CN112041405A - Surface protective film - Google Patents

Abstract

Provided is a surface protection film which does not easily peel off from an adherend, can suppress re-peeling with time even if the initial peeling force after being attached to the adherend is large, and has low staining of the adherend surface due to attachment to the adherend. The surface protection film of the present invention is a surface protection film having an adhesive layer, wherein the adhesive layer of the surface protection film is bonded to a glass plate and left at a temperature of 23 ℃ for 30 minutes, the peel force A when the surface protection film is peeled from the glass plate at a peel angle of 180 degrees and a peel speed of 300 mm/minute is 0.024N/25mm to 0.50N/25mm at a temperature of 23 ℃ and the peel force A when the adhesive layer of the surface protection film is bonded to the glass plate and left at a temperature of 100 ℃ for 2 days, the surface protection film is peeled from the glass plate at a peel angle of 180 degrees and a peel speed of 300 mm/minute at a temperature of 23 ℃, and the rate of increase with time of the peel force calculated by (B/A) × 100 is 1000% or less assuming that the peel force at this time is B.

Description

Surface protective film

Technical Field

The present invention relates to a surface protective film.

Background

In the manufacturing process of optical members and electronic members, in order to prevent surface damage of the optical members and the electronic members during processing, assembly, inspection, transportation, and the like, a surface protective film is generally attached to the exposed surfaces of the optical members and the electronic members. Such a surface protection film is peeled off from an optical member or an electronic member at a timing when surface protection is not required (patent document 1).

In the optical member and the electronic member to which such a surface protective film is attached, when the surface protective film is to be peeled as described above, it is important to be able to smoothly peel only at the interface between the surface protective film and the optical member or the electronic member.

However, when an optical member or an electronic member includes a member that is easily broken, such as a thin glass or a barrier film, and the surface protective film to be attached is to be peeled, the member that is easily broken may be broken by a peeling force even when a conventional surface protective film having a light peeling property is used.

In the manufacturing process of optical members and electronic members, surface protective films attached to the exposed surfaces of the optical members and the electronic members are often stored in a state of being kept attached to each other in order to prevent damage to the surfaces of the optical members and the electronic members during processing, assembly, inspection, transportation, and the like. In this case, when the conventional surface protective film is stored while being kept in an adhered state, there is a problem that the adhesive strength is increased with time and re-peeling occurs.

Therefore, a surface protection film having a lighter peelability, i.e., an ultra-light peelability, than a conventional surface protection film having a light peelability has been reported (patent document 2).

By imparting an ultra-light peelability to the surface protective film, the initial peeling force after attachment can be reduced, and the occurrence of heavy peeling over time can be suppressed. However, when the surface protective film is provided with an ultra-light peelability, the surface protective film attached to the exposed surface of the optical member or the electronic member may peel off in the manufacturing process depending on, for example, conditions of the manufacturing process of the optical member or the electronic member.

On the other hand, if the initial peeling force after the surface protective film is stuck is increased in order to suppress the peeling as described above, there is a problem that the peeling force increases with time and re-peeling occurs.

As a method for reducing the peeling force, it is considered to include a large amount of a conventional peeling agent in a pressure-sensitive adhesive layer included in a surface protective film. However, such a method has the following problems: when the surface protective film is peeled off after being attached to an adherend such as an optical member or an electronic member, the degree of contamination of the adherend surface by the peeling agent becomes large, and even if it is desired to reattach the surface protective film to the contaminated adherend surface, the attachment becomes difficult due to the contamination of the adherend surface.

As described above, there are the following requirements: typically, in the production process of optical members and electronic members, a surface protective film attached to an adherend is less likely to peel off; even if the initial peeling force after the surface protection film is attached to an adherend is large, the re-peeling over time can be suppressed; the staining property of the adherend surface caused by attaching the surface protective film can be reduced.

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open publication No. 2016-

Patent document 2: japanese patent laid-open publication No. 2017-160422

Disclosure of Invention

Problems to be solved by the invention

The present invention addresses the problem of providing a surface protecting film which does not easily peel off from an adherend, can suppress re-peeling over time even when the initial peeling force after attachment to the adherend is large, and has low staining of the adherend surface due to attachment to the adherend.

Means for solving the problems

The surface protective film of the present invention is a surface protective film having an adhesive layer,

the adhesive layer of the surface protective film is bonded to a glass plate and left at a temperature of 23 ℃ for 30 minutes, and then the surface protective film is peeled from the glass plate at a peeling angle of 180 degrees at a peeling speed of 300 mm/min at a temperature of 23 ℃ with a peeling force A of 0.024N/25mm to 0.50N/25mm,

the pressure-sensitive adhesive layer of the surface protective film is bonded to a glass plate and left at a temperature of 100 ℃ for 2 days, and then the surface protective film is peeled from the glass plate at a peeling angle of 180 degrees and a peeling speed of 300 mm/min at a temperature of 23 ℃, and when the peeling force at this time is B, the rate of increase with time of the peeling force calculated by (B/A) × 100 is 1000% or less.

In one embodiment, the adhesive layer of the surface protective film is bonded to a glass plate and left at 23 ℃ for 7 days, and then the surface protective film is peeled from the glass plate at a peeling angle of 180 degrees and a peeling speed of 300 mm/min at 23 ℃, and when the peeling force at this time is C, the rate of increase with time of the peeling force calculated by (C/a) × 100 is 160% or less.

In one embodiment, the surface protection film of the present invention has a residual adhesion rate to a glass plate at 23 ℃ of 50% or more.

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

In one embodiment, the adhesive composition comprises a fatty acid ester.

In one embodiment, the silicone additive is at least 1 selected from the group consisting of a silicone bond-containing compound, a hydroxyl group-containing silicone compound, and a crosslinkable functional group-containing silicone compound.

In one embodiment, the fluorine-containing additive is at least 1 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 1 selected from the group consisting of urethane prepolymer, polyol, acrylic resin, rubber resin, and silicone resin.

The surface protective film of the present invention is attached to the optical member of the present invention.

The surface protective film of the present invention is attached to the electronic component of the present invention.

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, there can be provided a surface protecting film which is not easily peeled from an adherend, can suppress re-peeling with time even if the initial peeling force after the attachment to the adherend is large, and has low staining of the adherend surface due to the attachment to the adherend.

Drawings

Fig. 1 is a schematic cross-sectional view of a surface protection film according to an embodiment of the present invention.

Detailed Description

Surface protective film (A)

The surface protection film of the present invention has an adhesive layer. The surface protection film of the present invention may be provided with any other suitable member as long as it has an adhesive layer, within a range not impairing the effects of the present invention. Typically, the surface protection film of the present invention has a base material layer and an adhesive layer.

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

In fig. 1, an arbitrary appropriate release liner (also referred to as a release sheet or a separator, not shown) may be provided on the surface of the pressure-sensitive adhesive layer 2 opposite to the base material layer 1 for protection and the like until the use. Examples of the release liner include release liners in which the surface of a substrate (liner substrate) such as paper or plastic film is treated with silicone, and release liners in which the surface of a substrate (liner substrate) such as paper or plastic film is laminated with a polyolefin resin. Examples of the plastic film as the spacer base material include a polyethylene film, a polypropylene film, a polybutylene film, a polybutadiene film, a polymethylpentene film, a polyvinyl chloride film, a vinyl chloride copolymer film, a polyethylene terephthalate film, a polybutylene terephthalate film, a polyurethane film, an ethylene-vinyl acetate copolymer film, and the like. The plastic film as the base material of the gasket is preferably a polyethylene film.

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

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

In the surface-protecting film of the present invention, after the adhesive layer of the surface-protecting film is bonded to a glass plate and left at 23 ℃ for 30 minutes, the peel force A at a peel angle of 180 degrees and a peel speed of 300 mm/minute is preferably 0.024N/25mm to 0.50N/25mm, more preferably 0.024N/25mm to 0.40N/25mm, still more preferably 0.024N/25mm to 0.30N/25mm, particularly preferably 0.024N/25mm to 0.20N/25mm, and most preferably 0.024N/25mm to 0.10N/25mm when the surface-protecting film is peeled from the glass plate at 23 ℃. When the peeling force a is within the above range, the surface protection film of the present invention may become less likely to peel from an adherend. When the peeling force a is within the above range, the surface protection film of the present invention adhered to the exposed surface of the optical member or the electronic member is typically less likely to peel off in the production process of the optical member or the electronic member. The details of the measurement of the peeling force a will be described later.

In the surface protecting film of the present invention, after the adhesive layer of the surface protecting film is adhered to a glass plate and left at 100 ℃ for 2 days, the peel force B at a peel angle of 180 degrees and a peel speed of 300 mm/min when the surface protecting film is peeled from the glass plate at 23 ℃ is preferably 0.20N/25mm to 1.0N/25mm, more preferably 0.25N/25mm to 0.95N/25mm, still more preferably 0.30N/25mm to 0.90N/25mm, particularly preferably 0.35N/25mm to 0.85N/25mm, and most preferably 0.40N/25mm to 0.80N/25 mm. When the peeling force B is within the above range, the surface protection film of the present invention can suppress re-peeling with time. The details of the measurement of the peeling force B will be described later.

In the surface protection film of the present invention, the rate of increase in the peeling force a and the peeling force B with time calculated by (B/a) × 100 is preferably 1000% or less, more preferably 950% or less, still more preferably 900% or less, particularly preferably 850% or less, and most preferably 800% or less. The lower limit of the rate of increase of the peeling force with time is preferably 450% or more. When the rate of increase of the peeling force with time is within the above range, the surface protection film of the present invention can suppress re-peeling with time even when the initial peeling force after the surface protection film is attached to an adherend is large.

In the surface-protecting film of the present invention, after the adhesive layer of the surface-protecting film is adhered to a glass plate and left at 23 ℃ for 7 days, the peel force C at a peel angle of 180 degrees and a peel speed of 300 mm/min is preferably 0.024N/25mm to 0.50N/25mm, more preferably 0.024N/25mm to 0.40N/25mm, still more preferably 0.024N/25mm to 0.30N/25mm, particularly preferably 0.024N/25mm to 0.20N/25mm, and most preferably 0.024N/25mm to 0.10N/25mm, when the surface-protecting film is peeled from the glass plate at 23 ℃. When the peeling force C is within the above range, the surface protection film of the present invention can suppress re-peeling with time. The details of the measurement of the peeling force C will be described later.

In the surface protection film of the present invention, the rate of increase in the peeling force a and the peeling force C with time, which is calculated by (C/a) × 100, is preferably 160% or less, more preferably 155% or less, still more preferably 150% or less, particularly preferably 145% or less, and most preferably 140% or less. The lower limit of the rate of increase of the peeling force with time is preferably 80% or more. When the rate of increase of the peeling force with time is within the above range, the surface protection film of the present invention can suppress re-peeling with time even when the initial peeling force after the surface protection film is attached to an adherend is large.

The surface protection film of the present invention has a residual adhesion ratio of preferably 50% or more, more preferably 60% to 100%, even more preferably 70% to 100%, particularly preferably 80% to 100%, and most preferably 85% to 100%. When the residual adhesion ratio is within the above range, the surface protecting film of the present invention can exhibit an effect of reducing staining of the surface of an adherend due to adhesion to the adherend. The details of the measurement of the residual adhesion ratio will be described later.

The surface protective film of the present invention can be produced by any suitable method. Such a production method can be carried out by any appropriate production method such as the following method

(1) Method for coating solution or hot melt of material for forming adhesive layer on base layer,

(2) A method of applying a solution or hot melt of a material for forming an adhesive layer on a separator and transferring the formed adhesive layer to a base layer,

(3) A method of extruding a material for forming the adhesive layer to form a coating on the base material layer,

(4) A method of extruding the substrate layer and the adhesive layer in two or more layers,

(5) A method of laminating an adhesive layer on a substrate layer in a single layer or a method of laminating an adhesive layer and a laminate layer in two layers,

(6) A method of laminating two or more layers of an adhesive layer and a substrate layer-forming material such as a film or a laminate layer.

As a method of coating, for example, a roll coating method, a comma coating method, a die coating method, a reverse coating method, a screen printing method, a gravure coating method, or the like can be used.

A-1. substrate layer

The base material layer may be 1 layer only, or may be 2 or more layers. The substrate layer may be a stretched substrate layer.

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

For the purpose of forming a roll which is easy to unwind, for example, a surface of the substrate layer to which the pressure-sensitive adhesive layer is not attached may be subjected to a release treatment by adding a fatty acid amide, a polyethyleneimine, a long-chain alkyl additive, or the like to the substrate layer, or may be provided with a coating layer formed of any suitable release agent such as a silicone-based, long-chain alkyl-based, or fluorine-based release agent.

As the material of the base layer, any suitable material can be used depending on the application. Examples thereof include plastics, paper, metal films, and nonwoven fabrics. Preferably plastic. That is, the base material layer is preferably a plastic film. The base layer may be made of 1 kind of material, or may be made of 2 or more kinds of materials. For example, it may be made of 2 or more kinds of plastics.

Examples of the plastic include polyester resins, polyamide resins, and polyolefin resins. Examples of the polyester resin include polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate. Examples of the polyolefin-based resin include homopolymers of olefin monomers and copolymers of olefin monomers. Specific examples of the polyolefin-based resin include homopolypropylene; propylene copolymers such as block, random and graft copolymers containing an ethylene component as a copolymer component; reactor TPO; low density, high density, linear low density, ultra low density, and other ethylene-based polymers; ethylene copolymers such as ethylene-propylene copolymers, ethylene-vinyl acetate copolymers, ethylene-methyl acrylate copolymers, ethylene-ethyl acrylate copolymers, ethylene-butyl acrylate copolymers, ethylene-methacrylic acid copolymers, and ethylene-methyl methacrylate copolymers; and the like.

The base layer may contain any suitable additive as required. Examples of additives that can be contained in the base layer include antioxidants, ultraviolet absorbers, light stabilizers, antistatic agents, fillers, and pigments. The kind, number, and amount of the additives that can be contained in the base material layer can be appropriately set according to the purpose. In particular, when the material of the base material layer is plastic, it is preferable to contain some of the above additives for the purpose of preventing deterioration and the like. From the viewpoint of improving weather resistance and the like, particularly preferred examples of the additives include an antioxidant, an ultraviolet absorber, a light stabilizer and a filler.

As the antioxidant, any suitable antioxidant can be used. Examples of such antioxidants include phenol antioxidants, phosphorus processing heat stabilizers, lactone processing heat stabilizers, sulfur heat stabilizers, and phenol/phosphorus antioxidants. The content ratio of the antioxidant is preferably 1 wt% or less, more preferably 0.5 wt% or less, and further preferably 0.01 wt% to 0.2 wt% with respect to the base resin of the base layer (when the base layer is a blend, the blend is the base resin).

As the ultraviolet absorber, any suitable ultraviolet absorber can be used. Examples of such an ultraviolet absorber include benzotriazole-based ultraviolet absorbers, triazine-based ultraviolet absorbers, and benzophenone-based ultraviolet absorbers. The content of the ultraviolet absorber is preferably 2% by weight or less, more preferably 1% by weight or less, and still more preferably 0.01% by weight to 0.5% by weight, based on the base resin forming the base layer (when the base layer is a blend, the blend is the base resin).

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

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

Further, for the purpose of imparting antistatic properties, preferred examples of the additive include inorganic, low-molecular-weight and high-molecular-weight antistatic agents such as surfactants, inorganic salts, polyols, metal compounds and carbon. In particular, from the viewpoint of stain and maintenance of adhesiveness, a high molecular weight antistatic agent and carbon are preferable.

Adhesive layer A-2

The adhesive layer may be composed of an adhesive. The adhesive may be formed from an adhesive composition.

The adhesive layer may be formed by any suitable method. Examples of such a method include a method in which a pressure-sensitive adhesive composition is applied to a base material layer to form a pressure-sensitive adhesive layer on the base material layer. Examples of such coating methods include roll coating, gravure coating, reverse coating, roll brushing, spray coating, air knife coating, and extrusion coating using a die coater or the like.

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

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

The content ratio of the base polymer to the total amount of the silicone additive and the fluorine additive in the adhesive composition is preferably 50 to 100 wt%, more preferably 60 to 100 wt%, even more preferably 70 to 100 wt%, particularly preferably 75 to 100 wt%, and most preferably 80 to 100 wt%. When the total content ratio of the base polymer, the silicone additive, and the fluorine additive in the adhesive composition is within the above range, the surface protective film of the present invention can further exhibit the following effects: the release from the adherend can be further suppressed, and the releasability with time can be further suppressed, and the staining of the adherend surface due to the attachment to the adherend is low.

The content of the silicone additive and/or the fluorine additive in the pressure-sensitive adhesive composition is preferably 0.001 to 50 parts by weight, more preferably 0.005 to 25 parts by weight, further preferably 0.01 to 10 parts by weight, further preferably 0.01 to 1 part by weight, further preferably 0.01 to 0.50 parts by weight, particularly preferably 0.01 to 0.30 parts by weight, and most preferably 0.01 to 0.28 parts by weight, based on the total amount of the silicone additive and the fluorine additive, relative to 100 parts by weight of the base polymer. When the content of the silicone additive and/or the fluorine additive in the adhesive composition is within the above range, the surface protective film of the present invention can further exhibit the following effects: the release from the adherend can be further suppressed, and the releasability with time can be further suppressed, and the staining of the adherend surface due to the attachment to the adherend is low.

That is, when the silicone additive is contained in the pressure-sensitive adhesive composition but the fluorine-containing additive is not contained, the content ratio of the silicone additive is preferably 0.001 to 50 parts by weight, more preferably 0.005 to 25 parts by weight, further preferably 0.01 to 10 parts by weight, further preferably 0.01 to 1 part by weight, further preferably 0.01 to 0.50 parts by weight, particularly preferably 0.01 to 0.30 parts by weight, and most preferably 0.01 to 0.28 parts by weight, based on 100 parts by weight of the base polymer. When the content of the silicone additive in the adhesive composition is within the above range, the surface protective film of the present invention can further exhibit the following effects: the release from the adherend can be further suppressed, and the releasability with time can be further suppressed, and the staining of the adherend surface due to the attachment to the adherend is low.

When the pressure-sensitive adhesive composition does not contain a silicone additive but contains a fluorine additive, the content of the fluorine additive is preferably 0.001 to 50 parts by weight, more preferably 0.005 to 25 parts by weight, even more preferably 0.01 to 10 parts by weight, even more preferably 0.01 to 1 part by weight, even more preferably 0.01 to 0.50 parts by weight, particularly preferably 0.01 to 0.30 parts by weight, and most preferably 0.01 to 0.28 parts by weight, based on 100 parts by weight of the base polymer. When the content of the fluorine-based additive in the adhesive composition is within the above range, the surface protective film of the present invention can further exhibit the following effects: the release from the adherend can be further suppressed, and the releasability with time can be further suppressed, and the staining of the adherend surface due to the attachment to the adherend is low.

When both the organosilicon additive and the fluorine additive are contained in the adhesive composition, the total content of the organosilicon additive and the fluorine additive is preferably 0.001 to 50 parts by weight, more preferably 0.005 to 25 parts by weight, further preferably 0.01 to 10 parts by weight, further preferably 0.01 to 1 part by weight, further preferably 0.01 to 0.50 parts by weight, particularly preferably 0.01 to 0.30 parts by weight, and most preferably 0.01 to 0.28 parts by weight, based on 100 parts by weight of the base polymer. When the total content of the silicone additive and the fluorine additive in the binder composition is within the above range, the surface protection film of the present invention can further exhibit the following effects: the release from the adherend can be further suppressed, and the releasability with time can be further suppressed, and the staining of the adherend surface due to the attachment to the adherend is low.

< A-2-1. base Polymer >

The base polymer is preferably at least 1 selected from urethane prepolymer, polyol, acrylic resin, rubber resin, and silicone resin. When the base polymer is at least 1 selected from the group consisting of urethane prepolymer, polyol, acrylic resin, rubber resin, and silicone resin, the surface protective film of the present invention can further exhibit the following effects: the release from the adherend can be further suppressed, and the releasability with time can be further suppressed, and the staining of the adherend surface due to the attachment to the adherend is low.

[ A-2-1-a. urethane prepolymer ]

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

As the polyester polyol (a1), any suitable polyester polyol can be used. Examples of such a polyester polyol (a1) include a polyester polyol obtained by reacting an acid component with a diol component. Examples of the acid component include terephthalic acid, adipic acid, azelaic acid, sebacic acid, phthalic anhydride, isophthalic acid, trimellitic acid, and the like. Examples of the diol component include ethylene glycol, propylene glycol, diethylene glycol, butylene glycol, 1, 6-hexanediol, 3-methyl-1, 5-pentanediol, 3' -dimethylolheptane, polyoxyethylene glycol, polyoxypropylene glycol, 1, 4-butanediol, neopentyl glycol, and butylethylpentanediol, and examples of the polyol component include glycerin, trimethylolpropane, and pentaerythritol. Examples of the polyester polyol (a1) include polyester polyols obtained by ring-opening polymerization of lactones such as polycaprolactone, poly (. beta. -methyl-. gamma. -valerolactone) and polycaprolactone.

The molecular weight of the polyester polyol (a1) may be from a low molecular weight to a high molecular weight. The molecular weight of the polyester polyol (a1) is preferably 100 to 100000 in number average molecular weight. If the number average molecular weight is less than 100, the reactivity may be high and gelation may easily occur. When the number average molecular weight exceeds 100000, the reactivity may be lowered and the cohesive force of the polyurethane polyol itself may be reduced. The amount of the polyester polyol (a1) used is preferably 0 to 90 mol% in the polyol constituting the polyurethane polyol.

As the polyether polyol (a2), any suitable polyether polyol can be used. Examples of such polyether polyol (a2) include polyether polyols obtained by polymerizing an ethylene oxide (oxirane) compound such as ethylene oxide, propylene oxide, butylene oxide, or tetrahydrofuran using water, a low molecular weight polyol such as propylene glycol, ethylene glycol, glycerin, or trimethylolpropane, as an initiator. Specific examples of such polyether polyol (a2) include polyether polyols having a functional group of 2 or more, such as polypropylene glycol, polyethylene glycol, and polytetramethylene glycol.

The polyether polyol (a2) may have any molecular weight from a low molecular weight to a high molecular weight. The polyether polyol (a2) preferably has a number average molecular weight of 100 to 100000. If the number average molecular weight is less than 100, the reactivity may be high and gelation may easily occur. When the number average molecular weight exceeds 100000, the reactivity may be lowered and the cohesive force of the polyurethane polyol itself may be reduced. The amount of the polyether polyol (a2) used is preferably 0 to 90 mol% in the polyol constituting the polyurethane polyol.

The polyether polyol (a2) may be used in combination with, if necessary, a diol such as ethylene glycol, 1, 4-butanediol, neopentyl glycol, butylethylpentanediol, glycerin, trimethylolpropane or pentaerythritol, or a polyamine such as ethylenediamine, N-aminoethylethanolamine, isophoronediamine or xylylenediamine.

The polyether polyol (a2) may be a 2-functional polyether polyol alone, or a polyether polyol having a number average molecular weight of 100 to 100000 and at least 3 hydroxyl groups in 1 molecule may be partially or entirely used. When a polyether polyol having a number average molecular weight of 100 to 100000 and at least 3 hydroxyl groups in 1 molecule is used as a part or all of the polyether polyol (a2), the balance between the adhesive strength and the removability can be improved. When the number average molecular weight of such polyether polyol is less than 100, the reactivity may be high and gelation may be likely to occur. When the number average molecular weight of such a polyether polyol exceeds 100000, the reactivity may be lowered and the cohesive force of the polyurethane polyol itself may be reduced. The number average molecular weight of such polyether polyol is more preferably 100 to 10000.

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, araliphatic polyisocyanates, and alicyclic polyisocyanates.

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

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

Examples of the araliphatic polyisocyanate include ω, ω '-diisocyanate-1, 3-dimethylbenzene, ω' -diisocyanate-1, 4-diethylbenzene, 1, 4-tetramethylxylylene diisocyanate, 1, 3-tetramethylxylylene 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, 6-cyclohexane diisocyanate, 4' -methylenebis (cyclohexyl isocyanate), 1, 4-bis (isocyanatomethyl) cyclohexane, and 1, 4-bis (isocyanatomethyl) cyclohexane.

As the organic polyisocyanate compound (a3), trimethylolpropane adduct, biuret formed by reaction with water, trimer having an isocyanurate ring, and the like can be used in combination.

As the catalyst that can be used in obtaining the polyurethane polyol, any suitable catalyst can be used. Examples of such a catalyst include tertiary amine compounds and organometallic compounds.

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

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

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

Examples of the non-tin compound include titanium compounds such as dibutyltitanium dichloride, tetrabutyl titanate, butoxytitanium trichloride, etc.; lead compounds such as lead oleate, lead 2-ethylhexoate, lead benzoate, and lead naphthenate; iron compounds such as iron 2-ethylhexanoate and iron acetylacetonate; cobalt compounds such as cobalt benzoate and cobalt 2-ethylhexanoate; zinc compounds such as zinc naphthenate and zinc 2-ethylhexanoate; zirconium compounds such as zirconium naphthenate; and the like.

When a catalyst is used for obtaining a polyurethane polyol, in a system in which 2 kinds of polyols, i.e., a polyester polyol and a polyether polyol, are present, there is a problem that gelation or turbidity of a reaction solution is likely to occur in a system in which a catalyst is used alone due to a difference in reactivity. Therefore, these problems can be solved by using 2 kinds of catalysts when obtaining the polyurethane polyol, so that it becomes easy to control the reaction rate, the selectivity of the catalyst, and the like. Examples of the combination of 2 kinds of catalysts include tertiary amine/organic metal type, tin type/non-tin type, and tin type/tin type, preferably tin type/tin type, and more preferably a combination of dibutyltin dilaurate and tin 2-ethylhexanoate. The compounding ratio thereof is preferably less than 1, and more preferably 0.2 to 0.6, in terms of weight ratio, of tin 2-ethylhexanoate/dibutyltin dilaurate. When the compounding ratio is 1 or more, gelation may easily occur due to the balance of catalytic activity.

In the case of using a catalyst when obtaining a polyurethane polyol, the amount of the catalyst used is preferably 0.01 to 1.0% by weight relative to the total amount of the polyester polyol (a1), the polyether polyol (a2) and the organic polyisocyanate compound (a 3).

In the case of using a catalyst in obtaining the polyurethane polyol, the reaction temperature is preferably less than 100 ℃, more preferably from 85 ℃ to 95 ℃. When the temperature is 100 ℃ or higher, the reaction rate and the control of the crosslinked structure may become difficult, and it may become difficult to obtain a polyurethane polyol having a predetermined molecular weight.

The polyurethane polyol can be obtained without using a catalyst. In this case, the reaction temperature is preferably 100 ℃ or higher, more preferably 110 ℃ or higher. When the polyurethane polyol is obtained without a catalyst, the reaction is preferably carried out for 3 hours or more.

Examples of the method for obtaining the polyurethane polyol include the following methods: 1) a method of charging the entire amount of polyester polyol, polyether polyol, catalyst and organic polyisocyanate into a flask; 2) a method of adding polyester polyol, polyether polyol and a catalyst to a flask and adding an organic polyisocyanate dropwise. As a method for obtaining the polyurethane polyol, the method of 2) is preferable in terms of controlling the reaction.

Any suitable solvent may be used in obtaining the polyurethane polyol. Examples of such a solvent include methyl ethyl ketone, ethyl acetate, toluene, xylene, and acetone. Among these solvents, toluene is preferred.

[ A-2-1-b. polyol ]

Examples of the polyol include preferably polyester polyol, polyether polyol, polycaprolactone polyol, polycarbonate polyol and castor oil polyol. The polyol is more preferably a polyether polyol.

The polyester polyol can be obtained, for example, by esterification of a polyol component with 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, 2-butyl-2-ethyl-1, 3-propanediol, 2, 4-diethyl-1, 5-pentanediol, 1, 2-hexanediol, 1, 6-hexanediol, 1, 8-octanediol, 1, 9-nonanediol, 2-methyl-1, 8-octanediol, 1, 8-decanediol, octadecanediol, glycerin, trimethylolpropane, pentaerythritol, hexanetriol, and polypropylene glycol. 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, dimer acid, 2-methyl-1, 4-cyclohexanedicarboxylic acid, 2-ethyl-1, 4-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, isophthalic acid, terephthalic acid, 1, 4-naphthalenedicarboxylic acid, 4' -biphenyldicarboxylic acid, and acid anhydrides thereof.

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

Examples of the polycaprolactone polyol include caprolactone-based polyester diols obtained by ring-opening polymerization of a cyclic ester monomer such as-caprolactone and σ -valerolactone.

Examples of the polycarbonate polyol include: a polycarbonate polyol obtained by subjecting the polyol component and phosgene to a polycondensation reaction; polycarbonate polyols obtained by ester exchange condensation of the above polyol component with a carbonic acid diester such as dimethyl carbonate, diethyl carbonate, dipropyl carbonate, diisopropyl carbonate, dibutyl carbonate, ethylbutyl carbonate, ethylene carbonate, propylene carbonate, diphenyl carbonate, or dibenzyl carbonate; a copolymerized polycarbonate polyol obtained by using 2 or more of the above polyol components in combination; polycarbonate polyols obtained by subjecting the above-mentioned various polycarbonate polyols and a carboxyl group-containing compound to an esterification reaction; polycarbonate polyols obtained by etherification of the above-mentioned various polycarbonate polyols with a hydroxyl group-containing compound; polycarbonate polyols obtained by subjecting the above-mentioned various polycarbonate polyols and an ester compound to an ester exchange reaction; polycarbonate polyols obtained by subjecting the above-mentioned various polycarbonate polyols and a hydroxyl group-containing compound to an ester exchange reaction; polyester polycarbonate polyols obtained by polycondensation of the above polycarbonate polyols with dicarboxylic acid compounds; a copolymerized polyether polycarbonate polyol obtained by copolymerizing the above-mentioned various polycarbonate polyols with an alkylene oxide; and the like.

Examples of the castor oil polyol include castor oil polyols obtained by reacting a castor oil fatty acid with the above polyol component. Specifically, for example, a castor oil polyol obtained by reacting a castor oil fatty acid with polypropylene glycol is exemplified.

The number average molecular weight Mn of the polyol is preferably 300 to 100000, more preferably 400 to 75000, still more preferably 450 to 50000, and particularly preferably 500 to 30000. When the number average molecular weight Mn of the polyol is within the above range, the surface protection film of the present invention can be more hardly peeled from an adherend, and the re-peeling over time can be further suppressed.

The polyol preferably contains a polyol (A1) having 3 OH groups and a number average molecular weight Mn of 300 to 100000. The number of the polyhydric alcohols (a1) may be only 1, or may be 2 or more.

The content of the polyol (a1) in the polyol 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. When the content ratio of the polyol (a1) in the polyol is within the above range, the surface protection film of the present invention can be more resistant to peeling from an adherend, and can further suppress re-peeling over time.

The number average molecular weight Mn of the polyol (A1) is preferably 1000 to 100000, more preferably 1200 to 80000, still more preferably 1500 to 70000, still more preferably 1750 to 50000, particularly preferably 1500 to 40000, and most preferably 2000 to 30000. When the number average molecular weight Mn of the polyol (a1) is within the above range, the surface protection film of the present invention can be more resistant to peeling from an adherend, and re-peeling over time can be further suppressed.

The polyol may contain a polyol (A2) having 3 or more OH groups and a number average molecular weight Mn of 20000 or less. The number of the polyhydric alcohols (a2) may be only 1, or may be 2 or more. The number average molecular weight Mn of the polyol (A2) is preferably 100 to 20000, more preferably 150 to 10000, further preferably 200 to 7500, particularly preferably 300 to 6000, most preferably 300 to 5000. When the number average molecular weight Mn of the polyol (a2) is out of the above range, the surface protection film of the present invention may have a high increase in peeling force with time. Examples of the polyol (a2) include preferably a polyol (triol) having 3 OH groups, a polyol (tetraol) having 4 OH groups, a polyol (pentaol) having 5 OH groups, and a polyol (hexaol) having 6 OH groups.

The total amount of the polyol (tetrahydric alcohol) having 4 OH groups, the polyol (pentahydric alcohol) having 5 OH groups, and the polyol (hexahydric alcohol) having 6 OH groups as the polyol (a2) is preferably 70% by weight or less, more preferably 60% by weight or less, further preferably 40% by weight or less, and particularly preferably 30% by weight or less, in terms of the content ratio in the polyol. When the total amount of the polyol (tetrahydric alcohol) having 4 OH groups, the polyol (pentahydric alcohol) having 5 OH groups, and the polyol (hexahydric alcohol) having 6 OH groups, which are the polyol (a2), in the polyol is in the above range, the pressure-sensitive adhesive layer having excellent transparency can be provided, and the surface-protecting film of the present invention can be more resistant to peeling from an adherend and can further suppress re-peeling over time.

The content of the polyol (a2) in the polyol is preferably 95 wt% or less, and more preferably 0 wt% to 75 wt%. When the content ratio of the polyol (a2) in the polyol is within the above range, the surface protection film of the present invention can be more resistant to peeling from an adherend, and can further suppress re-peeling over time.

The content of the polyol having 4 or more OH groups and a number average molecular weight Mn of 20000 or less as the polyol (a2) is preferably less than 70% by weight, more preferably 60% by weight or less, still more preferably 50% by weight or less, particularly preferably 40% by weight or less, and most preferably 30% by weight or less, based on the total amount of the polyol. When the content ratio of the polyol having 4 or more OH groups and a number average molecular weight Mn of 20000 or less as the polyol (a2) is in the above range with respect to the entire polyol, a pressure-sensitive adhesive layer having excellent transparency can be provided, and the surface protection film of the present invention can be more resistant to peeling from an adherend, and can further suppress re-peeling over time.

[ A-2-1-c. acrylic resin ]

As the acrylic resin, any suitable acrylic adhesive such as a known acrylic adhesive described in, for example, japanese patent application laid-open No. 2013-241606 can be used as long as the effects of the present invention are not impaired.

The acrylic resin may contain any appropriate component within a range not impairing the effects of the present invention. Examples of such components include resin components other than acrylic resins, tackifiers, inorganic fillers, organic fillers, metal powders, pigments, foils, softeners, antioxidants, electrical conduction agents, ultraviolet absorbers, antioxidants, light stabilizers, surface lubricants, leveling agents, corrosion inhibitors, heat stabilizers, polymerization inhibitors, lubricants, solvents, catalysts, and the like.

[ A-2-1-d. rubber-based resin ]

As the rubber-based resin, any suitable rubber-based adhesive such as a known rubber-based adhesive described in, for example, japanese patent application laid-open publication No. 2015-074771 can be used as long as the effects of the present invention are not impaired. These may be 1 kind only or 2 or more kinds.

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

[ A-2-1-e. Silicone resin ]

As the silicone-based adhesive, any suitable silicone-based adhesive such as the known silicone-based adhesive described in, for example, japanese patent application laid-open publication No. 2014-047280 can be used as long as the effects of the present invention are not impaired. These may be 1 kind only or 2 or more kinds.

The silicone resin may contain any suitable component within a range not impairing the effects of the present invention. Examples of such components include resin components other than silicone resins, tackifiers, inorganic fillers, organic fillers, metal powders, pigments, foils, softeners, anti-aging agents, conductive agents, ultraviolet absorbers, antioxidants, light stabilizers, surface lubricants, leveling agents, corrosion inhibitors, heat stabilizers, polymerization inhibitors, lubricants, solvents, catalysts, and the like.

< A-2-2. Silicone additive >

The silicone additive may be any suitable silicone additive as long as the effects of the present invention are not impaired. The silicone additive preferably includes at least 1 selected from a silicone bond-containing compound, a hydroxyl group-containing silicone compound, and a crosslinkable functional group-containing silicone compound.

The number of the silicone additives may be only 1, or may be 2 or more.

Examples of the compound having a siloxane bond include polyether-modified polyorganosiloxanes obtained by introducing polyether groups into the main chain or side chain of a polyorganosiloxane skeleton (such as polydimethylsiloxane), polyester-modified polyorganosiloxanes obtained by introducing polyester groups into the main chain or side chain of a polyorganosiloxane skeleton, polyorganosiloxanes obtained by introducing organic compounds into the main chain or side chain of a polyorganosiloxane skeleton, silicone-modified (meth) acrylic resins obtained by introducing polyorganosiloxanes into (meth) acrylic resins, silicone-modified organic compounds obtained by introducing polyorganosiloxanes into organic compounds, and silicone-containing organic compounds obtained by copolymerizing organic compounds and organosilicon compounds. Examples of commercially available products of such siloxane bond-containing polymers include those having a trade name "LE-302" (manufactured by Kyoeisha chemical Co., Ltd.), and BYK-series leveling agents ("BYK-300", "BYK-301/302", "BYK-306", "BYK-307", "BYK-310", "BYK-315", "BYK-313", "BYK-320", "BYK-322", "BYK-323", "BYK-325", "BYK-330", "BYK-331", "BYK-333", "BYK-337", "BYK-341", "BYK-344", "BYK-345/346", "BYK-347", "BYK-348", "BYK-349", "BYK-370", "BYK-375", "BYK-377"), "BYK-378", "BYK-UV 3500", "BYK-UV 3510", "BYK-UV 3570", "BYK-3550", "BYK-SILCLEAN 3700", "BYK-SILCLEAN 3720", etc.), AC series leveling agents ("AC FS 180", "AC FS 360", "AC S20", etc.) manufactured by Algin Chemie, POLYFLOW series leveling agents ("POLYFLOW KL-400X", "POLYFLOW KL-400 HF", "POLYFLOW KL-401", "POLYW KL-402", "POLYFLOW KL-403", "POLYFLOW KL-404", etc.) manufactured by Kp series leveling agents ("KP-323", "KP-326", "KP-341", "104", "KP-110", "KP-112", etc.) manufactured by Kyoto chemical industries, etc.), X series leveling agents ("KP-22 KP series" manufactured by Kyoto chemical Co., Ltd, KF series, Dow Corning Toray Co., Ltd., "LP-7001", "LP-7002", "8032 ADDITIVE", "57 ADDITIVE", "L-7604", "FZ-2110", "FZ-2105", "67 ADDITIVE", "8618 ADDITIVE", "3 ADDITIVE", "56 ADDITIVE", etc.).

Examples of the hydroxyl group-containing silicone compound include polyether-modified polyorganosiloxanes obtained by introducing polyether groups into the main chain or side chain of a polyorganosiloxane skeleton (such as polydimethylsiloxane), polyester-modified polyorganosiloxanes obtained by introducing polyester groups into the main chain or side chain of a polyorganosiloxane skeleton, polyorganosiloxanes introduced into organic compounds obtained by introducing organic compounds into the main chain or side chain of a polyorganosiloxane skeleton, organosilicon-modified (meth) acrylic resins obtained by introducing polyorganosiloxanes into (meth) acrylic resins, organosilicon-modified organic compounds obtained by introducing polyorganosiloxanes into organic compounds, and organosilicon-containing organic compounds obtained by copolymerizing organic compounds and organosilicon compounds. Of these, the hydroxyl group may be contained in the polyorganosiloxane skeleton, or may be contained in a polyether group, a polyester group, a (meth) acryloyl group, or an organic compound. Examples of commercially available products of such hydroxyl group-containing silicones include trade names "X-22-4015", "X-22-4039", "KF 6000", "KF 6001", "KF 6002", "KF 6003", "X-22-170 BX", "X-22-170 DX", "X-22-176F" (manufactured by shin-Etsu chemical Co., Ltd.) "BYK-370", "BYK-SILCLEAN 3700" and "BYK-SILCLEAN 3720" manufactured by BYK Japan KK..

Examples of the crosslinkable functional group-containing silicone compound include polyether-modified polyorganosiloxanes obtained by introducing polyether groups into the main chain or side chain of a polyorganosiloxane skeleton (such as polydimethylsiloxane), polyester-modified polyorganosiloxanes obtained by introducing polyester groups into the main chain or side chain of a polyorganosiloxane skeleton, polyorganosiloxanes introduced into organic compounds obtained by introducing organic compounds into the main chain or side chain of a polyorganosiloxane skeleton, silicone-modified (meth) acrylic resins obtained by introducing polyorganosiloxanes into (meth) acrylic resins, silicone-modified organic compounds obtained by introducing polyorganosiloxanes into organic compounds, and silicone-containing organic compounds obtained by copolymerizing organic compounds and organosilicon compounds. Of these, the crosslinkable functional group may be one having a polyorganosiloxane skeleton, or may be one having 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 products of such an isocyanate group-containing silicone include "BY 16-855", "SF 8413", "BY 16-839", "SF 8421", "BY 16-750", "BY 16-880", "BY 16-152C", KF-868 "," KF-865 "," KF-864 "," KF-859 "," KF-393 "," KF-860 "," KF-880 "," KF-8004 "," KF-8002 "," KF-8005 "," KF-867 "," KF-8021 "," KF-869 "," KF-861 "," X-22-343 "," KF-101 "," X-22-2000 "," X-22-4741 ", manufactured BY Dow Corning Toray Co., Ltd, "KF-1002", "KF-2001", "X-22-3701E", "X-22-164A", "X-22-164B", "X-22-164 AS", "X-22-2445", etc.

< A-2-3 > fluorine-based additive >

The fluorine-based additive may be any suitable fluorine-based additive within a range not impairing the effects of the present invention. The fluorine-containing additive preferably includes at least 1 kind selected from a fluorine-containing compound, a hydroxyl group-containing fluorine-containing compound, and a crosslinkable functional group-containing fluorine-containing compound.

The fluorine-containing additive may be 1 kind or 2 or more kinds.

Examples of the fluorine-containing compound include a compound having a fluoroaliphatic hydrocarbon skeleton, a fluorine-containing organic compound obtained by copolymerizing an organic compound and a fluorine compound, and a fluorine-containing compound containing an organic compound. Examples of the fluoroaliphatic hydrocarbon skeleton include fluoro C1-C10 alkanes such as fluoromethane, fluoroethane, fluoropropane, fluoroisopropane, fluorobutane, fluoroisobutane, fluorotert-butane, fluoropentane, and fluorohexane. Examples of commercially available products of such fluorine-containing compounds include leveling agents of Surflon series (for example, "S-242", "S-243", "S-420", "S-611", "S-651" and "S-386" manufactured by Ltd.), leveling agents of BYK series (for example, "BYK-340") manufactured by BYK Japan KK., leveling agents of AC series (for example, "AC 110 a" and "AC 100 a" manufactured by Algin Chemie), leveling agents of MEGAFACE series (for example, "MEGAFACE F-114", "MEGAFACE F-410", "MEGAFACE F-444", "MEGAFACE EXPTP-2066", "MEGAFACE F-430", "MEGAFACE F-SF", "MEGAFACE F-477", "MEGAFACE F-552", "MEGAFACE F-472", "MEGAFACE F-554"), "MEGAFACE F-555", "MEGAFACE R-94", "MEGAFACE RS-72-K", "MEGAFACE RS-75", "MEGAFACE F-556", "MEGAFACE EXPTF-1367", "MEGAFACE EXPTF-1437", "MEGAFACE F-558", "MEGAFACE EXPTF-1537", etc.), FC series leveling agents ("FC-4430", "FC-4432", etc.) manufactured by Sumitomo 3M Limited, Ftergent series leveling agents ("Ftergent 100", "Ftergent 100C", "Ftergent 110", "Ftergent 150 CH", "Ftergent A-K", "Ftergent 501", "Ftergent 250", "Ftergent 222F", "Ftergent 208G", "Ftergent 300", "Ftergent 310", "Ftergent 400, SW 400", etc.), North series leveling agents ("PF A-136A" ", PF" manufactured by North chemical industries, Inc, "PF-156A", "PF-151N", "PF-636", "PF-6320", "PF-656", "PF-6520", "PF-651", "PF-652", "PF-3320", etc.), etc.

Examples of the hydroxyl group-containing fluorine-based compound include conventionally known resins, and examples thereof include hydroxyl group-containing fluororesins described in pamphlet of International publication No. 94/06870, Japanese patent application laid-open No. 8-12921, Japanese patent application laid-open No. 10-72569, Japanese patent application laid-open No. 4-275379, pamphlet of International publication No. 97/11130, and pamphlet of International publication No. 96/26254. Examples of the other hydroxyl-containing fluororesin include fluoroolefin copolymers described in, for example, Japanese patent application laid-open Nos. 8-231919, 10-265731, 10-204374 and 8-12922. Further, there may be mentioned a copolymer of a compound having a fluorinated alkyl group in a hydroxyl group-containing compound, a fluorine-containing organic compound obtained by copolymerizing a fluorine-containing compound in a hydroxyl group-containing compound, a fluorine-containing compound containing a hydroxyl group-containing organic compound, and the like. Examples of commercially available products of such a hydroxyl group-containing fluorine compound include a trade name "LUMIFLON" (manufactured by Asahi Glass Co., Ltd.), a trade name "Cefralcoat" (manufactured by Central Glass Co., Ltd.), a trade name "Zaflo" (manufactured by Toyo Seisakusho Co., Ltd.), a trade name "ZEFFLE" (manufactured by DAIKIN INDUSTRIES, Ltd.), a trade name "MEGAFACE F-571" and a trade name "FLUONATE" (manufactured by DIC).

Examples of the crosslinkable functional group-containing fluorine-based compound include a carboxylic acid compound having a fluorinated alkyl group such as perfluorooctanoic acid, a copolymer of a compound having a fluorinated alkyl group in the crosslinkable functional group-containing compound, a fluorine-containing organic compound obtained by copolymerizing a fluorine-containing compound in the crosslinkable functional group-containing compound, a fluorine-containing compound containing the crosslinkable functional group-containing compound, and the like. Examples of commercially available products of such crosslinkable functional group-containing fluorine-based compounds include, for example, trade names "MEGAFACE F-570", "MEGAFACE RS-55", "MEGAFACE RS-56", "MEGAFACE RS-72-K", "MEGAFACE RS-75", "MEGAFACE RS-76-E", "MEGAFACE RS-76-NS", "MEGAFACE RS-78" and "MEGAFACE RS-90" (available from DIC).

< A-2-4. urethane resin >

The urethane prepolymer and the polyol as the base polymer may be each combined with the polyfunctional isocyanate compound (B) to be components of a composition for forming a urethane resin. By using the above-described substance as a component of the composition for forming a urethane resin, the surface protection film of the present invention can be more hardly peeled from an adherend, and the re-peeling with time can be further suppressed.

The composition for forming a urethane resin may contain any appropriate other component within a range not impairing the effects of the present invention. Examples of such components include resin components other than urethane-based resins, tackifiers, inorganic fillers, organic fillers, metal powders, pigments, foils, softeners, anti-aging agents, conductive agents, ultraviolet absorbers, antioxidants, light stabilizers, surface lubricants, leveling agents, corrosion inhibitors, heat stabilizers, polymerization inhibitors, lubricants, solvents, catalysts, and the like.

The composition for forming a urethane resin preferably contains an anti-deterioration agent such as an antioxidant, an ultraviolet absorber, and a light stabilizer. The composition for forming a urethane resin contains a deterioration preventing agent, and therefore, even when the formed pressure-sensitive adhesive layer is stored in a heated state after being attached to an adherend, the composition is less likely to cause adhesive residue or the like on the adherend and has excellent adhesive residue prevention properties. The number of the deterioration preventing agents may be only 1, or may be 2 or more. As the deterioration preventing agent, an antioxidant is particularly preferable.

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

Examples of the radical chain inhibitor include a phenol-based antioxidant and an amine-based antioxidant.

Examples of the peroxide decomposer include a sulfur-based antioxidant, a phosphorus-based antioxidant and the like.

Examples of the phenol antioxidant include monophenol antioxidants, bisphenol antioxidants, and high-molecular phenol antioxidants.

Examples of the monophenol-based antioxidant include 2, 6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2, 6-di-t-butyl-4-ethylphenol, and stearyl β - (3, 5-di-t-butyl-4-hydroxyphenyl) propionate.

Examples of the bisphenol-based antioxidant include 2,2 '-methylenebis (4-methyl-6-tert-butylphenol), 2' -methylenebis (4-ethyl-6-tert-butylphenol), 4 '-thiobis (3-methyl-6-tert-butylphenol), 4' -butylidenebis (3-methyl-6-tert-butylphenol), 3, 9-bis [1, 1-dimethyl-2- [ β - (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy ] ethyl ]2,4,8, 10-tetraoxaspiro [5,5] undecane, and the like.

Examples of the high-molecular-weight phenolic antioxidant include 1,1, 3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 1,3, 5-trimethyl-2, 4, 6-tris (3, 5-di-t-butyl-4-hydroxybenzyl) benzene, tetrakis- [ methylene-3- (3 ', 5 ' -di-t-butyl-4 ' -hydroxyphenyl) propionate ] methane, bis [3,3 ' -bis- (4 ' -hydroxy-3 ' -t-butylphenyl) butanoic acid ] diol ester, 1,3, 5-tris (3 ', 5 ' -di-t-butyl-4 ' -hydroxybenzyl) -s-triazine-2, 4,6- (1H, 5-bis (3,5 ' -di-t-butyl-4 ' -hydroxybenzyl) butyrate, 3H, 5H) triones, tocopherols, and the like.

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

Examples of the phosphorus-based antioxidant include triphenyl phosphite, diphenylisodecyl phosphite, and phenyldiisodecyl phosphite.

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

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

Examples of the benzotriazole-based ultraviolet absorber include 2- (2 '-hydroxy-5' -methylphenyl) benzotriazole, 2- (2 '-hydroxy-5' -tert-butylphenyl) benzotriazole, 2- (2 '-hydroxy-3', 5 '-di-tert-butylphenyl) benzotriazole, 2- (2' -hydroxy-3 '-tert-butyl-5' -methylphenyl) -5-chlorobenzotriazole, 2- (2 '-hydroxy-3', 5 '-di-tert-butylphenyl) 5-chlorobenzotriazole, 2- (2' -hydroxy-3 ', 5' -di-tert-amylphenyl) benzotriazole, 2- (2 '-hydroxy-4' -octyloxyphenyl) benzotriazole, 2-bis (t-butylphenyl) benzotriazole, and mixtures thereof, 2- [2 '-hydroxy-3' - (3 ", 4", 5 ", 6" -tetrahydrophthalimidomethyl) -5 '-methylphenyl ] benzotriazole, 2' -methylenebis [4- (1,1,3, 3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol ], 2- (2 '-hydroxy-5' -methacryloxyphenyl) -2H-benzotriazole, and the like.

Examples of the salicylic acid-based ultraviolet absorber include phenyl salicylate, p-tert-butyl phenyl salicylate, and p-octyl phenyl salicylate.

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

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

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

Examples of the ultraviolet stabilizer include nickel bis (octylphenyl) sulfide, [2, 2' -thiobis (4-tert-octylphenol) ] -n-butylamine nickel, 3, 5-di-tert-butyl-4-hydroxybenzylphosphonate monoethyl ester nickel complex, nickel dibutyldithiocarbamate, a benzoate-type quencher, and nickel dibutyldithiocarbamate.

[ A-2-4-a. urethane-based resin formed from a composition containing a urethane prepolymer and a polyfunctional isocyanate compound (B) ]

The urethane resin formed from the composition containing the urethane prepolymer and the polyfunctional isocyanate compound (B) includes, for example, a urethane resin formed from a composition containing a urethane polyol as the urethane prepolymer and the polyfunctional isocyanate compound (B).

The number of urethane prepolymers may be only 1, or may be 2 or more.

The number of the polyfunctional isocyanate compounds (B) may be only 1, or may be 2 or more.

As the polyfunctional isocyanate compound (B), any suitable polyfunctional isocyanate compound that can be used in the urethanization reaction can be used. Examples of the polyfunctional isocyanate compound (B) include polyfunctional aliphatic isocyanate compounds, polyfunctional alicyclic isocyanates, and polyfunctional aromatic isocyanate compounds.

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

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 tetramethylxylylene diisocyanate, and the like.

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

Examples of the polyfunctional isocyanate compound (B) include trimethylolpropane adducts, biuret products obtained by reaction with water, and trimers having an isocyanurate ring of the above polyfunctional isocyanate compounds. In addition, they may be used in combination.

The composition containing the urethane prepolymer and the polyfunctional isocyanate compound (B) may contain any suitable other components within a range not impairing the effects of the present invention. Examples of such other components include resin components other than the urethane resin, a thickener, an inorganic filler, an organic filler, metal powder, a pigment, a foil, a softener, an antioxidant, a conductive agent, an ultraviolet absorber, an antioxidant, a light stabilizer, a surface lubricant, a leveling agent, an anticorrosive agent, a heat stabilizer, a polymerization inhibitor, a lubricant, a solvent, a catalyst, and the like.

As a method for forming a polyurethane-based resin from a composition containing a urethane prepolymer and a polyfunctional isocyanate compound (B), any suitable production method can be employed as long as it is a method for producing a polyurethane-based resin using a so-called "urethane prepolymer" as a raw material.

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

The equivalent ratio of NCO groups to OH groups in the urethane prepolymer and the polyfunctional isocyanate compound (B) is preferably 5.0 or less, more preferably 0.01 to 4.75, still more preferably 0.02 to 4.5, particularly preferably 0.03 to 4.25, and most preferably 0.05 to 4.0 in terms of NCO groups/OH groups. When the equivalent ratio of NCO groups/OH groups is within the above range, the surface-protecting film of the present invention can be more resistant to peeling from an adherend, and can further suppress re-peeling over time.

The content of the polyfunctional isocyanate compound (B) is preferably 0.01 to 30% by weight, more preferably 0.05 to 25% by weight, still more preferably 0.1 to 20% by weight, particularly preferably 0.5 to 17.5% by weight, and most preferably 1 to 15% by weight, based on the urethane prepolymer. When the content ratio of the polyfunctional isocyanate compound (B) is within the above range, the surface-protecting film of the present invention can be more hardly peeled from an adherend, and the re-peeling over time can be further suppressed.

[ A-2-4-b. urethane resin formed from a composition containing a polyol and a polyfunctional isocyanate compound (B) ]

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

The number of the polyhydric alcohols may be only 1, or may be 2 or more.

The number of the polyfunctional isocyanate compounds (B) may be only 1, or may be 2 or more.

As the polyfunctional isocyanate compound (B), the aforementioned can be applied.

The equivalent ratio of NCO groups to OH groups in the polyol (A) and the polyfunctional isocyanate compound (B) is preferably 5.0 or less, more preferably 0.1 to 3.0, further preferably 0.2 to 2.5, particularly preferably 0.3 to 2.25, and most preferably 0.5 to 2.0 in terms of NCO groups/OH groups. When the equivalent ratio of NCO groups/OH groups is within the above range, the surface-protecting film of the present invention can be more resistant to peeling from an adherend, and can further suppress re-peeling over time.

The content of the polyfunctional isocyanate compound (B) is preferably 1.0 to 30% by weight, more preferably 1.5 to 27% by weight, even more preferably 2.0 to 25% by weight, particularly preferably 2.3 to 23% by weight, and most preferably 2.5 to 20% by weight, based on the polyol. When the content ratio of the polyfunctional isocyanate compound (B) is within the above range, the surface-protecting film of the present invention can be more hardly peeled from an adherend, and the re-peeling over time can be further suppressed.

Specifically, the polyurethane resin is preferably formed by curing a composition containing a polyol and a polyfunctional isocyanate compound (B). As a method for forming a urethane resin by curing a composition containing a polyol and a polyfunctional isocyanate compound (B), any appropriate method such as a urethanization reaction method using bulk polymerization, solution polymerization, or the like can be employed within the range not impairing the effects of the present invention.

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

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

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

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

Examples of the titanium compound include dibutyltitanium dichloride, tetrabutyl titanate, butoxytitanium trichloride, and the like.

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

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

Examples of the cobalt-based 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, and 1, 8-diazabicyclo (5,4,0) -undec-7-ene.

The number of the catalyst may be only 1, or may be 2 or more. In addition, a catalyst, a crosslinking retarder, and the like may be used in combination. The amount of the catalyst is preferably 0.005 to 1.00% by weight, more preferably 0.01 to 0.75% by weight, further preferably 0.01 to 0.50% by weight, particularly preferably 0.01 to 0.20% by weight, based on the polyol. When the amount of the catalyst is within the above range, the surface-protecting film of the present invention can be more hardly peeled from an adherend, and the re-peeling over time can be further suppressed.

In the composition containing the polyol and the polyfunctional isocyanate compound (B), any suitable other component may be contained within a range not impairing the effects of the present invention. Examples of such other components include resin components other than the urethane resin, a thickener, an inorganic filler, an organic filler, metal powder, a pigment, a foil, a softener, an antioxidant, a conductive agent, an ultraviolet absorber, an antioxidant, a light stabilizer, a surface lubricant, a leveling agent, an anticorrosive agent, a heat stabilizer, a polymerization inhibitor, a lubricant, a solvent, a catalyst, and the like.

< A-2-5. fatty acid ester >

The adhesive composition preferably comprises a fatty acid ester. The number of the fatty acid esters may be only 1, or may be 2 or more. When the adhesive composition contains a fatty acid ester, the surface protective film of the present invention can further exhibit the following effects: the release from the adherend can be further suppressed, and the releasability with time can be further suppressed, and the staining of the adherend surface due to the attachment to the adherend is low.

The number average molecular weight Mn of the fatty acid ester is preferably 100 to 800, more preferably 150 to 750, further preferably 200 to 700, particularly preferably 200 to 650, and most preferably 200 to 600. When the number average molecular weight Mn of the fatty acid ester is within the above range, the surface protection film of the present invention can further exhibit the following effects: the release from the adherend can be further suppressed, and the releasability with time can be further suppressed, and the staining of the adherend surface due to the attachment to the adherend is low.

As the fatty acid ester, any suitable fatty acid ester may be used within a range not impairing the effects of the present invention. Examples of such fatty acid esters include polyoxyethylene bisphenol a laurate, butyl stearate, 2-ethylhexyl palmitate, 2-ethylhexyl stearate, monoglyceride behenate, cetyl 2-ethylhexanoate, isopropyl myristate, isopropyl palmitate, cholesterol isostearate, lauryl methacrylate, methyl cocoate, methyl laurate, methyl oleate, methyl stearate, myristyl myristate, octyldodecyl myristate, pentaerythritol monooleate, pentaerythritol monostearate, pentaerythritol tetrapalmitate, stearyl stearate, isotridecyl stearate, triglyceryl 2-ethylhexanoate, butyl laurate, and octyl oleate.

When the adhesive composition contains a fatty acid ester, the content of the fatty acid ester is preferably 0.01 to 50 parts by weight, more preferably 0.05 to 45 parts by weight, even more preferably 0.1 to 40 parts by weight, even more preferably 0.3 to 35 parts by weight, even more preferably 0.5 to 30 parts by weight, particularly preferably 0.5 to 25 parts by weight, and most preferably 0.5 to 20 parts by weight, based on 100 parts by weight of the base polymer. When the content ratio of the fatty acid ester is within the above range with respect to 100 parts by weight of the base polymer, the surface protective film of the present invention can further exhibit the following effects: the release from the adherend can be further suppressed, and the releasability with time can be further suppressed, and the staining of the adherend surface due to the attachment to the adherend is low.

< A-2-6. other ingredients >

The adhesive composition may contain any suitable other component within a range not impairing the effects of the present invention. Examples of such other components include other resin components, tackifiers, inorganic fillers, organic fillers, metal powders, pigments, foils, softeners, antioxidants, conductive agents, ultraviolet absorbers, antioxidants, light stabilizers, surface lubricants, leveling agents, anticorrosion agents, heat stabilizers, polymerization inhibitors, lubricants, solvents, catalysts, and the like.

The adhesive composition may comprise an ionic liquid comprising a fluoro organic anion. By including an ionic liquid containing a fluorine organic anion in the adhesive composition, an adhesive composition having very excellent antistatic properties can be provided. Such ionic liquids may be only 1 type, or may be 2 or more types.

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

As the ionic liquid, any suitable ionic liquid may be used as long as it contains a fluorinated organic anion, within the range that does not impair the effects of the present invention. The ionic liquid is preferably an ionic liquid composed of a fluorine organic anion and an onium cation. By using an ionic liquid composed of a fluorine organic anion and an onium cation as the ionic liquid, an adhesive composition having extremely excellent antistatic properties can be provided.

As the onium cation which can constitute the ionic liquid, any suitable onium cation may be used within a range not impairing the effects of the present invention. The onium cation is preferably at least 1 selected from the group consisting of nitrogen-containing onium cations, sulfur-containing onium cations, and phosphorus-containing onium cations. By selecting these onium cations, an adhesive composition extremely excellent in antistatic property can be provided.

The onium cation capable of constituting the ionic liquid is preferably at least 1 kind selected from cations having structures represented by general formulae (1) to (5).

In the general formula (1), Ra represents a C4-20 hydrocarbon group and may contain a hetero atom, and Rb and Rc may be the same or different and represent hydrogen or a C1-16 hydrocarbon group and may contain a hetero atom. In the case where the nitrogen atom contains a double bond, there is no Rc.

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

In the general formula (3), Rh represents a hydrocarbon group having 2 to 20 carbon atoms and may contain a hetero atom, and Ri, Rj and Rk are the same or different and represent hydrogen or a hydrocarbon group 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, and Rl, Rm, Rn, and Ro are the same or different and represent a hydrocarbon group having 1 to 20 carbon atoms and may contain a hetero atom. Wherein, when Z is a sulfur atom, Ro 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, a cation having a pyrrole skeleton, and the like.

Specific examples of the cation represented by the general formula (1) include pyridinium cations such as 1-ethylpyridinium cation, 1-butylpyridinium cation, 1-hexylpyridinium cation, 1-ethyl-3-methylpyridinium cation, 1-butyl-3-methylpyridinium cation, 1-hexyl-3-methylpyridinium cation, 1-butyl-4-methylpyridinium cation, 1-octyl-4-methylpyridinium cation, 1-butyl-3, 4-dimethylpyridinium cation, and 1, 1-dimethylpyrrolidinium cation; 1-ethyl-1-methylpyrrolidinium cation, 1-methyl-1-propylpyrrolidinium cation, 1-methyl-1-butylpyrrolidinium cation, 1-methyl-1-pentylpyrrolidinium cation, 1-methyl-1-hexylpyrrolidinium cation, 1-methyl-1-heptylpyrrolidinium cation, 1-ethyl-1-propylpyrrolidinium cation, 1-ethyl-1-butylpyrrolidinium cation, 1-ethyl-1-pentylpyrrolidinium cation, 1-ethyl-1-hexylpyrrolidinium cation, 1-ethyl-1-heptylpyrrolidinium cation, 1-dipropylpyrrolidinium cation, 1-propylpyrrolidinium cation, 1-ethylpyrrolidinium cation, 1-propylpyrrolidinium cation, and mixtures thereof, Pyrrolidinium cations such as 1-propyl-1-butylpyrrolidinium cation and 1, 1-dibutylpyrrolidinium cation; 1-propylpiperidinium cation, 1-pentylpiperidinium cation, 1-methyl-1-ethylpiperidinium cation, 1-methyl-1-propylpiperidinium cation, 1-methyl-1-butylpiperidinium cation, 1-methyl-1-pentylpiperidinium cation, 1-methyl-1-hexylpiperidinium cation, 1-methyl-1-heptylpiperidinium cation, 1-ethyl-1-propylpiperidinium cation, 1-ethyl-1-butylpiperidinium cation, 1-ethyl-1-pentylpiperidinium cation, 1-ethyl-1-hexylpiperidinium cation, 1-ethyl-1-heptylpiperidinium cation, 1-ethyl-1-pentylpiperidinium cation, 1-ethyl-1-hexylpiperidinium cation, 1-ethyl, Piperidinium cations such as 1-propyl-1-butylpiperidinium cation, 1-dimethylpiperidinium cation, 1-dipropylpiperidinium cation and 1, 1-dibutylpiperidinium cation; 2-methyl-1-pyrroline cation; 1-ethyl-2-phenylindole cation; 1, 2-dimethylindole cation; a 1-ethyl carbazole cation; and the like.

Among these, from the viewpoint of further exhibiting the effect of the present invention, preferred examples thereof include pyridinium cations such as 1-ethylpyridinium cation, 1-butylpyridinium cation, 1-hexylpyridinium cation, 1-ethyl-3-methylpyridinium cation, 1-butyl-3-methylpyridinium cation, 1-hexyl-3-methylpyridinium cation, 1-butyl-4-methylpyridinium cation, and 1-octyl-4-methylpyridinium cation; 1-ethyl-1-methylpyrrolidinium cation, 1-methyl-1-propylpyrrolidinium cation, 1-methyl-1-butylpyrrolidinium cation, 1-methyl-1-pentylpyrrolidinium cation, 1-methyl-1-hexylpyrrolidinium cation, 1-methyl-1-heptylpyrrolidinium cation, pyrrolidinium cations such as 1-ethyl-1-propylpyrrolidinium cation, 1-ethyl-1-butylpyrrolidinium cation, 1-ethyl-1-pentylpyrrolidinium cation, 1-ethyl-1-hexylpyrrolidinium cation, and 1-ethyl-1-heptylpyrrolidinium cation; 1-methyl-1-ethylpiperidinium cation, 1-methyl-1-propylpiperidinium cation, 1-methyl-1-butylpiperidinium cation, 1-methyl-1-pentylpiperidinium cation, 1-methyl-1-hexylpiperidinium cation, 1-methyl-1-heptylpiperidinium cation, piperidinium cations such as 1-ethyl-1-propylpiperidinium cation, 1-ethyl-1-butylpiperidinium cation, 1-ethyl-1-pentylpiperidinium cation, 1-ethyl-1-hexylpiperidinium cation, 1-ethyl-1-heptylpiperidinium cation, and 1-propyl-1-butylpiperidinium cation; and the like, more preferably 1-hexylpyridinium cation, 1-ethyl-3-methylpyridinium cation, 1-butyl-3-methylpyridinium cation, 1-octyl-4-methylpyridinium cation, 1-methyl-1-propylpyrrolidinium cation, 1-methyl-1-propylpiperidinium cation.

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

Specific examples of the cation represented by the general formula (2) include, for example, a1, 3-dimethylimidazolium cation, a1, 3-diethylimidazolium cation, a 1-ethyl-3-methylimidazolium cation, a 1-butyl-3-methylimidazolium cation, a 1-hexyl-3-methylimidazolium cation, a 1-octyl-3-methylimidazolium cation, a 1-decyl-3-methylimidazolium cation, a 1-dodecyl-3-methylimidazolium cation, a 1-tetradecyl-3-methylimidazolium cation, a1, 2-dimethyl-3-propylimidazolium cation, a 1-ethyl-2, 3-dimethylimidazolium cation, a, Imidazolium cations such as 1-butyl-2, 3-dimethylimidazolium cation and 1-hexyl-2, 3-dimethylimidazolium cation; tetrahydropyrimidinium cations such as 1, 3-dimethyl-1, 4,5, 6-tetrahydropyrimidinium cation, 1,2, 3-trimethyl-1, 4,5, 6-tetrahydropyrimidinium cation, 1,2,3, 4-tetramethyl-1, 4,5, 6-tetrahydropyrimidinium cation, 1,2,3, 5-tetramethyl-1, 4,5, 6-tetrahydropyrimidinium cation; dihydropyrimidinium cations such as 1, 3-dimethyl-1, 4-dihydropyrimidinium cation, 1, 3-dimethyl-1, 6-dihydropyrimidinium cation, 1,2, 3-trimethyl-1, 4-dihydropyrimidinium cation, 1,2, 3-trimethyl-1, 6-dihydropyrimidinium cation, 1,2,3, 4-tetramethyl-1, 4-dihydropyrimidinium cation, and 1,2,3, 4-tetramethyl-1, 6-dihydropyrimidinium cation; and the like.

Among these, from the viewpoint of further exhibiting the effect of the present invention, 1, 3-dimethylimidazolium cation, 1, 3-diethylimidazolium cation, 1-ethyl-3-methylimidazolium cation, 1-butyl-3-methylimidazolium cation, 1-hexyl-3-methylimidazolium cation are preferable, imidazolium cations such as 1-octyl-3-methylimidazolium cation, 1-decyl-3-methylimidazolium cation, 1-dodecyl-3-methylimidazolium cation, and 1-tetradecyl-3-methylimidazolium cation, and more preferably 1-ethyl-3-methylimidazolium cation and 1-hexyl-3-methylimidazolium cation.

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

Specific examples of the cation represented by the general formula (3) include pyrazolium cations such as 1-methylpyrazolium cation, 3-methylpyrazolium cation, 1-ethyl-2, 3, 5-trimethylpyrazolium cation, 1-propyl-2, 3, 5-trimethylpyrazolium cation, and 1-butyl-2, 3, 5-trimethylpyrazolium cation; pyrazolinium cations such as 1-ethyl-2, 3, 5-trimethylpyrazolinium cation, 1-propyl-2, 3, 5-trimethylpyrazolinium cation, and 1-butyl-2, 3, 5-trimethylpyrazolinium cation; and the like.

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

Specific examples of the cation represented by the general formula (4) include tetramethylammonium cation, tetraethylammonium cation, tetrabutylammonium cation, tetrapentylammonium cation, tetrahexylammonium cation, tetraheptylammonium cation, triethylmethylammonium cation, tributylethylammonium cation, trimethylpropylammonium cation, trimethyldecylammonium cation, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium cation, glycidyltrimethylammonium cation, trimethylsulfonium cation, triethylsulfonium cation, tributylsulfonium cation, trihexsulfonium cation, diethylmethylsulfonium cation, dibutylethylsulfonium cation, dimethyldecylsulfonium cation, tetramethylphosphonium cation, tetraethylphosphonium cation, tetrabutylphosphonium cation, tetrahexylphosphonium cation, tetrabutylphosphonium cation, tetrabutylammonium cation, tetrabutylphosphonium cation, etc, Tetraoctylphosphonium cation, triethylmethylphosphonium cation, tributylethylphosphonium cation, trimethyldecylphosphonium cation, diallyldimethylammonium cation, and the like.

Of these, asymmetric tetraalkylammonium cations such as triethylmethylammonium cation, tributylethylammonium cation, trimethyldecylammonium cation, diethylmethylsulfinium cation, dibutylethylsulfonium cation, dimethyldecylsulfinium cation, triethylmethylphosphonium cation, tributylethylphosphonium cation, trimethyldecylphosphonium cation and the like, trialkylsulfinium cation, tetraalkylphosphonium cation, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium cation, glycidyltrimethylammonium cation, diallyldimethylammonium cation, N-dimethyl-N-ethyl-N-propylammonium cation, N-dimethyl-N-ethyl-N-butylammonium cation, N-dimethyl-N-ethylbutylammonium cation, and the like are preferable from the viewpoint of further exhibiting the effects of the present invention, N, N-dimethyl-N-ethyl-N-pentylammonium cation, N-dimethyl-N-ethyl-N-hexylammonium cation, N-dimethyl-N-ethyl-N-heptylammonium cation, N-dimethyl-N-ethyl-N-nonylammonium cation, N-dimethyl-N, N-dipropylammonium cation, N-diethyl-N-propyl-N-butylammonium cation, N-dimethyl-N-propyl-N-pentylammonium cation, N-dimethyl-N-propyl-N-hexylammonium cation, N-dimethyl-N-propyl-N-heptylammonium cation, N-dimethyl-N-propyl-N-hexylammonium, N, N-dimethyl-N-butyl-N-hexylammonium cation, N-diethyl-N-butyl-N-heptylammonium cation, N-dimethyl-N-pentyl-N-hexylammonium cation, N-dimethyl-N, N-dihexylammonium cation, trimethylheptylammonium cation, N-diethyl-N-methyl-N-propylammonium cation, N-diethyl-N-methyl-N-pentylammonium cation, N-diethyl-N-methyl-N-heptylammonium cation, N-diethyl-N-propyl-N-pentylammonium cation, N-diethyl-N-pentyl-ammonium cation, N-diethyl-N-pentyl-N-hexylammonium cation, N, Triethylpropylammonium cation, triethylpentylammonium cation, triethylheptylammonium cation, N-dipropyl-N-methyl-N-ethylammonium cation, N-dipropyl-N-methyl-N-pentylammonium cation, N-dipropyl-N-butyl-N-hexylammonium cation, N-dipropyl-N, N-dihexylammonium cation, N-dibutyl-N-methyl-N-pentylammonium cation, N-dibutyl-N-methyl-N-hexylammonium cation, trioctylmethylammonium cation, N-methyl-N-ethyl-N-propyl-N-pentylammonium cation, and the like, more preferably the trimethyl propyl ammonium cation.

As the fluoroorganic anion that can constitute the ionic liquid, any suitable fluoroorganic anion can be used within a range that does not impair the effects of the present invention. Such fluoroorganic anions may be fully fluorinated (perfluorinated) or partially fluorinated.

Examples of such a fluorine organic anion include a fluorinated arylsulfonate, a perfluoroalkanesulfonate, a bis (fluorosulfonyl) imide, a bis (perfluoroalkanesulfonyl) imide, a cyano perfluoroalkanesulfonylamide, a bis (cyano) perfluoroalkanesulfonyl methide, a cyano-bis- (perfluoroalkanesulfonyl) methide, a tris (perfluoroalkanesulfonyl) methide, a trifluoroacetate, a perfluoroalkylide, a tris (perfluoroalkanesulfonyl) methide, and a (perfluoroalkanesulfonyl) trifluoroacetamide.

Among these fluorine organic anions, perfluoroalkyl sulfonate, bis (fluorosulfonyl) imide and bis (perfluoroalkanesulfonyl) imide are more preferable, and more specifically, trifluoromethane sulfonate, pentafluoroethane sulfonate, heptafluoropropane sulfonate, nonafluorobutane sulfonate, bis (fluorosulfonyl) imide and bis (trifluoromethanesulfonyl) imide are more preferable.

Specific examples of the ionic liquid may be suitably selected from combinations of the above-mentioned cationic components and the above-mentioned anionic components. Specific examples of such ionic liquids include 1-hexylpyridinium bis (fluorosulfonyl) imide, 1-ethyl-3-methylpyridinium trifluoromethanesulfonate, 1-ethyl-3-methylpyridinium pentafluoroethane sulfonate, 1-ethyl-3-methylpyridinium heptafluoropropane sulfonate, 1-ethyl-3-methylpyridinium nonafluorobutane sulfonate, 1-butyl-3-methylpyridinium trifluoromethanesulfonate, 1-butyl-3-methylpyridinium bis (trifluoromethanesulfonyl) imide, 1-butyl-3-methylpyridinium bis (pentafluoroethanesulfonyl) imide, 1-octyl-4-methylpyridinium bis (fluorosulfonyl) imide, and mixtures thereof, 1, 1-dimethylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-ethylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-propylpyrrolidinium bis (fluorosulfonyl) imide, 1-methyl-1-butylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-pentylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-hexylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-heptylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-ethyl-1-propylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-Ethyl-1-butylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-Ethyl-1-pentylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-Ethyl-1-hexylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-Ethyl-1-heptylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-dipropylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-propyl-1-butylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-dibutylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-propylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-pentylpiperidinium bis (trifluoromethanesulfonyl) imide, 1, 1-dimethylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-ethylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-propylpiperidinium bis (fluorosulfonyl) imide, 1-methyl-1-butylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-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 (trifluoromethanesulfonyl) imide, 1-Ethyl-1-pentylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-Ethyl-1-hexylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-Ethyl-1-heptylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-dipropylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-propyl-1-butylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-dibutylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-dimethylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-ethylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-Ethyl-1-pyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-propylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-butylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-pentylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-hexylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-heptylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-propylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-butylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-pentylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-hexylpyrrolidinium bis (pentafluoro, 1-Ethyl-1-hexylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-Ethyl-1-heptylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-dipropylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-propyl-1-butylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-dibutylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-propylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-pentylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-dimethylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-ethylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-propylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-butylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-pentylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-hexylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-heptylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-propylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-butylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-pentylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-hexylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-Ethyl-1-heptylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-dipropylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-propyl-1-butylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-dibutylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-3-methylimidazolium trifluoroacetate, 1-ethyl-3-methylimidazolium heptafluorobutyrate, 1-ethyl-3-methylimidazolium trifluoromethanesulfonate, 1-ethyl-3-methylimidazolium heptafluoropropane sulfonate, 1-ethyl-3-methylimidazolium nonafluorobutane sulfonate, 1-ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide, 1-ethyl-3-methylimidazolium bis (fluorosulfonyl) imide, 1-ethyl-3-methylimidazolium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-3-methylimidazolium tris (trifluoromethanesulfonyl) methide, 1-butyl-3-methylimidazolium trifluoroacetate, 1-butyl-3-methylimidazolium heptafluorobutyrate, 1-butyl-3-methylimidazolium trifluoromethanesulfonate, 1-butyl-3-methylimidazolium perfluorobutanesulfonate, 1-butyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide, 1-hexyl-3-methylimidazolium trifluoromethanesulfonate, 1-hexyl-3-methylimidazolium bis (fluorosulfonyl) imide, 1, 2-dimethyl-3-propylimidazolium bis (trifluoromethanesulfonyl) imide, 1-ethyl-2, 3, 5-trimethylpyrazolium bis (trifluoromethanesulfonyl) imide, 1-propyl-2, 3, 5-trimethylpyrazolium bis (trifluoromethanesulfonyl) imide, 1-butyl-2, 3, 5-trimethylpyrazolium bis (trifluoromethanesulfonyl) imide, 1-ethyl-2, 3, 5-trimethylpyrazolium bis (pentafluoroethanesulfonyl) imide, 1-propyl-2, 3, 5-trimethylpyrazolium bis (pentafluoroethanesulfonyl) imide, 1-butyl-2, 3, 5-trimethylpyrazolium bis (pentafluoroethanesulfonyl) imide, 1-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) imide, N-dimethyl-N-ethyl-N-propylammonium bis (trifluoromethanesulfonyl) imide, N-dimethyl-N-ethyl-N-butylammonium bis (trifluoromethanesulfonyl) imide, N-dimethyl-N-ethyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, N-trimethyl-N-propylammonium bis (trifluoromethanesulfonyl) imide, N-dimethyl-N-ethyl-N-, N, N-dimethyl-N-ethyl-N-hexylammonium bis (trifluoromethanesulfonyl) imide, N-dimethyl-N-ethyl-N-heptylammonium bis (trifluoromethanesulfonyl) imide, N-dimethyl-N-ethyl-N-nonylammonium bis (trifluoromethanesulfonyl) imide, N-dimethyl-N, N-dipropylammonium bis (trifluoromethanesulfonyl) imide, N-dimethyl-N-propyl-N-butylammonium bis (trifluoromethanesulfonyl) imide, N-dimethyl-N-propyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, N-dimethyl-N-propyl-N-hexylammonium bis (trifluoromethanesulfonyl) imide, N-dimethyl-N-hexyl-ammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-propyl-N-heptylammonium bis (trifluoromethanesulfonyl) imide, N-dimethyl-N-butyl-N-hexylammonium bis (trifluoromethanesulfonyl) imide, N-dimethyl-N-butyl-N-heptylammonium bis (trifluoromethanesulfonyl) imide, N-dimethyl-N-pentyl-N-hexylammonium bis (trifluoromethanesulfonyl) imide, N-dimethyl-N, N-dihexylammonium bis (trifluoromethanesulfonyl) imide, trimethylheptylammonium bis (trifluoromethanesulfonyl) imide, N-diethyl-N-methyl-N-propylammonium bis (trifluoromethanesulfonyl) imide, N-dimethyl-N-propyl-N-heptylammonium bis (trifluoromethanesulfonyl) imide, N-dimethyl-N-hexyl-N-hexylammonium bis (trifluoromethanesulfonyl) imide, N-dimethyl-N-propylammonium, N, N-diethyl-N-methyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, N-diethyl-N-methyl-N, N-heptylammonium bis (trifluoromethanesulfonyl) imide, N-diethyl-N-propyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, triethylpropylammonium bis (trifluoromethanesulfonyl) imide, triethylpentylammonium bis (trifluoromethanesulfonyl) imide, triethylheptylammonium bis (trifluoromethanesulfonyl) imide, N-dipropyl-N-methyl-N-ethylammonium bis (trifluoromethanesulfonyl) imide, N-dipropyl-N-methyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, N, N-dipropyl-N-butyl-N-hexylammonium bis (trifluoromethanesulfonyl) imide, N-dipropyl-N, N-dihexylammonium bis (trifluoromethanesulfonyl) imide, N-dibutyl-N-methyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, N-dibutyl-N-methyl-N-hexylammonium bis (trifluoromethanesulfonyl) imide, trioctylmethylammonium bis (trifluoromethanesulfonyl) imide, N-methyl-N-ethyl-N-propyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, 1-butylpyridinium (trifluoromethanesulfonyl) trifluoroacetamide, 1-butyl-3-methylpyridinium (trifluoromethanesulfonyl) trifluoroacetamide, 1-ethyl-3-methylimidazolium (trifluoromethanesulfonyl) trifluoroacetamide, tetrahexylammonium bis (trifluoromethanesulfonyl) imide, diallyldimethylammonium trifluoromethanesulfonate, diallyldimethylammonium bis (trifluoromethanesulfonyl) imide, diallyldimethylammonium bis (pentafluoroethanesulfonyl) imide, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium trifluoromethanesulfonate, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium bis (trifluoromethanesulfonyl) imide, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium bis (pentafluoroethanesulfonyl) imide, N-, Glycidyl trimethylammonium trifluoromethanesulfonate, glycidyl trimethylammonium bis (trifluoromethanesulfonyl) imide, glycidyl trimethylammonium bis (pentafluoroethanesulfonyl) imide, diallyldimethylammonium bis (trifluoromethanesulfonyl) imide, diallyldimethyl bis (pentafluoroethanesulfonyl) imide, lithium bis (trifluoromethanesulfonyl) imide, lithium bis (fluorosulfonyl) imide, and the like.

Among these ionic liquids, 1-hexylpyridinium bis (fluorosulfonyl) imide, 1-ethyl-3-methylpyridinium trifluoromethanesulfonate, 1-ethyl-3-methylpyridinium pentafluoroethane sulfonate, 1-ethyl-3-methylpyridinium heptafluoropropane sulfonate, 1-ethyl-3-methylpyridinium nonafluorobutane sulfonate, 1-butyl-3-methylpyridinium trifluoromethanesulfonate, 1-butyl-3-methylpyridinium bis (trifluoromethanesulfonyl) imide, 1-octyl-4-methylpyridinium bis (fluorosulfonyl) imide, 1-methyl-1-propylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-ethyl-3-methylpyridinium heptafluoropropane sulfonate, 1-ethyl-3-methylpyridinium nonafluorobutane sulfonate, 1-butyl-3-methylpyridinium trifluoromethanesulfonate, 1-butyl-3-methylpyridinium bis (trifluoromethanesulfonyl) imide, 1-octyl, 1-methyl-1-propylpyrrolidinium bis (fluorosulfonyl) imide, 1-methyl-1-propylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-propylpiperidinium bis (fluorosulfonyl) imide, 1-ethyl-3-methylimidazolium trifluoromethanesulfonate, 1-ethyl-3-methylimidazolium heptafluoropropanesulfonate, 1-ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide, 1-ethyl-3-methylimidazolium bis (fluorosulfonyl) imide, 1-hexyl-3-methylimidazolium bis (fluorosulfonyl) imide, trimethylpropylammonium bis (trifluoromethanesulfonyl) imide, lithium bis (trifluoromethanesulfon, Lithium bis (fluorosulfonyl) imide.

The ionic liquid may be commercially available, or may be synthesized as described below. The method for synthesizing the ionic liquid is not particularly limited as long as the target ionic liquid can be obtained, and generally, a halide method, a hydroxide method, an acid ester method, a complexation method, a neutralization method, and the like, which are described in the literature "ionic liquid-first line and future of development" (published by CMC Group), can be used.

In the following, the halide method, the hydroxide method, the acid ester method, the complex method, and the neutralization method are exemplified by nitrogen-containing onium salts, and other ionic liquids such as other sulfur-containing onium salts and phosphorus-containing onium salts can be obtained by the same method.

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

The obtained halide is reacted with an anion structure (A) having a target ionic liquid^-) The acid (HA) or salt (MA, M are cations forming a salt with the target anion such as ammonium, lithium, sodium, potassium) to obtain the target ionic liquid (R₄NA)。

(1)R₃N+RX→R₄NX(X：Cl，Br，l)

(2)R₄NX+HA→R₄NA+HX

(3)R₄NX+MA→R₄NA+MX(M：NH₄Li, Na, K, Ag, etc.)

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

The obtained hydroxide is subjected to the reaction of the reaction formulae (7) to (8) in the same manner as in the halogenation method described above, thereby obtaining the target ionic liquid (R)₄NA)。

(4)R₄NX+H₂O→R₄NOH+1/2H₂+1/2X₂(X：Cl，Br，I)

(5)R₄NX+P-OH→R₄NOH + P-X (P-OH: OH type ion exchange resin)

(6)R₄NX+1/2Ag₂O+1/2H₂O→R₄NOH+AgX

(7)R₄NOH+HA→R₄NA+H₂O

(8)R₄NOH+MA→R₄NA+MOH(M：NH₄Li, Na, K, Ag, etc.)

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

The obtained acid ester compound is subjected to the reaction of the reaction formulae (10) to (11) in the same manner as in the halogenation method described above, thereby obtaining the target ionic liquid (R)₄NA). Further, by using methyl trifluoromethanesulfonate, methyl trifluoroacetate or the like as an acid ester, an ionic liquid can be obtained as it is.

(9)R₃N+ROY→R₄NOY

(OY：

Etc.)

(10)R₄NOY+HA→R₄NA+HOY

(OY：

In the case of (a) in (b),

)

(11)R₄NOY+MA→R₄NA+MOY(M：NH₄li, Na, K, Ag, etc.)

The neutralization method is a method in which the neutralization is carried out by a reaction represented by the reaction formula (12)The method is carried out. Can be prepared by reacting a tertiary amine with CF₃COOH，CF₃SO₃H，(CF₃SO₂)₂NH、(CF₃SO₂)₃CH、(C₂F₅SO₂)₂NH, etc.

(12)R₃N+HZ→R₃HN⁺Z-

[Hz：CF₃COOH，CF₃SO₃H，(CF₃SO₂)₂NH，(CF₃SO₂)₃CH，(C₂F₅SO₂)₂Organic acids such as NH]

R in the above reaction formulae (1) to (12) represents hydrogen or a hydrocarbon group having 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 between the polymer to be used and the ionic liquid, and therefore cannot be generally defined, and is usually preferably 0.001 to 50 parts by weight, more preferably 0.01 to 40 parts by weight, further preferably 0.01 to 30 parts by weight, particularly preferably 0.01 to 20 parts by weight, and most preferably 0.01 to 10 parts by weight, based on 100 parts by weight of the base polymer. By adjusting the amount of the ionic liquid to be blended within the above range, an adhesive composition having very excellent antistatic properties can be provided. If the amount of the ionic liquid added is less than 0.01 part by weight, sufficient antistatic properties may not be obtained. When the amount of the ionic liquid added exceeds 50 parts by weight, the adherend tends to be contaminated more.

The adhesive composition may contain the modified silicone oil within a range not impairing the effects of the present invention. By allowing the adhesive composition to contain the modified silicone oil, the effect of antistatic properties can be exhibited. In particular, the effect of antistatic properties can be more effectively exhibited by using the ionic liquid in combination.

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

As the modified silicone oil, any suitable modified silicone oil can be used within a range not impairing the effects of the present invention. Examples of such modified silicone oils include those available from shin-Etsu chemical industries, Ltd.

The modified silicone oil is preferably a polyether-modified silicone oil. By using the polyether-modified silicone oil, the antistatic property can be further effectively exhibited.

Examples of the polyether-modified silicone oil include a side chain type polyether-modified silicone oil, an both-terminal type polyether-modified silicone oil, and the like. Of these, both-end type polyether-modified silicone oils are preferable from the viewpoint of sufficiently exhibiting the effect of antistatic properties more effectively.

"use in B

The surface protective film of the present invention can exhibit the following effects: can be less easily peeled from an adherend, can be inhibited from being re-peeled over time, and staining of the adherend surface due to attachment to the adherend is low. Therefore, the resin composition can be suitably used for surface protection of optical members and electronic members. The surface protective film of the present invention is attached to the optical member of the present invention. The surface protective film of the present invention is attached to the electronic component of the present invention.

Examples

The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples at all. The test and evaluation methods in examples and the like are as follows. In the case of "part(s)", unless otherwise specified, it means "part(s) by weight", and in the case of "%" it means "% by weight", unless otherwise specified.

< peeling force A from glass plate (after leaving at 23 ℃ C. for 30 minutes) >

The pressure-sensitive adhesive layer side from which the surface protection film (width 25 mm. times. length 140mm) of the separator was peeled was bonded to a glass plate (soda-lime glass, Songlanza corporation) by reciprocating 1 time with a 2kg hand roller, and left at an ambient temperature of 23 ℃ for 30 minutes.

The evaluation sample obtained as described above was measured with a tensile tester. As the tensile testing machine, the product name "Autograph AG-Xplus HS 6000 mm/min high speed model (AG-50NX plus)" manufactured by Shimadzu corporation was used. The test specimen for evaluation was set in a tensile testing machine, and a tensile test was started. Specifically, the load at the time of peeling the surface protection film from the glass plate was measured, and the average load at that time was taken as the peeling force a of the surface protection film from the glass plate. The conditions for the tensile test were set as test environment temperature: 23 ℃ and peel angle: 180 degrees, peeling speed (stretching speed): 300 mm/min.

< peeling force B from glass plate (after leaving at a temperature of 100 ℃ C. for 2 days) >

The pressure-sensitive adhesive layer side from which the surface protection film (width 25 mm. times. length 140mm) of the separator was peeled was bonded to a glass plate (soda-lime glass, Songlanzui Co., Ltd.) by reciprocating 1 time with a 2kg hand roller, and the plate was left to stand at 100 ℃ for 2 days.

The evaluation sample obtained as described above was measured with a tensile tester. As the tensile testing machine, the product name "Autograph AG-Xplus HS 6000 mm/min high speed model (AG-50NX plus)" manufactured by Shimadzu corporation was used. The test specimen for evaluation was set in a tensile testing machine, and a tensile test was started. Specifically, the load at the time of peeling the surface protection film from the glass plate was measured, and the average load at that time was taken as the peeling force B of the surface protection film from the glass plate. The conditions for the tensile test were set as test environment temperature: 23 ℃ and peel angle: 180 degrees, peeling speed (stretching speed): 300 mm/min.

< peeling force C from glass plate (after leaving at a temperature of 23 ℃ C. for 7 days) >

The pressure-sensitive adhesive layer side from which the surface protection film (width 25 mm. times. length 140mm) of the separator was peeled was bonded to a glass plate (soda-lime glass, Songlanza corporation) by reciprocating 1 time with a 2kg hand roller, and the plate was left to stand at a temperature of 23 ℃ for 7 days.

The evaluation sample obtained as described above was measured with a tensile tester. As the tensile testing machine, the product name "Autograph AG-Xplus HS 6000 mm/min high speed model (AG-50NX plus)" manufactured by Shimadzu corporation was used. The test specimen for evaluation was set in a tensile testing machine, and a tensile test was started. Specifically, the load at the time of peeling the surface protection film from the glass plate was measured, and the average load at that time was taken as the peeling force C of the surface protection film from the glass plate. The conditions for the tensile test were set as test environment temperature: 23 ℃ and peel angle: 180 degrees, peeling speed (stretching speed): 300 mm/min.

< residual adhesion to glass plate at 23 >

The pressure-sensitive adhesive layer side of the surface protection film from which the separator was peeled was adhered to the entire surface of a glass plate (1.35 mm. times.10 cm, made of Sonlang Nitri) by reciprocating 1 time with a 2kg hand roller, and after storing for 24 hours in an atmosphere of 23 ℃ and 55% RH humidity, the surface protection film was peeled at a speed of 0.3 m/min to prepare a treated glass plate.

Next, a No.31B tape (manufactured by Nindon electric Co., Ltd., substrate thickness: 25 μm) cut into a length of 150mm and a width of 19mm was applied to the surface of the treated glass plate from which the surface protective film was peeled by reciprocating the tape 1 time with a 2kg hand roller in an atmosphere of 23 ℃ and a humidity of 55% RH. After curing at 23 ℃ under an atmosphere of 55% RH for 30 minutes, the cured product was cured at a peel angle of: 180 degrees, peeling speed: the adhesive force a was measured by peeling at 300 mm/min.

The adhesive force b of the No.31B tape 19mm wide was measured in the same manner as above for a glass plate (1.35 mm. times.10 cm, made of Sonlang Nitri) which had not been subjected to the treatment of bonding and peeling the surface protective film as described above.

The residual adhesion ratio was calculated by the following formula.

Residual adhesion rate (%) (adhesive force a/adhesive force b) × 100

The residual adhesion ratio is an index of how much the components of the pressure-sensitive adhesive layer of the surface protective film are transferred to the surface of the adherend and stained. The higher the value of the residual adhesion ratio, the less likely the component of the pressure-sensitive adhesive layer contaminates the surface of the adherend, and the lower the value of the residual adhesion ratio, the more likely the component of the pressure-sensitive adhesive layer contaminates the surface of the adherend.

[ production example 1]

In a polymerization experimental apparatus equipped with a 1L round-bottomed separable flask, a detachable lid, a separatory funnel, a thermometer, a nitrogen inlet tube, a Liebig condenser, a vacuum sealer, a stirring bar, and a stirring blade, polypropylene glycol (product name "SANNIX PP-2000", manufactured by Sanyo chemical Co., Ltd.) was charged: 150g, polyester Polyol (product name "Kuraray Polyol P-2010", KURAAY CO., LTD system): 150g of toluene (manufactured by Tosoh corporation) as a solvent: 110g of dibutyltin (IV) dilaurate as a catalyst (Wako pure chemical industries, Ltd.): 0.041g, nitrogen substitution was performed at room temperature for 1 hour while stirring. Then, hexamethylene diisocyanate (product name "HDI", manufactured by Tosoh corporation) was added under stirring with nitrogen flowing in: 33.5g, controlled by a water bath so that the temperature of the solution in the experimental apparatus became 90. + -. 2 ℃ and kept for 4 hours, and then polypropylene glycol (product name "GP 1000", manufactured by Sanyo chemical Co., Ltd.) was added: 74.9g, the temperature of the solution in the experimental apparatus was controlled to 90. + -. 2 ℃ by a water bath and kept for 2 hours, and then hexamethylene diisocyanate (trade name "HDI", manufactured by Tosoh Corp.) was added: 25.4g, controlled with a water bath so that the temperature of the solution in the experimental apparatus became 90. + -. 2 ℃ and held for 2 hours, to obtain a urethane prepolymer solution A. In the course of polymerization, toluene is preferably added dropwise in order to prevent decrease in stirring property due to temperature control and viscosity increase during polymerization. The total amount of toluene added dropwise was 320 g. The solid content concentration of the urethane prepolymer solution a was 50% by weight.

[ example 1]

As shown in table 1, The urethane prepolymer solution a obtained in production example 1 was mixed in an amount of 100 parts by weight in terms of solid content of The polymer, an isocyanate-based crosslinking agent (trade name "CORONATE HL", manufactured by Nippon Polyurethane Industry co., ltd.) in an amount of 5.2 parts by weight in terms of solid content, a heat resistant stabilizer (trade name "IRGANOX 1010", manufactured by BASF) in an amount of 0.5 parts by weight in terms of solid content, a fluorine-containing polymer (trade name "F-571", manufactured by DIC corporation) in an amount of 0.01 parts by weight in terms of solid content, and a fatty acid ester (trade name "SALACOS 816", manufactured by Nisshin oilo Group, ltd.) in an amount of 1 part by weight in terms of solid content were mixed, and diluted with ethyl acetate so that The total solid content became 45 parts by weight, to obtain an adhesive composition (1).

The obtained adhesive composition (1) was applied to a polyester resin substrate (trade name "T100-75S", thickness 75 μm, manufactured by Mitsubishi resin corporation) so that the thickness after drying became 75 μm, cured at a drying temperature of 130 ℃ for a drying time of 3 minutes, and dried. In this manner, the pressure-sensitive adhesive layer (1) formed from the pressure-sensitive adhesive composition (1) was produced on the substrate.

Next, a surface-protecting film (1) was obtained by bonding a silicone-treated surface of a 25 μm thick polyester resin separator (trade name "MRF 25", thickness 25 μm, manufactured by Mitsubishi Chemical Corporation) having one surface subjected to silicone treatment to the surface of the obtained adhesive layer (1).

The obtained surface protection film (1) was aged at room temperature for 7 days and evaluated. The release sheet was peeled off immediately before evaluation. The results are shown in Table 2.

[ example 2]

A pressure-sensitive adhesive layer (2) formed from The pressure-sensitive adhesive composition (2) was prepared in The same manner as in example 1 except that The blending amount of The fatty acid ester (trade name "SALACOS 816", manufactured by The Nisshin oigio Group, ltd.) was changed to 5 parts by weight in terms of solid content as shown in table 1, and a surface protection film (2) was obtained. The results are shown in Table 2.

[ example 3 ]

An adhesive layer (3) formed from The adhesive composition (3) was prepared in The same manner as in example 1 except that The blending amount of The fatty acid ester (trade name "SALACOS 816", manufactured by The Nisshin oigio Group, ltd.) was changed to 15 parts by weight in terms of solid content as shown in table 1, and a surface protective film (3) was obtained. The results are shown in Table 2.

[ example 4 ]

A pressure-sensitive adhesive layer (4) formed from the pressure-sensitive adhesive composition (4) was produced in the same manner as in example 1 except that the blending amount of the fluoropolymer (trade name "F-571", manufactured by DIC corporation) was changed to 0.05 parts by weight in terms of solid content as shown in Table 1, and a surface protection film (4) was obtained. The results are shown in Table 2.

[ example 5]

A pressure-sensitive adhesive layer (5) comprising a pressure-sensitive adhesive composition (5) was produced in The same manner as in example 1 except that The amount of The fluoropolymer (trade name "F-571", manufactured by DIC corporation) was changed to 0.05 parts by weight in terms of solid content and The amount of The fatty acid ester (trade name "SALACOS 816", manufactured by The Nisshin OilliO Group, Ltd.) was changed to 5 parts by weight in terms of solid content, as shown in Table 1, to obtain a surface-protecting film (5). The results are shown in Table 2.

[ example 6 ]

A pressure-sensitive adhesive layer (6) comprising a pressure-sensitive adhesive composition (6) was produced in The same manner as in example 1 except that The amount of The fluoropolymer (trade name "F-571", manufactured by DIC corporation) was changed to 0.05 parts by weight in terms of solid content and The amount of The fatty acid ester (trade name "SALACOS 816", manufactured by The Nisshin OilliO Group, Ltd.) was changed to 15 parts by weight in terms of solid content, as shown in Table 1, to obtain a surface-protecting film (6). The results are shown in Table 2.

[ example 7 ]

As shown in table 1, an adhesive layer (7) formed from an adhesive composition (7) was produced in The same manner as in example 1 except that The blending amount of an isocyanate-based crosslinking agent (trade name "CORONATE HL", manufactured by Nippon Polyurethane Industry co., ltd.) was changed to 3.9 parts by weight in terms of solid content and The blending amount of a fatty acid ester (trade name "SALACOS 816", manufactured by The Nisshin oilo Group, ltd.) was changed to 5 parts by weight in terms of solid content, thereby obtaining a surface protection film (7). The results are shown in Table 2.

[ example 8 ]

A pressure-sensitive adhesive layer (8) comprising a pressure-sensitive adhesive composition (8) was produced in The same manner as in example 1 except that The compounding amount of an isocyanate-based crosslinking agent (trade name "CORONATE HL", manufactured by Nippon Polyurethane Industry Co., Ltd.) was changed to 3.9 parts by weight in terms of solid content, The compounding amount of a fluoropolymer (trade name "F-571", manufactured by DIC) was changed to 0.05 parts by weight in terms of solid content, and The compounding amount of a fatty acid ester (trade name "SALACOS 816", manufactured by The Nisshin OilliO Group, manufactured by Ltd.) was changed to 5 parts by weight in terms of solid content, as shown in Table 1, thereby obtaining a surface-protecting film (8). The results are shown in Table 2.

[ example 9 ]

An adhesive layer (9) comprising an adhesive composition (9) was prepared in The same manner as in example 1 except that The compounding amount of an isocyanate-based crosslinking agent (trade name "CORONATE HL", manufactured by Nippon Polyurethane Industry co., ltd.) was changed to 2.6 parts by weight in terms of solid content, The compounding amount of a fluoropolymer (trade name "F-571", manufactured by DIC corporation) was changed to 0.10 parts by weight in terms of solid content, and The compounding amount of a fatty acid ester (trade name "SALACOS 816", manufactured by The Nisshin oilo Group, ltd.) was changed to 5 parts by weight in terms of solid content, as shown in table 1, to obtain a surface protective film (9). The results are shown in Table 2.

[ example 10 ]

An adhesive layer (10) comprising an adhesive composition (10) was produced in The same manner as in example 1 except that The compounding amount of an isocyanate-based crosslinking agent (trade name "CORONATE HL", manufactured by Nippon Polyurethane Industry co., ltd.) was changed to 2.6 parts by weight in terms of solid content, The compounding amount of a fluoropolymer (trade name "F-571", manufactured by DIC corporation) was changed to 0.20 parts by weight in terms of solid content, and The compounding amount of a fatty acid ester (trade name "SALACOS 816", manufactured by The Nisshin oilo Group, ltd.) was changed to 5 parts by weight in terms of solid content, as shown in table 1, thereby obtaining a surface protective film (10). The results are shown in Table 2.

[ example 11 ]

A pressure-sensitive adhesive layer (11) formed from a pressure-sensitive adhesive composition (11) was produced in the same manner as in example 1 except that the amount of the isocyanate-based crosslinking agent (trade name "CORONATE HL", manufactured by Nippon Polyurethane Industry co., ltd.) was changed to 9.5 parts by weight in terms of solid content, as shown in table 1, to obtain a surface protection film (11). The results are shown in Table 2.

[ example 12 ]

A pressure-sensitive adhesive layer (12) formed from a pressure-sensitive adhesive composition (12) was produced in the same manner as in example 1 except that the amount of the isocyanate-based crosslinking agent (trade name "CORONATE HL", manufactured by Nippon Polyurethane Industry co., ltd.) was changed to 12.7 parts by weight in terms of solid content, as shown in table 1, to obtain a surface protection film (12). The results are shown in Table 2.

[ example 13 ]

As shown in Table 1, a pressure-sensitive adhesive layer (13) formed from a pressure-sensitive adhesive composition (13) was produced in The same manner as in example 1 except that The compounding amount of a fatty acid ester (trade name "SALACOS 816", The Nisshin OilliO Group, manufactured by Ltd.) was changed to 5 parts by weight in terms of solid content using 0.05 parts by weight of a hydroxyl Group-containing silicone (trade name "X-22-4015", manufactured by shin-Etsu chemical Co., Ltd.) in terms of solid content instead of using a fluorine-containing polymer (trade name "F-571", manufactured by DIC corporation), and a surface protective film (13) was obtained. The results are shown in Table 2.

[ example 14 ]

As shown in table 1, an adhesive layer (14) formed from an adhesive composition (14) was produced in The same manner as in example 1 except that 3.2 parts by weight of an isocyanate-based crosslinking agent (trade name "CORONATE HX", Nippon Polyurethane Industry co., ltd. system) was used in terms of solid content instead of The isocyanate-based crosslinking agent (trade name "CORONATE HL", Nippon Polyurethane Industry co., ltd. system), and The amount of a fluorine-containing polymer (trade name "F-571", DIC corporation) was changed to 0.05 parts by weight in terms of solid content and The amount of a fatty acid ester (trade name "SALACOS 816", The nisshinshi oilo Group, ltd. system) was changed to 5 parts by weight in terms of solid content, thereby obtaining a surface protective film (14). The results are shown in Table 2.

[ example 15 ]

As shown in table 1, a pressure-sensitive adhesive layer (15) formed from a pressure-sensitive adhesive composition (15) was produced in The same manner as in example 1 except that an isocyanate-based crosslinking agent (trade name "CORONATE HX", manufactured by Nippon Polyurethane Industry co., ltd.) was used in an amount of 5.6 parts by weight in terms of solid content instead of using an isocyanate-based crosslinking agent (trade name "CORONATE HL", manufactured by Nippon Polyurethane Industry co., ltd.) and a fatty acid ester (trade name "SALACOS 816", manufactured by The Nisshin oilo Group, ltd.) was changed to 5 parts by weight in terms of solid content, thereby obtaining a surface-protecting film (15). The results are shown in Table 2.

[ comparative example 1]

As shown in table 1, a pressure-sensitive adhesive layer (C1) formed from a pressure-sensitive adhesive composition (C1) was prepared in The same manner as in example 1 except that The amount of The isocyanate-based crosslinking agent (trade name "CORONATE HL", manufactured by Nippon Polyurethane Industry co., ltd.) was changed to 3.9 parts by weight in terms of solid content, and a fluoropolymer (trade name "F-571", manufactured by DIC corporation) and a fatty acid ester (trade name "SALACOS 816", manufactured by Nisshin oigio Group, ltd.) were not used, to obtain a surface protection film (C1). The results are shown in Table 2.

[ comparative example 2]

As shown in table 1, a pressure-sensitive adhesive layer formed of The pressure-sensitive adhesive composition (C2) was prepared in The same manner as in example 1 except that a fluoropolymer (trade name "F-571", manufactured by DIC corporation) and a fatty acid ester (trade name "SALACOS 816", manufactured by The Nisshin oilo Group, ltd.) were not used, and a surface protective film (C2) was obtained. The results are shown in Table 2.

[ comparative example 3 ]

A pressure-sensitive adhesive layer (C3) composed of a pressure-sensitive adhesive composition (C3) was produced in The same manner as in example 1 except that The amount of The fluoropolymer (trade name "F-571", manufactured by DIC corporation) added was changed to 0.05 parts by weight in terms of solid content, and a fatty acid ester (trade name "SALACOS 816", manufactured by The Nisshin OilliO Group, Ltd.) was not used, as shown in Table 1, to obtain a surface-protecting film (C3). The results are shown in Table 2.

[ comparative example 4 ]

A pressure-sensitive adhesive layer composed of The pressure-sensitive adhesive composition (C4) was produced in The same manner as in example 1 except that The fatty acid ester (trade name "SALACOS 816", manufactured by The Nisshin oigio Group, ltd.) was changed to 5 parts by weight in terms of solid content, and a fluoropolymer (trade name "F-571", manufactured by DIC corporation) was not used, as shown in table 1, to obtain a surface protective film (C4). The results are shown in Table 2.

[ comparative example 5]

As shown in table 1, a pressure-sensitive adhesive layer (C5) formed from a pressure-sensitive adhesive composition (C5) was prepared in The same manner as in example 1 except that a silicone release agent (trade name "KS-776A", manufactured by shin-Etsu chemical Co., Ltd.) was used in an amount of 1.0 part by weight in terms of solid content instead of a fluorine-containing polymer (trade name "F-571", manufactured by DIC corporation) and a fatty acid ester (trade name "SALACOS 816", The Nisshin oigio Group, manufactured by ltd.) was not used, to obtain a surface protective film (C5). The results are shown in Table 2.

[ comparative example 6 ]

As shown in Table 1, a commercially available urethane prepolymer solution (trade name "CYABINE SH-109", TOYOCHEM CO., LTD. manufactured) was used in an amount of 100 parts by weight in terms of solid content instead of The urethane prepolymer solution A obtained in production example 1, an isocyanate-based crosslinking agent (trade name "CORONATE HX", Nippon Polyurethane Industry Co., Ltd.) was used in an amount of 3.6 parts by weight in terms of solid content instead of The isocyanate-based crosslinking agent (trade name "CORONATE HL", Nippon Polyurethane Industry Co., Ltd.) was used, The amount of a fluorine-containing polymer (trade name "F-", DIC corporation) was changed to 571 parts by weight in terms of solid content, a binder composition (trade name "SALACOS", The Nisshin OilliO Group, Ltd.) was not used, and a binder layer (C6, C816) was formed in The same manner as in example 1, a surface protective film (C6) was obtained. The results are shown in Table 2.

[ Table 1]

[ Table 2]

[ examples 16 to 30 ]

The surface protection films (1) to (15) obtained in examples 1 to 15 were each subjected to separator peeling, and the pressure-sensitive adhesive layer side was attached to a polarizing plate (product name "TEG 1465 DUHC" manufactured by hitto electrical corporation) as an optical member, to obtain an optical member to which a surface protection film was attached.

[ examples 31 to 45 ]

The surface protection films (1) to (15) obtained in examples 1 to 15 were each separated from each other, and the separator was attached to a conductive film (product name "ELECRYSTA V270L-TFMP" manufactured by ritong electrical corporation) as an electronic component on the pressure-sensitive adhesive layer side, to obtain an electronic component to which a surface protection film was attached.

Industrial applicability

The surface protection film of the present invention can be used for any suitable purpose. The surface protective film of the present invention is preferably used in the fields of optical members and electronic members.

Description of the reference numerals

1 base material layer

2 adhesive layer

10 surface protective film

Claims (10)

1. A surface protective film having an adhesive layer,

the adhesive layer of the surface protective film is bonded to a glass plate and left at a temperature of 23 ℃ for 30 minutes, and then the surface protective film is peeled from the glass plate at a peeling angle of 180 degrees at a peeling speed of 300 mm/min at a temperature of 23 ℃ with a peeling force A of 0.024N/25mm to 0.50N/25mm,

the pressure-sensitive adhesive layer of the surface protective film is bonded to a glass plate and left at a temperature of 100 ℃ for 2 days, and then the surface protective film is peeled from the glass plate at a peeling angle of 180 degrees and a peeling speed of 300 mm/min at a temperature of 23 ℃, and when the peeling force at this time is B, the rate of increase with time of the peeling force calculated by (B/A) × 100 is 1000% or less.

2. The surface protection film according to claim 1, wherein the adhesive layer of the surface protection film is bonded to a glass plate and left at 23 ℃ for 7 days, and then the surface protection film is peeled from the glass plate at a peeling angle of 180 degrees and a peeling speed of 300 mm/min at 23 ℃, and wherein a peeling force at this time is C, a peeling force increase rate calculated by (C/A) × 100 with time is 160% or less.

3. The surface protection film according to claim 1 or 2, wherein a residual adhesion rate to a glass plate at 23 ℃ is 50% or more.

4. The surface protection film according to any one of claims 1 to 3, wherein the adhesive constituting the adhesive layer is formed of an adhesive composition containing a base polymer and a silicone-based additive and/or a fluorine-based additive.

5. The surface protection film of claim 4, wherein the adhesive composition comprises a fatty acid ester.

6. The surface protection film according to claim 4 or 5, wherein the silicone additive is at least 1 selected from a silicone bond-containing compound, a hydroxyl group-containing silicone compound, and a crosslinkable functional group-containing silicone compound.

7. The surface protection film according to any one of claims 4 to 6, wherein the fluorine-based additive is at least 1 selected from a fluorine-containing compound, a hydroxyl group-containing fluorine-based compound, and a crosslinkable functional group-containing fluorine-based compound.

8. The surface protection film according to any one of claims 4 to 7, wherein the base polymer is at least 1 selected from a urethane prepolymer, a polyol, an acrylic resin, a rubber resin, and a silicone resin.

9. An optical member to which the surface protective film according to any one of claims 1 to 8 is attached.

10. An electronic component to which the surface protective film according to any one of claims 1 to 8 is attached.

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