloxane skeleton A polyester-modified polyorganosiloxane having a polyester group introduced therein, an organic compound-introduced polyorganosiloxane having an organic compound introduced into a main chain or side chain of a polyorganosiloxane skeleton, a silicone having a polyorganosiloxane introduced into a (meth) A modified (meth) acrylic resin, a silicone-modified organic compound in which a polyorganosiloxane is introduced into an organic compound, and a silicon-containing organic compound in which an organic compound and a silicone compound are copolymerized. In these, the crosslinkable functional group may have a polyorganosiloxane skeleton or 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", "BY16-750", "BY16-750", "BY16 KF-868 "," KF-864 "," KF-859 "," KF-393 ", and" KF-865 "manufactured by Shin-Etsu Chemical Co., KF-860 "," KF-880 "," KF-8004 "," KF-8002 "," KF-8005 " X-22-2000 "," X-22-4741 "," KF-1002 "," KF-2001 "," X- X-22-164A "," X-22-164B "," X-22-164AS "and" X-22-2445 ".

<Fluorine Additive>

Any suitable fluorine-based additive can be employed as long as the effect of the present invention is not impaired. Such a fluorine-based additive is preferably at least one selected from a fluorine-containing compound, a hydroxyl group-containing fluorine-containing compound, and a crosslinkable functional group-containing fluorine-containing compound.

The fluorine-based additive may be of 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 fluoroalkanes such as fluoromethane, fluoroethane, fluoropropane, fluoroisopropane, fluorobutane, fluoroisobutane, fluoro t-butane, fluoropentane, fluorohexane Fluoro C1-C10 alkane, and the like. Examples of such fluorine-containing compounds include commercially available products such as leveling agents ("S-242", "S-243", "S-420", "S-611 ("BYK-340") of the BYK series manufactured by Big Chem Japan Co., Ltd., a leveling agent of the AC series manufactured by Algin Chemie ("S-651" (MegaPark F-114, MegaPack F-410, MegaPack F-444, MegaPack F-444, etc.) MegaPark F-552 "," Mega Park F-553 "," Mega Park F-476 "," Mega Park F-556 "," Mega Park F-556 "and" Mega Park F- MegaPark RS-75 "," Mega Park F-556 "," Mega Park F-554 "," Mega Park F-555 "," Mega Park R-94 "," Mega Park RS-72-K " ("FC-TF-1367", "Megapack EXP TF-1437", "Megapack F-558", and "Megapack EXP TF-1537") and the FC series of leveling agents manufactured by Sumitomo 3M Co., 4430 &quot; (E.g., &quot; FC-4432 &quot;, etc.), leveling agents ("Fectgent 100", "Fogent 100C", "Fogent 110", "Fogent 150", "Fogent 150CH" Quot; Fotogent AK &quot;, &quot; FotGent 501 &quot;, &quot; FotGent 250 &quot;, &quot; FotGent 251 &quot;, &quot; FotGent 222F &quot;, &quot; FotGent 208G & (PF-136A, PF-156A, PF-151N, PF-636 and PF-6320) of the PF series manufactured by Kitamura Kagaku Sangyo Co., PF-652, PF-6520, PF-651, PF-652, and PF-3320), and the like.

As the hydroxyl group-containing fluorine compound, for example, conventionally known resins can be used, and examples thereof include pamphlets of International Publication Nos. 94/06870, 8-12921, 10-72569, A fluororesin containing a hydroxyl group described in Japanese Patent Application Laid-Open No. 4-275379, International Patent Publication No. 97/11130, and International Publication No. 96/26254. Other examples of the hydroxyl group-containing fluororesin include, for example, JP-A-8-231919, JP-A-10-265731, JP-A-10-204374, JP-A-8-12922 And the like, and the like. In addition, a copolymer of a compound having a fluorinated alkyl group in a hydroxyl group-containing compound, a fluorine-containing organic compound in which a fluorine-containing compound is copolymerized with a hydroxyl group-containing compound, and a fluorine- containing compound containing a hydroxyl group-containing organic compound. Examples of such hydroxyl group-containing fluorine-containing compounds include commercially available products such as those sold under the trade names of "Lumipulon" (manufactured by Asahi Glass Co., Ltd.), "Cefalcoat" (manufactured by Central Garris Co., Ltd.) (Manufactured by Daikin Industries, Ltd.), trade name "Megapack F-571", "Fluoronate" (manufactured by DIC Corporation), and the like.

Examples of the crosslinkable functional group-containing fluorine compound include a carboxylic acid compound having a fluorinated alkyl group such as perfluorooctanoic acid, a copolymer of a compound having an alkyl group fluorinated to a crosslinkable functional group-containing compound, a compound having a crosslinkable functional group- A fluorine-containing organic compound in which a fluorine-containing compound is copolymerized, and a fluorine-containing compound containing a crosslinkable functional group-containing compound. Examples of commercially available crosslinkable functional group-containing fluorinated compounds include commercially available products such as "Megafac F-570", "Megafac RS-55", "Megafac RS-56", "Megafac RS- MegaPac RS-75 "," MegaPac RS-75 "," MegaPac RS-75 "," MegaPac RS-75 " And the like.

<Other Ingredients>

The pressure-sensitive adhesive composition may contain any other appropriate components as long as the effect of the present invention is not impaired. Examples of such other components include other resin components, tackifiers, inorganic fillers, organic fillers, metal powders, pigments, foams, softeners, antioxidants, conductive agents, ultraviolet absorbers, antioxidants, light stabilizers, surface lubricants, A corrosion inhibitor, a heat stabilizer, a polymerization inhibitor, a lubricant, a solvent, a catalyst and the like.

The pressure-sensitive adhesive composition may contain a fatty acid ester. The fatty acid ester may be 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, still more preferably from 200 to 480, particularly preferably from 200 to 400, 350. 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 suitable fatty acid ester can be employed as long as the effect of the present invention is not impaired. Examples of such fatty acid esters include polyoxyethylene bisphenol A lauric acid ester, butyl stearate, 2-ethylhexyl palmitate, 2-ethylhexyl stearate, behenic acid monoglyceride, 2-ethylhexanoate, Methyl stearate, myristyl isostearate, isopropyl palmitate, cholesteryl isostearate, lauryl methacrylate, methyl coconut fatty acid methyl, methyl laurate, methyl oleate, methyl stearate, myristyl myristate, Dodecyl pentaerythritol monooleate, pentaerythritol monostearate, pentaerythritol tetrapalmitate, stearyl stearate, isostearyl stearate, 2-ethylhexanoic acid triglyceride, butyl laurate, octyl oleate And the like.

When the pressure-sensitive adhesive composition comprises a fatty acid ester, the content 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, More preferably 2 parts by weight to 40 parts by weight, particularly preferably 2.5 parts by weight to 35 parts by weight, and most preferably 3 parts by weight to 30 parts by weight.

The pressure-sensitive adhesive composition may contain an ionic liquid containing a fluoro organic anion. The pressure-sensitive adhesive composition includes an ionic liquid containing a fluoro organic anion, so that a pressure-sensitive adhesive composition having an excellent antistatic property can be provided. These ionic liquids may be of only one type, or two or more types.

In the present invention, an ionic liquid means a molten salt (ionic compound) which exhibits a liquid phase at 25 占 폚.

As the ionic liquid, any suitable ionic liquid can be employed as far as it does not impair the effects of the present invention, provided that it is an ionic liquid containing a fluoro organic anion. Such an ionic liquid is preferably an ionic liquid composed of a fluoro organic anion and an onium cation. By employing an ionic liquid composed of a fluoro organic anion and an onium cation as an ionic liquid, it is possible to provide a pressure-sensitive adhesive composition having an excellent antistatic property.

Any suitable onium cation can be employed as the onium cation that can constitute the ionic liquid, provided that the effect of the present invention is not impaired. The 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 cation, it is possible to provide a pressure-sensitive adhesive composition which is excellent in antistatic property.

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

In the general formula (1), R _a represents a hydrocarbon group of 4 to 20 carbon atoms, may contain a hetero atom, R _b and R _c may be the same or different and represent a hydrogen or a hydrocarbon group of 1 to 16 carbon atoms, And may contain a hetero atom. However, when the nitrogen atom contains a double bond, there is no R _c .

In the general formula (2), R _d represents a hydrocarbon group of 2 to 20 carbon atoms, may contain a hetero atom, and R _e , R _f and R _g may be the same or different and represent hydrogen or a hydrocarbon having 1 to 16 carbon atoms And may contain a hetero atom.

In the general formula (3), R _h represents a hydrocarbon group having 2 to 20 carbon atoms, which may contain a hetero atom, R _i , R _j and R _k are the same or different and represent hydrogen or a hydrocarbon having 1 to 16 carbon atoms And may contain a hetero atom.

In the general formula (4), Z represents a nitrogen atom, a sulfur atom or a phosphorus atom, R ₁ , R _m , R _n and R _o are the same or different and each represents a hydrocarbon group of 1 to 20 carbon atoms, . Provided that when Z is a sulfur atom, R _o is absent.

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, and a cation having a pyrrole skeleton.

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- Butyl-3-methylpyridinium cation, 1-hexyl-3-methylpyridinium cation, 1-butyl-4-methylpyridinium cation, 1-octyl- Pyridinium cations such as dimethylpyridinium cation and 1,1-dimethylpyrrolidinium cation; Methyl-1-propylpyrrolidinium cation, 1-methyl-1-butylpyrrolidinium cation, 1-methyl-1-pentylpyrrolidinium cation, 1- Methyl-1-heptylpyrrolidinium cation, a 1-ethyl-1-butylpyrrolidinium cation, a 1-ethyl-1-butylpyrrolidinium cation, Ethyl-1-hexylpyrrolidinium cation, 1-ethyl-1-heptylpyrrolidinium cation, 1,1-dipropylpyrrolidinium cation, 1-propyl-1-butyl Pyrrolidinium cations such as pyrrolidinium cation and 1,1-dibutylpyrrolidinium cation; 1-propylpiperidinium cation, 1-methylpiperidinium cation, 1-methyl-1-ethylpiperidinium cation, 1-methyl-1-propylpiperidinium cation, Methyl-1-heptylpiperidinium cation, 1-methyl-1-pentylpiperidinium cation, 1-methyl-1-pentylpiperidinium cation, Ethyl-1-butylpiperidinium cation, 1-ethyl-1-pentylpiperidinium cation, 1-ethyl-1-pentylpiperidinium cation, 1- Piperidinium cations such as propyl-1-butylpiperidinium cation, 1,1-dimethylpiperidinium cation, 1,1-dipropylpiperidinium cation and 1,1-dibutylpiperidinium cation; 2-methyl-1-pyrroline cations; 1-ethyl-2-phenylindole cations; 1,2-dimethylindole cations; 1-ethylcarbazole cations; And the like.

Of these, preferred are 1-ethylpyridinium cation, 1-butylpyridinium cation, 1-hexylpyridinium cation, 1-ethyl-3-methylpyridine Butyl-4-methylpyridinium cation such as 1-butyl-3-methylpyridinium cation, 1-hexyl-3-methylpyridinium cation, Cation; Methyl-1-propylpyrrolidinium cation, 1-methyl-1-butylpyrrolidinium cation, 1-methyl-1-pentylpyrrolidinium cation, 1- Methyl-1-heptylpyrrolidinium cation, a 1-ethyl-1-butylpyrrolidinium cation, a 1-ethyl-1-butylpyrrolidinium cation, Pyrrolidinium cations such as 1-pentylpyrrolidinium cation, 1-ethyl-1-hexylpyrrolidinium cation and 1-ethyl-1-heptylpyrrolidinium cation; Methyl-1-propylpiperidinium cation, 1-methyl-1-butylpiperidinium cation, 1-methyl-1-pentylpiperidinium cation, 1- Ethyl-1-propylpiperidinium cation, 1-ethyl-1-butylpiperidinium cation, 1-ethyl-1-pentylpiperidinium cation, Piperidinium cations such as 1-pentylpiperidinium cation, 1-ethyl-1-hexylpiperidinium cation, 1-ethyl-1-heptylpiperidinium cation and 1-propyl-1-butylpiperidinium cation; And more preferably 1-hexylpyridinium cation, 1-ethyl-3-methylpyridinium cation, 1-butyl-3-methylpyridinium cation, 1-octyl- , 1-methyl-1-propylpyrrolidinium cation, and 1-methyl-1-propylpiperidinium cation.

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

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-decyl-3-methylimidazolium cation, 1-decyl-3-methylimidazolium cation, 1- Methylimidazolium cation, 1-tetradecyl-3-methylimidazolium cation, 1,2-dimethyl-3-propylimidazolium cation, 1-ethyl-2,3-dimethylimidazolium cation Imidazolium cations such as 1-butyl-2,3-dimethylimidazolium cation and 1-hexyl-2,3-dimethylimidazolium cation; 1,3-dimethyl-1,4,5,6-tetrahydropyrimidinium cation, 1,2,3-trimethyl-1,4,5,6-tetrahydropyrimidinium cation, 1,2,3- Tetrahydropyrimidinium cations such as 4-tetramethyl-1,4,5,6-tetrahydropyrimidinium cation and 1,2,3,5-tetramethyl-1,4,5,6-tetrahydropyrimidinium cation, Midium cation; 1,3-dimethyl-1,4-dihydropyrimidinium cation, 1,3-dimethyl-1,6-dihydropyrimidinium cation, 1,2,3-trimethyl-1,4-dihydropyrimidine 1,2,3-trimethyl-1,6-dihydropyrimidinium cation, 1,2,3,4-tetramethyl-1,4-dihydropyrimidinium cation, 1,2,3- Dihydropyrimidinium cations such as 4-tetramethyl-1,6-dihydropyrimidinium cation and the like; And the like.

Among these, from the viewpoint that the effect of the present invention can be further enhanced, it is preferable to use a cation such as a 1,3-dimethylimidazolium cation, a 1,3-diethylimidazolium cation, 3-methylimidazolium cation, 1-hexyl-3-methylimidazolium cation, 1-octyl-3-methylimidazolium cation, 1-decyl- Methylimidazolium cation, 1-dodecyl-3-methylimidazolium cation, and 1-tetradecyl-3-methylimidazolium cation, and more preferably an imidazolium cation such as 1-ethyl- 1-hexyl-3-methylimidazolium cation.

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- Pyrazolium cations such as 5-trimethylpyrazolium cation, 1-propyl-2,3,5-trimethylpyrazolium cation and 1-butyl-2,3,5-trimethylpyrazolium cation; 1-ethyl-2,3,5-trimethylpyrazolinium cation, 1-propyl-2,3,5-trimethylpyrazolinium cation, 1-butyl-2,3,5-trimethylpyrazolinium cation, Zolinium cations; And the like.

Examples of the cation represented by the general formula (4) include tetraalkylammonium cations, trialkylsulfonium cations and tetraalkylphosphonium cations, and those in which a part of the alkyl group is substituted with an alkenyl group, an alkoxyl group, .

Specific examples of the cations represented by the general formula (4) include, for example, tetramethylammonium cations, tetraethylammonium cations, tetrabutylammonium cations, tetrapentylammonium cations, tetrahexylammonium cations, tetraheptylammonium cations, (2-methoxyethyl) ammonium cation, a glycidyltrimethylammonium cation, a trimethylsulfammonium cation, a trimethylammonium cation, an N, N-diethyl- And examples of the cation selected from the group consisting of a sulfonium cation, a sulfonium cation, a sulfonium cation, a sulfonium cation, a sulfonium cation, a sulfonium cation, a sulfonium cation, a sulfonium cation, Tetrabutylphosphonium cation, tetrahexylphosphonium cation, tetraoctylphosphonium cation, tetrabutylphosphonium cation, tetrabutylphosphonium cation, Diethylmethylphosphonium cation, tributylethylphosphonium cation, trimethyldecylphosphonium cation, diallyldimethylammonium cation, and the like.

Among them, from the viewpoint of further enhancing the effect of the present invention, it is preferable to use a cation such as triethylmethylammonium cation, tributylethylammonium cation, trimethyldecylammonium cation, diethylmethylsulfonium cation, dibutylethylsulfonium cation Tetramethylammonium cation, tetramethylammonium cation, tetramethylammonium cation, tetramethylammonium cation, tetramethylammonium cation, tetramethylammonium cation, tetramethylammonium cation, tetramethylammonium cation, tetramethylammonium cation, tetramethylammonium cation, tetramethylammonium cation, N-dimethyl-N-ethyl-N-propylammonium cation, N, N-dimethyl-N-ethyl-N-propylammonium cation, glycidyltrimethylammonium cation, diallyldimethylammonium cation, N-dimethyl-N-ethyl-N-butylammonium cation, N, N-dimethyl-N-ethyl-N-pentylammonium cation, N, N-dimethyl-N-ethyl-N-heptylammonium amount N, N-diethyl-N-propyl-N-butylammonium cation, N, N-dimethyl- N-dimethyl-N-propyl-N-pentylammonium cation, N, N-dimethyl- Dimethyl-N-butyl-N-hexylammonium cation, N, N-diethyl-N-butyl-N-heptylammonium cation, N, N, N-diethyl-N-methyl-N-pentylammonium cation, N, N-diethyl-N-methyl-N-propylammonium cation, , N, N-diethyl-N-methyl-N-heptylammonium cation, N, N-diethyl-N-propyl-N-pentylammonium cation, triethylpropylammonium cation, triethylpentylammonium cation, Ammonium cation, N, N-dipropyl-N-methyl-N-ethylammonium cation, N, N-dipropyl- N-dipropyl-N-methyl-N-pentylammonium cation, N, N-dipropyl-N, N-dihexylammonium cation, N, Ammonium cation, N, N-dibutyl-N-methyl-N-hexylammonium cation, trioctylmethylammonium cation and N-methyl-N-ethyl-N-propyl-N-pentylammonium cation. And preferably a trimethylpropylammonium cation.

As the fluoroorganic anion capable of constituting the ionic liquid, any appropriate fluoro organic anion can be employed as long as the effect of the present invention is not impaired. Such a fluoro organic anion may be completely fluorinated (perfluorinated) or partially fluorinated.

Examples of such fluoro organic anions include fluorinated arylsulfonate, perfluoroalkanesulfonate, bis (fluorosulfonyl) imide, bis (perfluoroalkanesulfonyl) imide, cyano perfluoro (Perfluoroalkanesulfonyl) methide, tris (perfluoroalkanesulfonyl) methide, trifluoroacetone (methanesulfonyl) methide, bis , Perfluoroalkalate, tris (perfluoroalkanesulfonyl) methide, (perfluoroalkanesulfonyl) trifluoroacetamide, and the like.

Among these fluoro organic anions, perfluoroalkylsulfonate, bis (fluorosulfonyl) imide and bis (perfluoroalkanesulfonyl) imide are more preferable. More specifically, for example, Heptafluoropropanesulfonate, nonafluorobutanesulfonate, bis (fluorosulfonyl) imide, and bis (trifluoromethanesulfonyl) imide. In the present invention,

As specific examples of the ionic liquid, a suitable selection can be made from a combination of the cation component and the anionic component. Specific examples of such ionic liquids include 1-hexylpyridinium bis (fluorosulfonyl) imide, 1-ethyl-3-methylpyridinium trifluoromethanesulfonate, 1-ethyl- Methylpyridinium heptafluoropropanesulfonate, 1-ethyl-3-methylpyridinium nonafluorobutanesulfonate, 1-butyl-3-methylpyridinium 1-butyl-3-methylpyridinium bis (trifluoromethanesulfonyl) imide, 1-butyl-3-methylpyridinium bis (pentafluoroethanesulfonyl) 1-methyl-1-ethylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1,1-dimethylpyrrolidinium bis (trifluoromethanesulfonyl) imide, (Trifluoromethanesulfonyl) imide, 1-methyl-1-propylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-propylpyrrolidinium bis 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) 1-propylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-ethyl-1-butylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-ethyl-1-pentylpyrrole Ethyl-1-hexylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-ethyl-1-heptylpyrrolidinium bis (trifluoromethanesulfonyl) imide, Propyl-1-butylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1,1-dipropylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1,1-dibutylpyrrolidinium bis ( (Trifluoromethanesulfonyl) imide, 1-propylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-pentylpiperidinium bis (trifluoromethanesulfonyl) imide, Dimethylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-ethylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-propylpiperidinium bis Methyl-1-propylpiperidinium bis (fluorosulfonyl) imide, 1-methyl-1-butylpiperidinium bis (trifluoromethanesulfonyl) imide, Methyl-1-pentylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-hexylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-methyl- 1-heptylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-ethyl-1-propylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-ethyl-1-butylpiperidinium Bis (trifluo Ethyl-1-pentylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-ethyl-1-hexylpiperidium bis (trifluoromethanesulfonyl) imide , 1-ethyl-1-heptylpiperidinium bis (trifluoromethanesulfonyl) imide, 1,1-dipropylpiperidinium bis (trifluoromethanesulfonyl) Butylpiperidinium bis (trifluoromethanesulfonyl) imide, 1,1-dibutylpiperidinium bis (trifluoromethanesulfonyl) imide, 1,1-dimethylpyrrolidinium bis (pentafluoro Methyl-1-ethylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-propylpyrrolidinium bis (pentafluoroethanesulfonyl) imide Methyl-1-butylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-pentylpyrrolidinium bis (pentafluoroethanesulfonyl) - hexylpyrrolidinium bis (pentaprene Methyl-1-heptylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-propylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, Ethyl-1-pentylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-butylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-hexylpyrrolidinium 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 Pentafluoroethane Methyl-1-ethylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-propylpiperidinium bis (pentafluoroethanesulfonyl) imide, Methyl-1-butylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-pentylpiperidinium bis (pentafluoroethanesulfonyl) imide, Methyl-1-heptylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-propylpiperidinium bis (pentafluoroethanesulfonyl) imide, 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) Dipropylpiperidinium bis (penta Propyl-1-butylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1,1-dibutylpiperidinium bis (pentafluoroethanesulfonyl) imide, Ethyl-3-methylimidazolium trifluoromethanesulfonate, 1-ethyl-3-methylimidazolium trifluoromethanesulfonate, 1-ethyl-3-methylimidazolium trifluoromethanesulfonate, Ethyl-3-methylimidazolium heptafluoropropanesulfonate, 1-ethyl-3-methylimidazolium nonafluorobutanesulfonate, 1-ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) Ethyl-3-methylimidazolium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-3-methylimidazoliumbis (fluorosulfonyl) imide, -3-methylimidazolium tris (trifluoromethanesulfonyl) methide, 1-butyl-3-methylimidazolium trifluoroacetate, 1-butyl-3-methylimidazolium heptaflu 3-methylimidazolium trifluoromethanesulfonate, 1-butyl-3-methylimidazolium perfluorobutanesulfonate, 1-butyl-3-methylimidazolium bis (tri 3-methylimidazolium bis (fluorosulfonyl) imide, 1-hexyl-3-methylimidazolium trifluoromethanesulfonate, 1-hexyl- Dimethyl-3-propylimidazolium bis (trifluoromethanesulfonyl) imide, 1-ethyl-2,3,5-trimethylpyrazoliumbis (trifluoromethanesulfonyl) , 3,5-trimethylpyrazoliumbis (trifluoromethanesulfonyl) imide, 1-butyl-2,3,5-trimethylpyrazoliumbis (trifluoromethanesulfonyl) imide, , 3,5-trimethylpyrazoliumbis (pentafluoroethanesulfonyl) imide, 1-propyl-2,3,5-trimethylpyrazoliumbis (pentafluoroethanesulfonyl) imide, , 3,5-trimethylpyrazoliumbis (penta Ethyl-2,3,5-trimethylpyrazolium (trifluoromethanesulfonyl) trifluoroacetamide, 1-propyl-2,3,5-trimethylpyrazolium ( (Trifluoromethanesulfonyl) trifluoroacetamide, 1-butyl-2,3,5-trimethylpyrazolium (trifluoromethanesulfonyl) trifluoroacetamide, trimethylpropylammonium bis (trifluoromethanesulfonyl) N-dimethyl-N-ethyl-N-butylammonium bis (trifluoromethanesulfonyl) imide, N-dimethyl-N-ethyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl- N-dimethyl-N-ethyl-N-heptylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl- (Trifluoromethanesulfo (Trifluoromethanesulfonyl) imide, N, N-dimethyl-N-propyl-N-butylammonium bis (trifluoromethanesulfonyl) imide, (Trifluoromethanesulfonyl) imide, N, N-dimethyl-N-propyl-N-hexylammonium bis (trifluoromethylsulfonyl) imide, N-dimethyl-N-butyl-N-hexylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl- N-dimethyl-N-butyl-N-heptylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-pentyl-N-hexylammonium bis (Trifluoromethanesulfonyl) imide, N, N-dimethyl-N, N-dihexylammonium bis (trifluoromethanesulfonyl) imide, trimethylheptylammonium bis (trifluoromethanesulfonyl) imide , N, N-diethyl-N-methyl-N-propylammonium bis (trifluoromethane N, N-diethyl-N-methyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, N, N-diethyl-N-propyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, triethylpropylammonium bis (trifluoromethanesulfonyl) imide, (Trifluoromethanesulfonyl) imide, triethylheptylammonium bis (trifluoromethanesulfonyl) imide, N, N-dipropyl-N-methyl- N, N-dipropyl-N-methyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, N, N-dipropyl- N, N-dipropyl-N, N-dibutylammonium bis (trifluoromethanesulfonyl) imide, N, N-dibutyl -N-methyl-N-pentylammonium bis (trifluoromethanesulfo Imide, N, N-dibutyl-N-methyl-N-hexylammonium bis (trifluoromethanesulfonyl) imide, trioctylmethylammonium bis (trifluoromethanesulfonyl) Propyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, 1-butylpyridinium (trifluoromethanesulfonyl) trifluoroacetamide, 1-butyl- (Trifluoromethanesulfonyl) trifluoroacetamide, 1-ethyl-3-methylimidazolium (trifluoromethanesulfonyl) trifluoroacetamide, tetrahexylammonium bis (trifluoromethane) (Pentafluoroethanesulfonyl) imide, diallyldimethylammonium trifluoromethanesulfonate, diallyldimethylammonium bis (trifluoromethanesulfonyl) imide, diallyldimethylammonium bis (pentafluoroethanesulfonyl) imide, N , N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium trifluoromethanesulfonate, N, (Trifluoromethanesulfonyl) imide, N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium bis (pentafluoroethane Glycidyltrimethylammonium bis (trifluoromethanesulfonyl) imide, glycidyltrimethylammonium bis (pentafluoroethanesulfonyl) imide, glycidyltrimethylammonium trifluoromethanesulfonate, glycidyltrimethylammonium bis (Pentafluoroethanesulfonyl) imide, lithium bis (trifluoromethanesulfonyl) imide, lithium bis (trifluoromethanesulfonyl) imide, diallyldimethylbis &Lt; RTI ID = 0.0 &gt; rosulfonyl) &lt; / RTI &gt; imide.

Of these ionic liquids, more preferred are 1-hexylpyridinium bis (fluorosulfonyl) imide, 1-ethyl-3-methylpyridinium trifluoromethanesulfonate, 1-ethyl- Ethyl-3-methylpyridinium heptafluoropropanesulfonate, 1-ethyl-3-methylpyridinium nonafluorobutanesulfonate, 1-butyl-3-methylpyridinium tri 1-butyl-3-methylpyridinium bis (trifluoromethanesulfonyl) imide, 1-octyl-4-methylpyridinium bis (fluorosulfonyl) imide, Propylpyrrolidinium bis (fluorosulfonyl) imide, 1-methyl-1-propylpiperidinium bis (trifluoromethanesulfonyl) imide, Methyl-1-propylpiperidinium bis (fluorosulfonyl) imide, 1-ethyl-3-methylimidazolium trifluoride Ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide, 1-ethyl-3-methyl (methylsulfonyl) imide, Imidazolium bis (fluorosulfonyl) imide, 1-hexyl-3-methylimidazolium bis (fluorosulfonyl) imide, trimethylpropylammonium bis (trifluoromethanesulfonyl) imide, lithium bis (Trifluoromethanesulfonyl) imide, and lithium bis (fluorosulfonyl) imide.

As the ionic liquid, a commercially available liquid may be used, but it may be synthesized as follows. The method for synthesizing an ionic liquid is not particularly limited as long as an intended ionic liquid can be obtained. Generally, the ionic liquid is synthesized by a method described in &quot; Ionic Liquid - Frontier and Future of Development &quot; A halide method, a hydroxide method, an acid ester method, an emulsion formation method, and a neutralization method are used.

Examples of the method for synthesizing the nitrogen containing onium salt are described below with respect to the halide method, the hydroxide method, the acid ester method, the method of forming an acid, and the neutralization method. However, other methods such as a sulfur containing onium salt, a phosphorus containing onium salt, The ionic liquid outside can also be obtained by the same method.

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

Ionic liquid anion structure (A ^-) of the objective and the resulting halide acid (HA) or a salt thereof with a (MA, M is a cation to form a negative ion and a salt for the purpose, such as ammonium, lithium, sodium, potassium) and And the desired ionic liquid (R ₄ NA) is obtained.

The hydroxide method is a method which is carried out by the reaction shown in the reaction formulas (4) to (8). First, a halide (R ₄ NX), the ion exchange membrane method electrolysis (reaction scheme 4), the hydroxide by reaction (Scheme 6) of OH-form ion-exchange resin method (reaction scheme 5), or of silver oxide (Ag ₂ O) (R ₄ NOH) (chlorine, bromine and iodine are used as halogens).

The target ionic liquid (R ₄ NA) is obtained by using the reaction of the reaction formulas (7) to (8) with the obtained hydroxide in the same manner as the halogenation method.

The acid ester method is a method carried out by the reaction shown in the reaction formulas (9) to (11). First, an acid ester is obtained by reacting a tertiary amine (R ₃ N) with an acid ester (reaction formula (9)). As acid ester, esters of inorganic acids such as sulfuric acid, sulfuric acid, phosphoric acid, phosphorous acid, and carbonic acid, methanesulfonic acid, , And esters of organic acids such as formic acid are used.

The target ionic liquid (R ₄ NA) is obtained by using the reaction of the reaction formulas (10) to (11) in the same manner as in the halogenation method for the acid ester obtained. Further, by using methyl trifluoromethane sulfonate, methyl trifluoroacetate or the like as the acid ester, a direct ionic liquid can be obtained.

The neutralization method is a method which is carried out by the reaction shown in the reaction formula (12). Tertiary amine and _{CF 3 COOH, CF 3 SO 3} H, (CF 3 SO 2) 2 NH, (CF 3 SO 2) 3 CH, (C 2 F 5 SO 2) 2 is obtainable by reacting an organic acid, such as NH have.

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

The amount of the ionic liquid to be blended varies depending on the compatibility of the polymer to be used and the ionic liquid and therefore can not be uniformly defined. In general, it is preferably 0.001 to 50 parts by weight per 100 parts by weight of the base polymer More preferably 0.01 part by weight to 30 parts by weight, particularly preferably 0.01 part by weight to 20 parts by weight, most preferably 0.01 part by weight to 10 parts by weight Wealth. By adjusting the amount of the ionic liquid to be within the above range, it is possible to provide a pressure-sensitive adhesive composition having an excellent antistatic property. If the amount of the ionic liquid is less than 0.01 part by weight, sufficient antistatic properties may not be obtained. If the above 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 insofar as the effect of the present invention is not impaired. When the pressure-sensitive adhesive composition contains a modified silicone oil, the effect of antistatic properties can be exhibited. Particularly, when used in combination with an ionic liquid, the effect of the antistatic property can be expressed more effectively.

When the pressure-sensitive adhesive composition contains a modified silicone oil, the content thereof is preferably 0.001 to 50 parts by weight, more preferably 0.005 to 40 parts by weight, relative to 100 parts by weight of the base polymer 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 expressed more effectively.

As the modified silicone oil, any appropriate modified silicone oil may be employed as long as the effect of the present invention is not impaired. As such a modified silicone oil, for example, a modified silicone oil available from Shin-Etsu Chemical Co., Ltd. may be mentioned.

The modified silicone oil is preferably a polyether-modified silicone oil. By employing a polyether-modified silicone oil, the effect of the antistatic property can be expressed more effectively.

Examples of the polyether-modified silicone oil include a side chain-type polyether-modified silicone oil and a polyether-modified silicone oil of both ends. Of these, polyether-modified silicone oil of both ends is preferable in that the effect of the antistatic property can be sufficiently and more effectively expressed.

«« Use »»

The surface protective film of the present invention has a cemented carbide releasability and has a low staining property on the surface of an adherend. Therefore, it can be suitably used for protecting the surfaces of optical members and electronic members. The optical member of the present invention is one to which the surface protective film of the present invention is adhered. The electronic member of the present invention is one to which the surface protective film of the present invention is adhered.

<Examples>

Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited to these examples at all. Tests and evaluation methods in Examples and the like are as follows. Unless otherwise noted, the term "part" means "part by weight" unless otherwise specified, and "%" means "% by weight" unless otherwise specified.

(Peel strength after 23 占 폚 for 30 minutes and peel strength after 80 占 폚 for 7 days) at a peeling speed of 6000 mm /

The peel strength when the polyethylene terephthalate film with a thickness of 25 占 퐉 was bonded to the pressure-sensitive adhesive layer and the polyethylene terephthalate film was peeled off at 23 占 폚 at a peel angle of 180 degrees and a peel rate of 6000 mm / min was measured as follows.

(SUS304 plate, manufactured by Nitto Denko Co., Ltd. under the trade designation "No.531") was applied on the entire surface of the surface of the surface protective film (50 mm wide × 140 mm long) separated from the separator by the pressure- Using a hand roller.

Then, a polyethylene terephthalate film (trade name: "Lamiron S-10", thickness: 25 μm, width: 25 mm) was adhered to the surface of the pressure-sensitive adhesive layer (temperature: 23 ° C., humidity: 65% 1 round trip).

The evaluation sample thus obtained was measured in a tensile test. As the tensile tester, "Autograph AG-Xplus HS 6000 mm / min high-speed model (AG-50NX plus)" manufactured by Shimadzu Corporation was used. After the sample for evaluation was set in a tensile tester, the sample was allowed to stand for 30 minutes at an environmental temperature of 23 占 폚 or for 7 days under a temperature environment of 80 占 폚, and then a tensile test was started. The conditions of the tensile test were a peeling angle of 180 degrees and a peeling speed (tensile speed) of 6000 mm / min. The load at the time of peeling the PET film from the surface protective film was measured, and the average load at that time was regarded as the peeling force of the surface protective film.

(Peel strength after 23 占 폚 for 30 minutes and peel force after 80 占 폚 for 7 days) at a peeling speed of 300 mm /

A peeling force when the polyethylene terephthalate film with a thickness of 25 占 퐉 was bonded to the pressure-sensitive adhesive layer and the polyethylene terephthalate film was peeled off at 23 占 폚, a peeling angle of 180 占 and a peeling speed of 300 mm / min was measured as follows.

(SUS304 plate, manufactured by Nitto Denko Co., Ltd. under the trade designation "No.531") was applied on the entire surface of the surface of the surface protective film (50 mm wide × 140 mm long) separated from the separator by the pressure- Using a hand roller.

Then, a polyethylene terephthalate film (trade name: "Lamiron S-10", thickness: 25 μm, width: 25 mm) was adhered to the surface of the pressure-sensitive adhesive layer (temperature: 23 ° C., humidity: 65% 1 round trip).

The evaluation sample thus obtained was subjected to a tensile test. As the tensile tester, "Autograph AG-Xplus HS 6000 mm / min high-speed model (AG-50NX plus)" manufactured by Shimadzu Corporation was used. After the sample for evaluation was set in a tensile tester, the sample was allowed to stand for 30 minutes at an environmental temperature of 23 占 폚 or for 7 days under a temperature environment of 80 占 폚, and then a tensile test was started. The conditions of the tensile test were a peeling angle of 180 degrees and a peeling speed (tensile speed) of 300 mm / min. The load at the time of peeling the PET film from the surface protective film was measured, and the average load at that time was regarded as the peeling force of the surface protective film.

&Lt; Residual adhesion rate >

The surface protective film was bonded to the entire surface of a glass plate (Matsunami Glass Co., 1.35 mm x 10 cm x 10 cm) with a hand roller and stored for 24 hours in an atmosphere at a temperature of 23 DEG C and a humidity of 55% RH, The surface protective film was peeled off at a rate of 0.3 m / min and a No. 31B tape (base material thickness: 25 탆) of 19 mm width cut with a length of 150 mm was laminated at a temperature of 23 캜 and a humidity of 55% RH Under an atmosphere of 2.0 kg roller. After curing for 30 minutes in an atmosphere at a temperature of 23 ° C and a humidity of 55% RH, a tensile tester ("Autograph AG-Xplus HS 6000mm / min high speed model (AG-50NX plus)" manufactured by Shimadzu Seisakusho Co., Ltd.) , Peeled off at a peeling angle of 180 degrees and at a tensile rate of 300 mm / min, and the adhesive force was measured.

Separately, the adhesive strength of a No. 31B tape having a width of 19 mm was similarly measured on a glass plate not subjected to the above-mentioned treatment, and the remaining adhesion rate was calculated by the following formula.

Residual adhesion rate (%) = (No.31B adhesion force to glass plate after surface protective film peeling / No.31B adhesion force to glass plate) 占 100

This residual adhesion rate is an index of the extent to which the adhesive component of the surface protective film is transferred to the surface and contaminated with the adherend. It can be said that the higher the value of the residual adhesion rate is, the better the surface protective film does not contaminate the adherend, and the lower the value of the residual adhesion rate, the more contaminated the surface of the adherend with the adhesive component.

(Peeling force after 23 占 폚 for 30 minutes and peeling force after 80 占 폚 for 7 days) at a peeling speed of 6000 mm /

The surface protective film (25 mm wide × 140 mm long) with the separator removed was bonded to glass (soda lime glass, Matsunamigasu Kogyo Kogyo Co., Ltd.) with reciprocating 2 kg hand rollers.

The evaluation sample thus obtained was measured by a tensile tester. As the tensile tester, "Autograph AG-Xplus HS 6000 mm / min high-speed model (AG-50NX plus)" manufactured by Shimadzu Corporation was used. After the sample for evaluation was set in a tensile tester, the sample was allowed to stand for 30 minutes at an environmental temperature of 23 占 폚 or for 7 days under a temperature environment of 80 占 폚, and then a tensile test was started. The conditions of the tensile test were a peeling angle of 180 degrees and a peeling speed (tensile speed) of 6000 mm / min. The load at the time of peeling the surface protective film from the glass was measured, and the average load at that time was defined as the peeling force of the surface protective film.

(Peeling force after 23 占 폚 for 30 minutes and peeling force after 80 占 폚 for 7 days) at a peeling speed of 300 mm /

The surface protective film (25 mm wide × 140 mm long) with the separator removed was bonded to glass (soda lime glass, Matsunamigasu Kogyo Kogyo Co., Ltd.) with reciprocating 2 kg hand rollers.

The evaluation sample thus obtained was measured by a tensile tester. As the tensile tester, "Autograph AG-Xplus HS 6000 mm / min high-speed model (AG-50NX plus)" manufactured by Shimadzu Corporation was used. After the sample for evaluation was set in a tensile tester, the sample was allowed to stand for 30 minutes at an environmental temperature of 23 占 폚 or for 7 days under a temperature environment of 80 占 폚, and then a tensile test was started. The conditions of the tensile test were a peeling angle of 180 degrees and a peeling speed (tensile speed) of 300 mm / min. The load at the time of peeling the surface protective film from the glass was measured, and the average load at that time was defined as the peeling force of the surface protective film.

[Example 1]

85 parts by weight of Prismol S3011 (manufactured by Asahi Glass Co., Ltd., Mn = 10000), which is a polyol having three OH groups, as a polyol (A), 3 parts by weight of a polyol having three hydroxyl groups, Sanenix GP- 13 parts by weight as a polyfunctional isocyanate compound (B), 13 parts by weight of a polyfunctional isocyanate compound (manufactured by Sankige Chemical Co., Ltd.), 3 parts by weight of SANONICS GP-1000 (manufactured by Sanyo Chemical Industries, Ltd., Mn = 1000) 18 parts by weight of Coronate HX (manufactured by Nippon Polyurethane Industry Co., Ltd.), which is a polyfunctional alicyclic isocyanate compound, 0.1 part by weight of a catalyst (manufactured by Nihon Kagaku Kogyo K.K., trade name: 20 parts by weight of myristic acid isopropyl (manufactured by Kao Corp., trade name: Exepal IPM, Mn = 270), 1 part by weight of 1-ethyl-3-methylimidazolium bis (fluoromethanesulfonyl) imide 1.5 parts by weight, trade name: AS110, manufactured by Ichigoshi Seiyaku Co., Ltd.) 0.02 parts by weight of a polyether-modified silicone oil (trade name: KF-6004, manufactured by Shin-Etsu Chemical Co., Ltd.), 0.25 parts by weight of a siloxane bond-containing polymer (trade name: LE-302 manufactured by Kyowa Shagaku KK) Ethyl acetate was added as a diluting solvent, and the mixture was stirred to prepare a pressure-sensitive adhesive composition (1).

The resulting pressure-sensitive adhesive composition (1) was applied to a substrate "LM Mirror S10" (thickness 38 μm, manufactured by Toray Industries, Inc.) containing a polyester resin so as to have a thickness of 10 μm after drying by a fountain roll, And dried for 30 seconds. Thus, a pressure-sensitive adhesive layer was formed on the substrate. Subsequently, a silicone-treated surface of a base material (separator) including a polyester resin having a thickness of 25 占 퐉, which had been subjected to silicone treatment on one side thereof, was bonded to the surface of the pressure-sensitive adhesive layer to obtain a surface protective film (1) with a separator.

The results are shown in Table 1.

[Example 2]

It is also possible to use a siloxane bond-containing polymer such as 1-ethyl-3-methylimidazolium bis (fluoromethanesulfonyl) imide (trade name: AS110 made by Daiichi Kogyo Seiyaku Co., Except that 0.25 parts by weight of a fluorine-containing polymer (trade name: F-571) was used instead of 0.25 parts by weight of a pressure-sensitive adhesive composition (trade name: LE-302, manufactured by KUBOTA CORPORATION) (2) was prepared, and a surface protective film (2) with a separator was obtained.

The results are shown in Table 1.

[Example 3]

The pressure-sensitive adhesive composition (3) was produced in the same manner as in Example 2 except that the amount of the fluorine-containing polymer (product of DIC, trade name: F-571) was changed to 1.00 parts by weight to obtain a surface protective film (3) with a separator.

The results are shown in Table 1.

[Example 4]

The pressure-sensitive adhesive composition (4) was prepared in the same manner as in Example 1 except that 0.30 part by weight of a fluorine-containing polymer (trade name: F-571) To obtain a film (4).

The results are shown in Table 1.

[Example 5]

Except that 0.30 part by weight of a fluorine-containing polymer (trade name: F-571) was used in place of 0.25 parts by weight of a siloxane bond-containing polymer (trade name: LE-302 manufactured by Kyowa Shagajaku K.K.) The pressure-sensitive adhesive composition (5) was produced in the same manner as in Example 1 to obtain a surface protective film (5) with a separator.

The results are shown in Table 1.

[Example 6]

As the polyol (A), 100 parts by weight of a polyol having three OH groups, Sanenix GP-3000 (manufactured by Sanyo Chemical Industries, Ltd., Mn = 3000), 100 parts by weight of a polyfunctional alicyclic isocyanate compound 18 parts by weight of Coronate HX (manufactured by Nippon Polyurethane Industry Co., Ltd.), 0.1 part by weight of a catalyst (manufactured by Nihon Kagaku Kogyo K.K., trade name: Nasem ferric oxide) 0.25 part by weight, trade name: X-22-4015, manufactured by Sekisui Chemical Co., Ltd.), ethyl acetate was added as a diluting solvent, and the mixture was stirred to prepare a pressure-sensitive adhesive composition (6).

The pressure-sensitive adhesive composition (6) was used in the same manner as in Example 1 to obtain a surface protective film (6) with a separator.

The results are shown in Table 1.

[Comparative Example 1]

85 parts by weight of Prismol S3011 (manufactured by Asahi Glass Co., Ltd., Mn = 10000), which is a polyol having three OH groups, as a polyol (A), 3 parts by weight of a polyol having three hydroxyl groups, Sanenix GP- 13 parts by weight as a polyfunctional isocyanate compound (B), 13 parts by weight of a polyfunctional isocyanate compound (manufactured by Sankige Chemical Co., Ltd.), 3 parts by weight of SANONICS GP-1000 (manufactured by Sanyo Chemical Industries, Ltd., Mn = 1000) , 18 parts by weight of Coronate HX (manufactured by Nippon Polyurethane Industry Co., Ltd.), which is a polyfunctional alicyclic isocyanate compound, 0.1 part by weight of a catalyst (trade name: Nasem ferric iron, manufactured by Nihon Kagaku Kogyo K.K.) Ethyl acetate was added thereto, followed by mixing and stirring to prepare a pressure-sensitive adhesive composition (C1).

The pressure-sensitive adhesive composition (C1) was used in the same manner as in Example 1 to obtain a surface protective film (C1) with a separator.

The results are shown in Table 1.

[Comparative Example 2]

Except that 0.02 part by weight of a polyether-modified silicone oil of both ends type (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KF-6004) was used in preparing the pressure-sensitive adhesive composition, Composition (C2) was prepared to obtain a surface protective film (C2) with a separator.

The results are shown in Table 1.

[Comparative Example 3]

As the polyol (A), 100 parts by weight of a polyol having three OH groups, Sanenix GP-3000 (manufactured by Sanyo Chemical Industries, Ltd., Mn = 3000), 100 parts by weight of a polyfunctional alicyclic isocyanate compound 18 parts by weight of Coronate HX (manufactured by Nippon Polyurethane Industry Co., Ltd.), 0.1 part by weight of a catalyst (manufactured by Nihon Kagaku Kogyo K.K., trade name: Nasem iron (II)) and ethyl acetate as a diluting solvent Followed by stirring to prepare a pressure-sensitive adhesive composition (C3).

The pressure-sensitive adhesive composition (C3) was used in the same manner as in Example 1 to obtain a surface protective film (C3) with a separator.

The results are shown in Table 1.

[Comparative Example 4]

(Trade name: AS110, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) and a siloxane bond-containing polymer (manufactured by Kyoeisha Chemical Co., Ltd.) (Trade name: LE-302) was not used as the pressure-sensitive adhesive composition (C4), to obtain a surface protective film (C4) with a separator.

The results are shown in Table 1.

[Comparative Example 5]

The amount of the myristic acid isopropyl (manufactured by Kao Corp., trade name: Exepal IPM, Mn = 270) was changed to 30 parts by weight and the polyether-modified silicone oil of both ends (Trade name: KF-6004, manufactured by Kagaku Kogyo K.K.) was used in an amount of 0.01 part by weight, a pressure-sensitive adhesive composition (C5) was produced to obtain a surface protective film (C5) with a separator .

The results are shown in Table 1.

[Comparative Example 6]

The pressure-sensitive adhesive composition was prepared in the same manner as in Comparative Example 1, except that 25 parts by weight of myristic acid isopropyl (25 parts by weight, trade name: Exepal IPM, Mn = 270, manufactured by Kao Corp.) ), And a surface protective film (C6) with a separator was obtained.

The results are shown in Table 1.

[Comparative Example 7]

(Shin-Etsu Chemical Co., Ltd., trade name: KS-6004) was used instead of 0.01 part by weight of polyether-modified silicone oil of both ends type (Shin-Etsu Chemical Co., 776A): 0.15 part by weight, the pressure-sensitive adhesive composition (C7) was prepared and a surface protective film (C7) with a separator was obtained.

The results are shown in Table 1.

[Example 7]

, 100 parts by weight of "Saibain SH-109" (solid content: 54%, fatty acid ester-containing, manufactured by Toyo Ink) as urethane prepolymer (C), 10 parts by weight of a polyfunctional alicyclic isocyanate compound, Coronate HX (Manufactured by Nippon Polyurethane Industry Co., Ltd.), 1.00 parts by weight of a fluorine-containing polymer (DIC, trade name: F-571) and 208 parts by weight of toluene as a diluting solvent were mixed, To prepare a pressure-sensitive adhesive composition (7).

The resulting pressure-sensitive adhesive composition (7) was coated on a substrate "LM Mirror S10" (38 μm thick, made by Toray Industries, Inc.) containing a polyester resin so as to have a thickness of 10 μm after drying by a fountain roll, And dried for 30 seconds. Thus, a pressure-sensitive adhesive layer was formed on the substrate. Subsequently, a silicone-treated surface of a base material (separator) comprising a polyester resin having a thickness of 25 占 퐉, which had been subjected to silicone treatment on one side thereof, was bonded to the surface of the pressure-sensitive adhesive layer to obtain a surface protective film 7 with a separator.

The results are shown in Table 2.

[Example 8]

The pressure-sensitive adhesive composition (8) was produced in the same manner as in Example 7 except that the amount of the fluorine-containing polymer (product of DIC, trade name: F-571) was changed to 2.00 parts by weight to obtain a surface protective film (8) with a separator.

The results are shown in Table 2.

[Example 9]

A pressure-sensitive adhesive composition (9) was produced in the same manner as in Example 7 except that the amount of the fluorine-containing polymer (product of DIC, trade name: F-571) was changed to 3.00 parts by weight, to obtain a surface protective film (9) with a separator.

The results are shown in Table 2.

[Example 10]

, 100 parts by weight of "Saibain SH-109" (solid content: 54%, fatty acid ester-containing, manufactured by Toyo Ink) as urethane prepolymer (C), 10 parts by weight of a polyfunctional alicyclic isocyanate compound, Coronate HX , 3.6 parts by weight of a fluorine-containing polymer (manufactured by Nippon Polyurethane Industry Co., Ltd.), 1.00 parts by weight of a fluorine-containing polymer (trade name: F-571, manufactured by DIC Co., Ltd.), and 208 parts by weight of toluene as a diluting solvent, To prepare a pressure-sensitive adhesive composition (10).

The resulting pressure-sensitive adhesive composition (10) was applied to a substrate "Lumirror S10" (38 μm thick, made by Toray Co., Ltd.) containing a polyester resin so as to have a thickness of 50 μm after drying by a fountain roll, And dried for 30 seconds. Thus, a pressure-sensitive adhesive layer was formed on the substrate. Subsequently, a silicone-treated surface of a base material (separator) including a polyester resin having a thickness of 25 占 퐉, which had been subjected to silicone treatment on one side thereof, 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 3 and 4.

[Example 11]

The pressure-sensitive adhesive composition (11) was produced in the same manner as in Example 10 except that the amount of the fluorine-containing polymer (product of DIC, trade name: F-571) was changed to 3.00 parts by weight to obtain a surface protective film (11) with a separator.

The results are shown in Tables 3 and 4.

[Example 12]

The pressure-sensitive adhesive composition (12) was produced in the same manner as in Example 10 except that the amount of the fluorine-containing polymer (product of DIC, trade name: F-571) was changed to 5.00 parts by weight to obtain a surface protective film (12) with a separator.

The results are shown in Tables 3 and 4.

[Comparative Example 8]

A pressure-sensitive adhesive composition (C8) was produced in the same manner as in Example 10 except that a fluorine-containing polymer (trade name: F-571, manufactured by DIC) was not used to obtain a surface protective film (C8) with a separator.

The results are shown in Tables 3 and 4.

[Comparative Example 9]

Except that the amount of the coronate HX (manufactured by Nippon Polyurethane Industry Co., Ltd.) was changed to 7.05 parts by weight and a fluorine-containing polymer (trade name: F-571) was not used, (C9) was prepared, and a surface protective film (C9) with a separator was obtained.

The results are shown in Tables 3 and 4.

[Example 13]

, 100 parts by weight of "Saibain SH-109" (solid content: 54%, fatty acid ester-containing, manufactured by Toyo Ink) as urethane prepolymer (C), 10 parts by weight of a polyfunctional alicyclic isocyanate compound, Coronate HX (Manufactured by Nippon Polyurethane Industry Co., Ltd.), 1.00 parts by weight of a fluorine-containing polymer (DIC, trade name: F-571) and 208 parts by weight of toluene as a diluting solvent were mixed, To thereby prepare a pressure-sensitive adhesive composition (13).

The resulting pressure-sensitive adhesive composition (13) was applied to a base material &quot; Lumirror S10 &quot; (38 탆 thick, made by Toray Industries, Inc.) containing a polyester resin so as to have a thickness of 50 탆 after drying by a fountain roll, And dried for 30 seconds. Thus, a pressure-sensitive adhesive layer was formed on the substrate. Subsequently, a silicone-treated surface of a substrate (separator) including a polyester resin having a thickness of 25 占 퐉, which had been subjected to a silicone treatment on one side thereof, 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 3 and 4.

[Example 14]

The pressure-sensitive adhesive composition (14) was produced in the same manner as in Example 13 except that the amount of the fluorine-containing polymer (trade name: F-571, manufactured by DIC Co., Ltd.) was changed to 3.00 parts by weight.

The results are shown in Tables 3 and 4.

[Example 15]

The pressure-sensitive adhesive composition (15) was produced in the same manner as in Example 13 except that the amount of the fluorine-containing polymer (trade name: F-571, manufactured by DIC Co., Ltd.) was changed to 5.00 parts by weight.

The results are shown in Tables 3 and 4.

[Comparative Example 10]

Except that 1 part by weight of a silicone releasing agent (trade name: KS-776A, manufactured by Shin-Etsu Chemical Co., Ltd.) was used instead of the fluorine-containing polymer (trade name: F- To thereby prepare a pressure-sensitive adhesive composition (C10), and a surface protective film (C10) with a separator was obtained.

The results are shown in Tables 3 and 4.

[Comparative Example 11]

Except that 3 parts by weight of a silicone releasing agent (trade name: KS-776A, manufactured by Shin-Etsu Chemical Co., Ltd.) was used instead of the fluorine-containing polymer (trade name: F- To prepare a pressure-sensitive adhesive composition (C11), and a surface protective film (C11) with a separator was obtained.

The results are shown in Tables 3 and 4.

[Comparative Example 12]

The thickness of the pressure-sensitive adhesive layer was changed to 10 mu m without using a fluorine-containing polymer (trade name: F-571, manufactured by DIC Co., Ltd.) with the use amount of Coronate HX (manufactured by Nippon Polyurethane Industry Co., Except that the pressure-sensitive adhesive composition (C12) was produced in the same manner as in Example 13 to obtain a surface protective film (C12) with a separator.

The results are shown in Tables 3 and 4.

[Comparative Example 13]

The thickness of the pressure-sensitive adhesive layer was 25 占 퐉 without using a fluorine-containing polymer (trade name: F-571, manufactured by DIC Co., Ltd.) in place of 17.7 parts by weight of Coronate HX (manufactured by Nippon Polyurethane Industry Co., Except that, the pressure-sensitive adhesive composition (C13) was produced in the same manner as in Example 13 to obtain a surface protective film (C13) with a separator.

The results are shown in Tables 3 and 4.

[Example 16]

85 parts by weight of Prismol S3011 (manufactured by Asahi Glass Co., Ltd., Mn = 10000), which is a polyol having three OH groups, as a polyol (A), 3 parts by weight of a polyol having three hydroxyl groups, Sanenix GP- 13 parts by weight as a polyfunctional isocyanate compound (B), 13 parts by weight of a polyfunctional isocyanate compound (manufactured by Sankige Chemical Co., Ltd.), 3 parts by weight of SANONICS GP-1000 (manufactured by Sanyo Chemical Industries, Ltd., Mn = 1000) , 17.7 parts by weight of a coronate HX (manufactured by Nippon Polyurethane Industry Co., Ltd.) as a polyfunctional alicyclic isocyanate compound, 0.3 part by weight of a fluorine-containing polymer (DIC, trade name: F-571) , And the mixture was stirred with a disper to prepare a pressure-sensitive adhesive composition (16).

The obtained pressure-sensitive adhesive composition (16) was applied to a substrate "LM Mirror S10" (thickness 38 μm, manufactured by Toray Industries Co., Ltd.) containing a polyester resin so as to have a thickness of 10 μm after drying by a fountain roll, And dried for 30 seconds. Thus, a pressure-sensitive adhesive layer was formed on the substrate. Subsequently, a silicone-treated surface of a substrate (separator) including a polyester resin having a thickness of 25 占 퐉, which had been subjected to silicone treatment on one side thereof, was bonded to the surface of the pressure-sensitive adhesive layer to obtain a surface protective film 16 with a separator.

The results are shown in Tables 3 and 4.

[Example 17]

The pressure-sensitive adhesive composition (17) was produced in the same manner as in Example 16 except that the thickness of the pressure-sensitive adhesive layer was 25 占 퐉 to obtain a surface protective film (17) with a separator.

The results are shown in Tables 3 and 4.

[Example 18]

85 parts by weight of Prismol S3011 (manufactured by Asahi Glass Co., Ltd., Mn = 10000), which is a polyol having three OH groups, as a polyol (A), 3 parts by weight of a polyol having three hydroxyl groups, Sanenix GP- 13 parts by weight as a polyfunctional isocyanate compound (B), 13 parts by weight of a polyfunctional isocyanate compound (manufactured by Sankige Chemical Co., Ltd.), 3 parts by weight of SANONICS GP-1000 (manufactured by Sanyo Chemical Industries, Ltd., Mn = 1000) 17.7 parts by weight of Coronate HX (manufactured by Nippon Polyurethane Industry Co., Ltd.) which is a polyfunctional alicyclic isocyanate compound, 0.3 parts by weight of a hydroxyl group-containing silicone (trade name: X-22-4015 available from Shinetsu Kagaku Kogyo K.K.) And 200 parts by weight of ethyl acetate as a diluting solvent were mixed and stirred with a disper to prepare a pressure-sensitive adhesive composition (18).

The resulting pressure-sensitive adhesive composition (18) was applied to a substrate "Lamiron S10" (38 μm thick, made by Toray Industries, Inc.) containing a polyester resin so as to have a thickness of 10 μm after drying by a fountain roll, And dried for 30 seconds. Thus, a pressure-sensitive adhesive layer was formed on the substrate. Subsequently, a silicone-treated surface of a substrate (separator) including a polyester resin having a thickness of 25 占 퐉, which had been subjected to silicone treatment on one side thereof, was bonded to the surface of the pressure-sensitive adhesive layer to obtain a surface protective film 18 with a separator.

The results are shown in Tables 3 and 4.

[Example 19]

A pressure-sensitive adhesive composition (19) was produced in the same manner as in Example 18 except that the thickness of the pressure-sensitive adhesive layer was 25 占 퐉 to obtain a surface protective film (19) with a separator.

The results are shown in Tables 3 and 4.

[Example 20]

The separator of the surface protective film 1 with a separator obtained in Example 1 was peeled off and the side of the pressure sensitive adhesive layer was adhered to a polarizing plate (trade name: "TEG1465DUHC" manufactured by Nitto Denko Corporation) Member.

[Example 21]

The separator of the surface protective film 2 with a separator obtained in Example 2 was peeled off and the side of the pressure sensitive adhesive layer was adhered to a polarizing plate (trade name: "TEG1465DUHC" manufactured by Nitto Denko Corporation) Member.

[Example 22]

The separator of the surface protective film 3 with a separator obtained in Example 3 was peeled off and the side of the pressure sensitive adhesive layer was adhered to a polarizing plate (trade name: "TEG1465DUHC" manufactured by Nitto Denko Corporation) Member.

[Example 23]

The separator of the surface protective film 4 with a separator obtained in Example 4 was peeled off and the side of the pressure sensitive adhesive layer was bonded to a polarizing plate (trade name: "TEG1465DUHC" manufactured by Nitto Denko Corporation) Member.

[Example 24]

The separator of the surface protective film 5 with a separator obtained in Example 5 was peeled off and the side of the pressure sensitive adhesive layer was adhered to a polarizing plate (trade name: "TEG1465DUHC" manufactured by Nitto Denko KK) Member.

[Example 25]

The separator of the surface protective film 6 with a separator obtained in Example 6 was peeled off and the side of the pressure sensitive adhesive layer was adhered to a polarizing plate (trade name: "TEG1465DUHC" manufactured by Nitto Denko Corporation) Member.

[Example 26]

The separator of the surface protective film 1 with a separator obtained in Example 1 was peeled off and the side of the pressure sensitive adhesive layer was adhered to a conductive film (ELECORA V270L-TFMP, trade name, manufactured by Nitto Denko K.K.) An electronic member to which a film was adhered was obtained.

[Example 27]

The separator of the surface protective film 2 with a separator obtained in Example 2 was peeled off and the side of the pressure sensitive adhesive layer was adhered to a conductive film (ELECORA V270L-TFMP, manufactured by Nitto Denko Co., Ltd.) An electronic member to which a film was adhered was obtained.

[Example 28]

The separator of the surface protective film 3 with a separator obtained in Example 3 was peeled off and the side of the pressure sensitive adhesive layer was adhered to a conductive film (trade name "Elecrista V270L-TFMP" made by Nitto Denko Corporation) An electronic member to which a film was adhered was obtained.

[Example 29]

The separator of the surface protective film 4 with a separator obtained in Example 4 was peeled off and the side of the pressure sensitive adhesive layer was adhered to a conductive film (ELECORA V270L-TFMP, trade name, manufactured by Nitto Denko K.K.) An electronic member to which a film was adhered was obtained.

[Example 30]

The separator of the surface protective film 5 with a separator obtained in Example 5 was peeled off and the side of the pressure sensitive adhesive layer was adhered to a conductive film (ELECORA V270L-TFMP, manufactured by Nitto Denko Co., Ltd.) An electronic member to which a film was adhered was obtained.

[Example 31]

The separator of the surface protective film 6 with a separator obtained in Example 6 was peeled off and the side of the pressure sensitive adhesive layer was adhered to a conductive film (ELECORA V270L-TFMP, manufactured by Nitto Denko Co., Ltd.) An electronic member to which a film was adhered was obtained.

[Example 32]

The separator of the surface protective film 7 with a separator obtained in Example 7 was peeled off and the side of the pressure sensitive adhesive layer was adhered to a polarizing plate (trade name: "TEG1465DUHC" manufactured by Nitto Denko Corporation) Member.

[Example 33]

The separator of the surface protective film 10 with a separator obtained in Example 10 was peeled off and the side of the pressure sensitive adhesive layer was adhered to a polarizing plate (trade name: "TEG1465DUHC" manufactured by Nitto Denko Corporation) Member.

[Example 34]

The separator of the surface protective film 13 with a separator obtained in Example 13 was peeled off and the side of the pressure sensitive adhesive layer was adhered to a polarizing plate (trade name: "TEG1465DUHC" manufactured by Nitto Denko Corporation) Member.

[Example 35]

The separator of the surface protective film 16 with a separator obtained in Example 16 was peeled off and the side of the pressure sensitive adhesive layer was adhered to a polarizing plate (trade name: "TEG1465DUHC" manufactured by Nitto Denko Corporation) Member.

[Example 36]

The separator of the surface protective film 18 with a separator obtained in Example 18 was peeled off and the side of the pressure sensitive adhesive layer was adhered to a polarizing plate (trade name: "TEG1465DUHC" manufactured by Nitto Denko Corporation) Member.

[Example 37]

The separator of the surface protective film 7 with a separator obtained in Example 7 was peeled off and the side of the pressure sensitive adhesive layer was adhered to a conductive film (trade name "Elecrista V270L-TFMP", made by NITTO DENKO CORPORATION) An electronic member to which a film was adhered was obtained.

[Example 38]

The separator of the surface protective film 10 with a separator obtained in Example 10 was peeled off and the side of the pressure sensitive adhesive layer was adhered to a conductive film (ELECORA V270L-TFMP, manufactured by Nitto Denko Co., Ltd.) An electronic member to which a film was adhered was obtained.

[Example 39]

The separator of the surface protective film 13 with a separator obtained in Example 13 was peeled off and the side of the pressure sensitive adhesive layer was adhered to a conductive film (trade name "Elecrista V270L-TFMP" made by Nitto Denko Corporation) An electronic member to which a film was adhered was obtained.

[Example 40]

The separator of the surface protective film 16 with a separator obtained in Example 16 was peeled off and the side of the pressure sensitive adhesive layer was adhered to a conductive film (ELECORA V270L-TFMP, made by Nitto Denko Co., Ltd.) An electronic member to which a film was adhered was obtained.

[Example 41]

The separator of the surface protective film 18 with a separator obtained in Example 18 was peeled off and the side of the pressure sensitive adhesive layer was adhered to a conductive film (ELECORA V270L-TFMP, manufactured by Nitto Denko Co., Ltd.) An electronic member to which a film was adhered was obtained.

&Lt; Industrial applicability >

The surface protective film of the present invention can be used in any suitable application. Preferably, the surface protective film of the present invention is preferably used in the fields of optical members and electronic members.

1: substrate layer
2: Pressure-sensitive adhesive layer
10: Surface protective film

Claims (18)

A surface protective film having a pressure-sensitive adhesive layer,
A polyethylene terephthalate film having a thickness of 25 占 퐉 was bonded to the pressure-sensitive adhesive layer and the polyethylene terephthalate film was peeled off at 23 占 폚 at a peeling angle of 180 degrees and a peeling rate of 6000 mm / N / 25 mm or more and 0.08 N / 25 mm or less,
The residual adhesion ratio is 50% or more,
Wherein 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 urethane prepolymer and a hydroxyl group-
Wherein the content of the hydroxyl group-containing fluorine-based additive relative to 100 parts by weight of the urethane prepolymer is 1 part by weight to 5 parts by weight. A polyethylene terephthalate film having a thickness of 25 占 퐉 was bonded to the pressure-sensitive adhesive layer and peeled from the pressure-sensitive adhesive layer at 23 占 폚 for 30 minutes after peeling the polyethylene terephthalate film at a peeling angle of 180 degrees and a peeling rate of 300 mm / Wherein the peel force is 0.001 N / 25 mm or more and 0.02 N / 25 mm or less. A surface protective film having a pressure-sensitive adhesive layer,
A polyethylene terephthalate film having a thickness of 25 占 퐉 was bonded to the pressure-sensitive adhesive layer, and after peeling the polyethylene terephthalate film at 80 占 폚 for 7 days at a peeling angle of 180 degrees and a peeling rate of 6000 mm / min, the peeling force was 0.001 N / 25 mm or more and 0.35 N / 25 mm or less,
The residual adhesion ratio is 50% or more,
Wherein 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 urethane prepolymer and a hydroxyl group-
Wherein the content of the hydroxyl group-containing fluorine-based additive relative to 100 parts by weight of the urethane prepolymer is 1 part by weight to 5 parts by weight. A polyethylene terephthalate film having a thickness of 25 占 퐉 was bonded to the pressure-sensitive adhesive layer and peeled from the polyethylene terephthalate film at 80 占 폚 at a peeling angle of 180 degrees and a peeling rate of 300 mm / min after 7 days at 80 占 폚 Wherein the peel force is 0.001 N / 25 mm or more and 0.07 N / 25 mm or less. A surface protective film having a pressure-sensitive adhesive layer,
A glass plate having a thickness of 1000 占 퐉 was bonded to the pressure-sensitive adhesive layer and peeled off at 23 占 폚 for 30 minutes from the glass plate at a peeling angle of 180 degrees and a peeling rate of 6000 mm / min from 0.001 N / 25 mm to 0.055 N / 25 mm or less,
The residual adhesion ratio is 50% or more,
Wherein 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 urethane prepolymer and a hydroxyl group-
Wherein the content of the hydroxyl group-containing fluorine-based additive relative to 100 parts by weight of the urethane prepolymer is 1 part by weight to 5 parts by weight. 6. The adhesive sheet according to claim 5, wherein the pressure-sensitive adhesive layer is a glass plate having a thickness of 1000 占 퐉 and is peeled off at 30 占 폚 at 23 占 폚 at a peeling angle of 180 degrees and a peeling rate of 300 mm / N / 25mm or more and 0.023N / 25mm or less. A surface protective film having a pressure-sensitive adhesive layer,
A glass plate having a thickness of 1,000 占 퐉 was bonded to the pressure-sensitive adhesive layer, and after 7 days at 80 占 폚, the peel strength from the glass plate when peeled off at a peeling angle of 180 degrees and a peeling rate of 6000 mm / min was 0.001 N / / 25 mm or less,
The residual adhesion ratio is 50% or more,
Wherein 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 urethane prepolymer and a hydroxyl group-
Wherein the content of the hydroxyl group-containing fluorine-based additive relative to 100 parts by weight of the urethane prepolymer is 1 part by weight to 5 parts by weight. A pressure-sensitive adhesive sheet according to claim 7, wherein the pressure-sensitive adhesive layer is bonded to a glass plate having a thickness of 1000 占 퐉 and peeled off from the glass plate at 80 占 폚 at a peeling angle of 180 degrees and a peeling rate of 300 mm / N / 25mm or more and 0.05N / 25mm or less. The surface protective film according to any one of claims 1 to 8, wherein the residual adhesion ratio is 65% or more. 9. The surface protective film according to any one of claims 1 to 8, wherein the pressure sensitive adhesive composition comprises a fatty acid ester. An optical member to which the surface protective film according to any one of claims 1 to 8 is adhered. An electronic member to which the surface protecting film according to any one of claims 1 to 8 is adhered. delete delete delete delete delete delete

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