WO2019208148A1 - Surface protection film - Google Patents

Abstract

Provided is a surface protection film which does not readily peel off the adherend and can be inhibited from coming to have an extremely high peel force with the lapse of time even when having a high initial peel force just after application to the adherend, and the application of which to adherends less soils the adherend surfaces. The surface protection film of the present invention includes a pressure-sensitive adhesive layer. This surface protection film, when applied to a glass plate by bonding the pressure-sensitive adhesive layer to the glass plate, allowed to stand at 23°C for 30 minutes, and then peeled at 23°C from the glass plate at a peel angle of 180° and a peel rate of 300 mm/min, has a peel force A of 0.024-0.50 N/25 mm. This surface protection film, when applied to a glass plate by bonding the pressure-sensitive adhesive layer thereof to the glass plate, allowed to stand at 100°C for 2 days, and then peeled at 23°C from the glass plate at a peel angle of 180° and a peel rate of 300 mm/min, has a peel force, which is expressed by B. Then the surface protection film has a degree of peel force increase with time, which is calculated by (B/A)×100, of 1,000% or less.

Description

Surface protection film

The present invention relates to a surface protective film.

In the manufacturing process of an optical member or an electronic member, in order to prevent the surface of the optical member or the electronic member from being damaged during processing, assembly, inspection, transportation, etc., in general, the optical member or the electronic member is used. A surface protective film is affixed on the exposed surface of the member. Such a surface protective film is peeled off from the optical member or the electronic member when the surface protection is no longer necessary (Patent Document 1).

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

However, when the optical member or the electronic member includes a member that is easily damaged, such as a thin glass or a barrier film, the conventional surface protective film with light releasability can be obtained by attempting to peel the attached surface protective film. Even if it is used, the fragile member may be damaged by the peeling force.

Further, in the manufacturing process of the optical member and the electronic member, the optical member and the exposed surface of the electronic member are prevented from being scratched on the surface of the optical member and the electronic member during processing, assembly, inspection, transportation, etc. The attached surface protective film is often stored while being attached. In this case, if the conventional surface protective film is stored while being adhered, there is a problem that the adhesive force increases with time, resulting in heavy peeling.

For this reason, a surface protective film having even lighter releasability, that is, ultra-light releasability compared to a conventional surface protective film having light releasability has been reported (Patent Document 2).

By imparting ultra-light peelability to the surface protective film, it is possible to reduce the initial peel force after being attached and to suppress heavy peeling over time. However, when ultra-light peelability is imparted to the surface protective film, for example, depending on the conditions of the manufacturing process of the optical member or the electronic member, the surface protective film may be attached to the exposed surface of the optical member or the electronic member during the manufacturing process. Further, the surface protective film may be peeled off.

On the other hand, if the initial peeling force after applying the surface protective film is increased in order to suppress the peeling as described above, there is a problem that the peeling force increases with time, resulting in heavy peeling.

As a means for reducing the peeling force, it can be considered that a large amount of a conventional release agent is contained in the pressure-sensitive adhesive layer of the surface protective film. However, with such means, when the surface protective film is applied to an adherend such as an optical member or an electronic member and then peeled off, the degree of contamination of the adherend surface by the release agent increases, and the contaminated Even if a new surface protection film is to be attached to the surface of the adherend, there is a problem that it is difficult to stick due to contamination of the adherend surface.

As described above, typically, in the manufacturing process of an optical member or an electronic member, it is difficult to cause the surface protective film attached to the adherend to peel off, and after the surface protective film is attached to the adherend. Therefore, it is required that even when the initial peeling force is large, heavy peeling over time can be suppressed, and contamination of the adherend surface by attaching a surface protective film can be reduced.

Japanese Unexamined Patent Publication No. 2016-17109 JP 2017-160422 A

The problem of the present invention is that it is not easily peeled off from the adherend, and even if the initial peeling force after being attached to the adherend is large, it is possible to suppress heavy peeling over time and sticking to the adherend. It is an object of the present invention to provide a surface protective film having low contamination on the surface of the adherend.

The surface protective film of the present invention is
A surface protective film having an adhesive layer,
The pressure-sensitive adhesive layer of the surface protective film was bonded to a glass plate and allowed to stand at a temperature of 23 ° C. for 30 minutes, and then the surface protective film was peeled from the glass plate at a temperature of 23 ° C. at a peeling angle of 180 degrees and a peeling speed of 300 mm / min. The peel force A when peeled off is 0.024 N / 25 mm to 0.50 N / 25 mm,
The pressure-sensitive adhesive layer of the surface protective film was bonded to a glass plate and allowed to stand at a temperature of 100 ° C. for 2 days, and then the surface protective film was peeled from the glass plate at a temperature of 23 ° C. at a peeling angle of 180 degrees and a peeling speed of 300 mm / min. When the peeling force at the time of peeling is B, the rate of increase in peeling force with time calculated by (B / A) × 100 is 1000% or less.

In one embodiment, the pressure-sensitive adhesive layer of the surface protective film is bonded to a glass plate and allowed to stand at 23 ° C. for 7 days, and then the surface protective film is peeled from the glass plate at a temperature of 23 ° C. at an angle of 180 degrees, When the peel force when peeled at a peel speed of 300 mm / min is C, the rate of increase in peel force with time calculated by (C / A) × 100 is 160% or less.

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

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

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

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

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

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

The optical member of the present invention has the surface protective film of the present invention attached thereto.

The electronic member of the present invention has the surface protective film of the present invention attached thereto.

According to the present invention, it is not easily peeled off from the adherend, and even if the initial peeling force after being attached to the adherend is large, it is possible to suppress heavy peeling over time and sticking to the adherend. Thus, it is possible to provide a surface protective film having low contamination on the adherend surface.

It is a schematic sectional drawing of the surface protection film by one Embodiment of this invention.

≪ << A. Surface protection film >>>>
The surface protective film of the present invention has an adhesive layer. As long as the surface protective film of the present invention has a pressure-sensitive adhesive layer, the surface protective film may include any appropriate other member as long as the effects of the present invention are not impaired. Typically, the surface protective film of the present invention has a base material layer and an adhesive layer.

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

In FIG. 1, the surface opposite to the base material layer 1 of the pressure-sensitive adhesive layer 2 is provided with any appropriate release liner (sometimes referred to as a release sheet or separator) for protection before use. May be provided (not shown). Examples of release liners include release liners in which the surface of a substrate (liner substrate) such as paper or plastic film is treated with silicone, and the surface of a substrate (liner substrate) such as paper or plastic film is made of a polyolefin resin. Examples include a laminated release liner. As a plastic film as a liner substrate, for example, polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate film, polybutylene terephthalate film, Examples include polyurethane films and ethylene-vinyl acetate copolymer films. The plastic film as the liner substrate is preferably a polyethylene film.

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

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

The surface protective film of the present invention is obtained by laminating the pressure-sensitive adhesive layer of the surface protective film on a glass plate and leaving it at a temperature of 23 ° C. for 30 minutes, and then peeling the surface protective film from the glass plate at a temperature of 23 ° C. at 180 °. The peeling force A when peeled at a peeling speed of 300 mm / min is preferably 0.024 N / 25 mm to 0.50 N / 25 mm, more preferably 0.024 N / 25 mm to 0.40 N / 25 mm, and still more preferably Is 0.024 N / 25 mm to 0.30 N / 25 mm, particularly preferably 0.024 N / 25 mm to 0.20 N / 25 mm, and most preferably 0.024 N / 25 mm to 0.10 N / 25 mm. If the peeling force A is within the above range, the surface protective film of the present invention can be easily peeled off from the adherend. If the peeling force A is within the above range, typically, the surface protective film of the present invention attached to an exposed surface of the optical member or the electronic member during the manufacturing process of the optical member or the electronic member. Peeling can be difficult to occur. The details of the measurement of the peeling force A will be described later.

The surface protective film of the present invention is obtained by laminating the pressure-sensitive adhesive layer of the surface protective film on a glass plate and leaving it at a temperature of 100 ° C. for 2 days, and then removing the surface protective film from the glass plate at a temperature of 23 ° C., 180 °, The peeling force B when peeled at a peeling speed of 300 mm / min is preferably 0.20 N / 25 mm to 1.0 N / 25 mm, more preferably 0.25 N / 25 mm to 0.95 N / 25 mm, and still more preferably Is 0.30 N / 25 mm to 0.90 N / 25 mm, particularly preferably 0.35 N / 25 mm to 0.85 N / 25 mm, and most preferably 0.40 N / 25 mm to 0.80 N / 25 mm. If the peeling force B is within the above range, the surface protective film of the present invention can be prevented from being heavily peeled over time. The details of the measurement of the peeling force B will be described later.

In the surface protective film of the present invention, with respect to the peeling force A and the peeling force B, the rate of increase in peel force with time calculated by (B / A) × 100 is preferably 1000% or less, more preferably 950%. Or less, more preferably 900% or less, particularly preferably 850% or less, and most preferably 800% or less. About the minimum of the said peeling force aging increase rate, Preferably it is 450% or more. When the rate of increase in peeling force with time is within the above range, the surface protective film of the present invention can suppress heavy peeling over time even if the initial peeling force after being attached to an adherend is large.

The surface protective film of the present invention was prepared by laminating the pressure-sensitive adhesive layer of the surface protective film on a glass plate and leaving it to stand at 23 ° C. for 7 days, and then peeling the surface protective film from the glass plate at a temperature of 23 ° C. at a peeling angle of 180 ° The peeling force C when peeling at a speed of 300 mm / min is preferably 0.024 N / 25 mm to 0.50 N / 25 mm, more preferably 0.024 N / 25 mm to 0.40 N / 25 mm, and even more preferably It is 0.024 N / 25 mm to 0.30 N / 25 mm, particularly preferably 0.024 N / 25 mm to 0.20 N / 25 mm, and most preferably 0.024 N / 25 mm to 0.10 N / 25 mm. If the peeling force C is within the above range, the surface protective film of the present invention can be prevented from being heavily peeled over time. The details of the measurement of the peeling force C will be described later.

In the surface protective film of the present invention, with respect to the peeling force A and the peeling force C, the rate of increase in peel force with time calculated by (C / A) × 100 is preferably 160% or less, more preferably 155%. Or less, more preferably 150% or less, particularly preferably 145% or less, and most preferably 140% or less. About the minimum of the said peeling force aging increase rate, Preferably it is 80% or more. When the rate of increase in peeling force with time is within the above range, the surface protective film of the present invention can suppress heavy peeling over time even if the initial peeling force after being attached to an adherend is large.

The surface protective film of the present invention has a residual adhesion rate of preferably 50% or more, more preferably 60% to 100%, still more preferably 70% to 100%, and particularly preferably 80% to 100%. %, Most preferably 85% to 100%. When the residual adhesion rate is within the above range, the surface protective film of the present invention can exhibit an effect that the adherend surface is less contaminated by being attached to the adherend. Details of the measurement of the residual adhesion rate will be described later.

The surface protective film of the present invention can be produced by any appropriate method. As such a manufacturing method, for example,
(1) A method of applying a solution of a material for forming an adhesive layer or a hot melt on a base material layer,
(2) A method of transferring a pressure-sensitive adhesive layer formed by applying a solution of a material for forming a pressure-sensitive adhesive layer or a hot melt on a separator onto a base material layer,
(3) A method of forming and applying the forming material of the pressure-sensitive adhesive layer onto the base material layer,
(4) A method of extruding a base material layer and an adhesive layer in two layers or multiple layers,
(5) A method of laminating a pressure-sensitive adhesive layer on a base material layer, or a method of laminating two pressure-sensitive adhesive layers together with a laminate layer,
(6) A method of laminating a pressure-sensitive adhesive layer and a base material layer forming material such as a film or a laminate layer in two or multiple layers,
It can be performed according to any appropriate production method.

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

<< A-1. Base material layer >>
Only one layer may be sufficient as a base material layer, and two or more layers may be sufficient as it. The base material layer may be stretched.

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

For the purpose of forming a wound body that can be easily rewound, for example, a fatty acid amide, a polyethyleneimine, a long-chain alkyl-based additive, Etc. can be added to perform a mold release treatment, or a coating layer made of any appropriate release agent such as silicone, long chain alkyl, or fluorine can be provided.

As the material of the base material layer, any appropriate material can be adopted depending on the application. For example, a plastic, paper, a metal film, a nonwoven fabric, etc. are mentioned. Preferably, it is a plastic. That is, the base material layer is preferably a plastic film. The base material layer may be composed of one kind of material or may be composed of two or more kinds of materials. For example, you may be comprised from 2 or more types 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 resin include olefin monomer homopolymers, olefin monomer copolymers, and the like. Specific examples of polyolefin resins include homopolypropylene; block-type, random-type, and graft-type propylene copolymers having an ethylene component as a copolymer component; reactor TPO; low density, high density, linear Low density, ultra-low density, etc. ethylene polymers; ethylene / propylene copolymer, ethylene / vinyl acetate copolymer, ethylene / methyl acrylate copolymer, ethylene / ethyl acrylate copolymer, ethylene / acrylic acid And ethylene copolymers such as butyl copolymer, ethylene / methacrylic acid copolymer, and ethylene / methyl methacrylate copolymer.

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

Any appropriate antioxidant can be adopted as the antioxidant. Examples of such antioxidants include phenol-based antioxidants, phosphorus-based processing heat stabilizers, lactone-based processing heat stabilizers, sulfur-based heat-resistant stabilizers, phenol-phosphorus-based antioxidants, and the like. The content of the antioxidant is preferably 1% by weight or less with respect to the base resin of the base layer (when the base layer is a blend, the blend is the base resin), more preferably It is 0.5% by weight or less, and more preferably 0.01% by weight to 0.2% by weight.

Any appropriate UV absorber can be adopted as the UV absorber. Examples of such UV absorbers include benzotriazole UV absorbers, triazine UV absorbers, and benzophenone UV absorbers. The content ratio of the ultraviolet absorber is preferably 2% by weight or less based on the base resin forming the base layer (when the base layer is a blend, the blend is the base resin), The content is preferably 1% by weight or less, more preferably 0.01% by weight to 0.5% by weight.

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

Any suitable filler can be adopted as the filler. 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 with respect to the base resin forming the base layer (when the base layer is a blend, the blend is the base resin), and more preferably Is 10 wt% or less, more preferably 0.01 wt% to 10 wt%.

Furthermore, as the additive, for the purpose of imparting antistatic properties, inorganic, low molecular weight and high molecular weight antistatic agents such as surfactants, inorganic salts, polyhydric alcohols, metal compounds, carbon and the like are also preferred. In particular, a high molecular weight antistatic agent and carbon are preferable from the viewpoint of contamination and adhesiveness maintenance.

<< A-2. Adhesive layer >>
The pressure-sensitive adhesive layer can be composed of a pressure-sensitive adhesive. The pressure-sensitive adhesive can be formed from a pressure-sensitive adhesive composition.

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

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

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

The content ratio of the total amount of the base polymer, the silicone-based additive and the fluorine-based additive in the pressure-sensitive adhesive composition is preferably 50% by weight to 100% by weight, more preferably 60% by weight to 100% by weight. More preferably, it is 70% to 100% by weight, particularly preferably 75% to 100% by weight, and most preferably 80% to 100% by weight. If the content ratio of the total amount of the base polymer, the silicone-based additive, and the fluorine-based additive in the pressure-sensitive adhesive composition is within the above range, the surface protective film of the present invention is more easily peeled off from the adherend. It can be difficult, heavy peeling over time can be further suppressed, and the effect that the adherend surface is less contaminated by being attached to the adherend can be more manifested.

The content of the silicone-based additive and / or fluorine-based additive in the pressure-sensitive adhesive composition is preferably 0.001 part by weight as the total amount of the silicone-based additive and the fluorine-based additive with respect to 100 parts by weight of the base polymer. -50 parts by weight, more preferably 0.005 parts by weight to 25 parts by weight, still more preferably 0.01 parts by weight to 10 parts by weight, still more preferably 0.01 parts by weight to 1 part by weight. More preferably 0.01 parts by weight to 0.50 parts by weight, particularly preferably 0.01 parts by weight to 0.30 parts by weight, and most preferably 0.01 parts by weight to 0.28 parts by weight. It is. If the content of the silicone-based additive and / or fluorine-based additive in the pressure-sensitive adhesive composition is within the above range, the surface protective film of the present invention can be more easily peeled off from the adherend, Heavy peeling can be further suppressed, and the effect that the adherend surface is less contaminated by being attached to the adherend can be more manifested.

That is, when the pressure-sensitive adhesive composition contains a silicone additive but no fluorine additive, the content of the silicone additive with respect to 100 parts by weight of the base polymer is preferably 0.001 to 50 parts by weight. Parts, more preferably 0.005 to 25 parts by weight, still more preferably 0.01 to 10 parts by weight, still more preferably 0.01 to 1 part by weight, The amount is preferably 0.01 part by weight to 0.50 part by weight, particularly preferably 0.01 part by weight to 0.30 part by weight, and most preferably 0.01 part by weight to 0.28 part by weight. If the content of the silicone-based additive in the pressure-sensitive adhesive composition is within the above range, the surface protective film of the present invention can be more easily peeled off from the adherend, and the heavy peeling over time is further suppressed. Thus, the effect that the adherend surface is less contaminated by being attached to the adherend can be further exhibited.

In the case where the adhesive composition does not contain a silicone additive but contains a fluorine additive, the content of the fluorine additive with respect to 100 parts by weight of the base polymer is preferably 0.001 to 50 parts by weight. Parts, more preferably 0.005 to 25 parts by weight, still more preferably 0.01 to 10 parts by weight, still more preferably 0.01 to 1 part by weight, The amount is preferably 0.01 part by weight to 0.50 part by weight, particularly preferably 0.01 part by weight to 0.30 part by weight, and most preferably 0.01 part by weight to 0.28 part by weight. If the content of the fluorine-containing additive in the pressure-sensitive adhesive composition is within the above range, the surface protective film of the present invention can be more easily peeled off from the adherend, and the heavy peeling over time is further suppressed. Thus, the effect that the adherend surface is less contaminated by being attached to the adherend can be further exhibited.

Further, when both the silicone additive and the fluorine additive are contained in the pressure-sensitive adhesive composition, the total content ratio of the silicone additive and the fluorine additive with respect to 100 parts by weight of the base polymer is preferably 0.00. 001 to 50 parts by weight, more preferably 0.005 to 25 parts by weight, still more preferably 0.01 to 10 parts by weight, still more preferably 0.01 to 1 part by weight. Parts by weight, more preferably 0.01 parts by weight to 0.50 parts by weight, particularly preferably 0.01 parts by weight to 0.30 parts by weight, and most preferably 0.01 parts by weight to 0. 28 parts by weight. If the total content of the silicone-based additive and the fluorine-based additive in the pressure-sensitive adhesive composition is within the above range, the surface protective film of the present invention can be more easily peeled off from the adherend. Heavy peeling can be further suppressed, and the effect that the adherend surface is less contaminated by being attached to the adherend can be more manifested.

<A-2-1. Base polymer>
The base polymer is preferably at least one selected from urethane prepolymers, polyols, acrylic resins, rubber resins, and silicone resins. If the base polymer is at least one selected from urethane prepolymers, polyols, acrylic resins, rubber resins, and silicone resins, the surface protective film of the present invention can be more easily removed from the adherend. Further, the heavy peeling over time can be further suppressed, and the effect that the adherend surface is less contaminated by being attached to the adherend can be further exhibited.

[A-2-1-a. Urethane prepolymer)
The urethane prepolymer is preferably a polyurethane polyol, more preferably a polyester polyol (a1) or a polyether polyol (a2), each alone or in a mixture of (a1) and (a2). It is obtained by reacting with the organic polyisocyanate compound (a3) under or without a catalyst.

Any appropriate polyester polyol may be used as the polyester polyol (a1). Examples of such polyester polyol (a1) include polyester polyols obtained by reacting an acid component and a glycol component. Examples of the acid component include terephthalic acid, adipic acid, azelaic acid, sebacic acid, phthalic anhydride, isophthalic acid, trimellitic acid, and the like. Examples of the glycol component include ethylene glycol, propylene glycol, diethylene glycol, butylene glycol, 1,6-hexane glycol, 3-methyl-1,5-pentanediol, 3,3′-dimethylol heptane, polyoxyethylene glycol, Polyoxypropylene glycol, 1,4-butanediol, neopentyl glycol, butylethylpentanediol, and polyol components include glycerin, trimethylolpropane, pentaerythritol and the like. Other examples of the polyester polyol (a1) include polyester polyols obtained by ring-opening polymerization of lactones such as polycaprolactone, poly (β-methyl-γ-valerolactone), and polyvalerolactone.

The molecular weight of the polyester polyol (a1) can be used from a low molecular weight to a high molecular weight. The molecular weight of the polyester polyol (a1) is preferably a number average molecular weight of 100 to 100,000. When the number average molecular weight is less than 100, the reactivity is increased and the gelation tends to occur. When the number average molecular weight exceeds 100,000, the reactivity is 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.

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

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

A part of the polyether polyol (a2), if necessary, may be glycols such as ethylene glycol, 1,4-butanediol, neopentyl glycol, butylethylpentanediol, glycerin, trimethylolpropane, pentaerythritol, They can be used in combination with polyamines such as ethylenediamine, N-aminoethylethanolamine, isophoronediamine, and xylylenediamine.

As the polyether polyol (a2), only a bifunctional polyether polyol may be used, or a polyether having a number average molecular weight of 100 to 100,000 and having at least 3 or more hydroxyl groups in one molecule. A part or all of the polyol may be used. When a polyether polyol (a2) having a number average molecular weight of 100 to 100,000 and having at least 3 or more hydroxyl groups in one molecule is used partly or entirely, adhesive strength and removability can be obtained. Balance can be good. In such a polyether polyol, if the number average molecular weight is less than 100, the reactivity becomes high and the gelation tends to occur. Moreover, in such a polyether polyol, when the number average molecular weight exceeds 100,000, the reactivity is lowered, and further, the cohesive force of the polyurethane polyol itself may be reduced. The number average molecular weight of such polyether polyol is more preferably 100 to 10,000.

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

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

Examples of the araliphatic polyisocyanate include ω, ω′-diisocyanate-1,3-dimethylbenzene, ω, ω′-diisocyanate-1,4-dimethylbenzene, ω, ω′-diisocyanate-1,4-diethylbenzene. 1,4-tetramethylxylylene diisocyanate, 1,3-tetramethylxylylene diisocyanate, and the like.

Examples of the alicyclic polyisocyanate include 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate, 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, and methyl-2. , 4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), 1,4-bis (isocyanate methyl) cyclohexane, 1,4-bis (isocyanate methyl) cyclohexane, etc. It is done.

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

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

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

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

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

Examples of non-tin compounds include titanium compounds such as dibutyltitanium dichloride, tetrabutyltitanate and butoxytitanium trichloride; lead compounds such as lead oleate, lead 2-ethylhexanoate, lead benzoate and lead naphthenate Iron compounds such as iron 2-ethylhexanoate and iron acetylacetonate; cobalt compounds such as cobalt benzoate and cobalt 2-ethylhexanoate; zinc compounds such as zinc naphthenate and zinc 2-ethylhexanoate; And zirconium-based compounds such as zirconium naphthenate.

When a catalyst is used in obtaining a polyurethane polyol, in a system in which two types of polyols, a polyester polyol and a polyether polyol, are present, due to the difference in reactivity, in a single catalyst system, gelation or a reaction solution is caused. The problem of becoming cloudy is likely to occur. Therefore, by using two kinds of catalysts when obtaining the polyurethane polyol, the reaction rate, the selectivity of the catalyst and the like can be easily controlled, and these problems can be solved. Examples of such a combination of two types of catalysts include tertiary amine / organometallic, tin / non-tin, and tin / tin, preferably tin / tin, more preferably Is a combination of dibutyltin dilaurate and tin 2-ethylhexanoate. The mixing ratio of tin 2-ethylhexanoate / dibutyltin dilaurate is preferably less than 1 and more preferably 0.2 to 0.6. If the blending ratio is 1 or more, gelation tends to occur due to the balance of catalytic activity.

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

When a catalyst is used in obtaining the polyurethane polyol, the reaction temperature is preferably less than 100 ° C., more preferably 85 ° C. to 95 ° C. If it is 100 ° C. or higher, it may be difficult to control the reaction rate and the crosslinked structure, and it may be difficult to obtain a polyurethane polyol having a predetermined molecular weight.

When obtaining the polyurethane polyol, it is not necessary to use a catalyst. In that case, reaction temperature becomes like this. Preferably it is 100 degreeC or more, More preferably, it is 110 degreeC or more. Moreover, when obtaining a polyurethane polyol without a catalyst, it is preferable to make it react for 3 hours or more.

For example, 1) polyester polyol, polyether polyol, catalyst, and organic polyisocyanate are charged into a flask. 2) polyester polyol, polyether polyol, and catalyst are charged into a flask and organic polyisocyanate is obtained. The method of adding by dripping is mentioned. As a method for obtaining the polyurethane polyol, the method 2) is preferable in controlling the reaction.

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

[A-2-1-b. Polyol)
Examples of the polyol preferably include polyester polyol, polyether polyol, polycaprolactone polyol, polycarbonate polyol, and castor oil-based polyol. The polyol is more preferably a polyether polyol.

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

Examples of the polyol component include ethylene glycol, diethylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2-butyl-2-ethyl-1 , 3-propanediol, 2,4-diethyl-1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 2-methyl -1,8-octanediol, 1,8-decanediol, octadecanediol, glycerin, trimethylolpropane, pentaerythritol, hexanetriol, polypropylene glycol and the like. Examples of the acid component include succinic acid, methyl succinic 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, 4,4'-biphenyldicarboxylic acid , And these acid anhydrides.

Examples of polyether polyols include water, low molecular weight polyols (propylene glycol, ethylene glycol, glycerin, trimethylolpropane, pentaerythritol, etc.), bisphenols (bisphenol A, etc.), dihydroxybenzenes (catechol, resorcin, hydroquinone, etc.), etc. And polyether polyols obtained by addition polymerization of alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide. Specific examples 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 cyclic ester monomers such as ε-caprolactone and σ-valerolactone.

Examples of the polycarbonate polyol include a polycarbonate polyol obtained by polycondensation reaction of the polyol component and phosgene; the polyol component, dimethyl carbonate, diethyl carbonate, diprovir carbonate, diisopropyl carbonate, dibutyl carbonate, ethyl butyl carbonate, ethylene carbonate, Polycarbonate polyol obtained by ester exchange condensation with carbonic acid diesters such as propylene carbonate, diphenyl carbonate and dibenzyl carbonate; copolymerized polycarbonate polyol obtained by using two or more of the above polyol components in combination; Polycarbonate polyol obtained by esterification reaction with a compound; the above-mentioned various polycarbonate polyols and a hydroxyl group-containing compound; Polycarbonate polyol obtained by etherification reaction; polycarbonate polyol obtained by transesterification of the various polycarbonate polyols and ester compounds; polycarbonate polyol obtained by transesterification of the various polycarbonate polyols and hydroxyl group-containing compounds; And polyester polycarbonate polyols obtained by polycondensation reaction of the various polycarbonate polyols with dicarboxylic acid compounds; copolymer polyether polycarbonate polyols obtained by copolymerizing the various polycarbonate polyols and alkylene oxides;

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

The number average molecular weight Mn of the polyol is preferably 300 to 100,000, more preferably 400 to 75,000, still more preferably 450 to 50,000, and particularly preferably 500 to 30,000. If the number average molecular weight Mn of the polyol is within the above range, the surface protective film of the present invention can be more easily peeled off from the adherend, and the heavy peeling over time can be further suppressed.

The polyol preferably contains a polyol (A1) having three OH groups and a number average molecular weight Mn of 300 to 100,000. As for a polyol (A1), only 1 type may be sufficient and 2 or more types may be sufficient.

The content ratio of the polyol (A1) in the polyol is preferably 5% by weight or more, more preferably 25% by weight to 100% by weight, and further preferably 50% by weight to 100% by weight. If the content ratio of the polyol (A1) in the polyol is within the above range, the surface protective film of the present invention can be more easily removed from the adherend, and the heavy peeling over time can be further suppressed.

The number average molecular weight Mn of the polyol (A1) is preferably 1000 to 100,000, more preferably 1200 to 80000, still more preferably 1500 to 70000, still more preferably 1750 to 50000, and particularly preferably 1500. -40000, most preferably 2000-30000. If the number average molecular weight Mn of the polyol (A1) is within the above range, the surface protective film of the present invention can be more easily removed from the adherend, and the heavy 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 polyol (A2) may be only one kind or two or more kinds. The number average molecular weight Mn of the polyol (A2) is preferably 100 to 20000, more preferably 150 to 10,000, still more preferably 200 to 7500, particularly preferably 300 to 6000, and most preferably 300. ~ 5000. When the number average molecular weight Mn of the polyol (A2) is out of the above range, particularly, there is a risk that the aging of the peeling force of the surface protective film of the present invention is increased. The polyol (A2) is preferably a polyol (triol) having 3 OH groups, a polyol (tetraol) having 4 OH groups, a polyol (pentaol) having 5 OH groups, and 6 OH groups. The polyol (hexaol) which has is mentioned.

The total amount of polyol (tetraol) having 4 OH groups, polyol (pentaol) having 5 OH groups, and polyol (hexaol) having 6 OH groups as the polyol (A2) is The content is preferably 70% by weight or less, more preferably 60% by weight or less, still more preferably 40% by weight or less, and particularly preferably 30% by weight or less. The total amount of the polyol (tetraol) having 4 OH groups, the polyol having 5 OH groups (pentaol), and the polyol having 6 OH groups (hexaol) as the polyol (A2) in the polyol. If the content ratio in the polyol is in the above range, an adhesive layer having excellent transparency can be provided, and the surface protective film of the present invention can be more easily peeled off from the adherend. Exfoliation can be further suppressed.

The content ratio of the polyol (A2) in the polyol is preferably 95% by weight or less, more preferably 0% by weight to 75% by weight. If the content ratio of the polyol (A2) in the polyol is within the above range, the surface protective film of the present invention can be more easily removed from the adherend, and the heavy peeling over time can be further suppressed.

As the polyol (A2), the content ratio of the polyol having 4 or more OH groups and a number average molecular weight Mn of 20000 or less is preferably less than 70% by weight, more preferably 60% by weight or less, based on the whole polyol. More preferably, it is 50% by weight or less, particularly preferably 40% by weight or less, and most preferably 30% by weight or less. If the content ratio of the polyol having a number average molecular weight Mn having 4 or more OH groups as the polyol (A2) is 20000 or less is within the above range with respect to the whole polyol, a pressure-sensitive adhesive layer excellent in transparency is provided. In addition, the surface protective film of the present invention can be more easily peeled off from the adherend, and the heavy peeling over time can be further suppressed.

[A-2-1-c. (Acrylic resin)
As the acrylic resin, any appropriate acrylic pressure-sensitive adhesive such as, for example, a known acrylic pressure-sensitive adhesive described in JP2013-241606A can be used as long as the effects of the present invention are not impaired.

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

[A-2-1-d. (Rubber resin)
As the rubber-based resin, any appropriate rubber-based pressure-sensitive adhesive such as a known rubber-based pressure-sensitive adhesive described in JP-A-2015-074771 can be employed as long as the effects of the present invention are not impaired. These may be only one kind or two or more kinds.

The rubber-based resin can contain any appropriate component as long as the effects of the present invention are not impaired. Examples of such components include resin components other than rubber-based resins, tackifiers, inorganic fillers, organic fillers, metal powders, pigments, foils, softeners, anti-aging agents, conductive agents, and ultraviolet absorption. Agents, 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 pressure-sensitive adhesive, any appropriate silicone-based pressure-sensitive adhesive such as a known silicone-based pressure-sensitive adhesive described in Japanese Patent Application Laid-Open No. 2014-047280 can be adopted as long as the effects of the present invention are not impaired. . These may be only one kind or two or more kinds.

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

<A-2-2. Silicone-based additive>
Any appropriate silicone-based additive can be adopted as the silicone-based additive as long as the effects of the present invention are not impaired. As such a silicone type additive, Preferably, at least 1 sort (s) chosen from a siloxane bond containing compound, a hydroxyl group containing silicone type compound, and a crosslinkable functional group containing silicone type compound is mentioned.

Only one type of silicone-based additive may be used, or two or more types may be used.

Examples of the siloxane bond-containing compound include a polyether-modified polyorganosiloxane having a polyether group introduced into the main chain or side chain of a polyorganosiloxane skeleton (such as polydimethylsiloxane), or the main chain or side chain of the polyorganosiloxane skeleton. Polyester-modified polyorganosiloxane with a polyester group introduced, organic compound-introduced polyorganosiloxane with an organic compound introduced into the main chain or side chain of the polyorganosiloxane skeleton, silicone-modified with a polyorganosiloxane introduced into a (meth) acrylic resin ( Examples thereof include a (meth) acrylic resin, a silicone-modified organic compound obtained by introducing polyorganosiloxane into an organic compound, and a silicone-containing organic compound obtained by copolymerizing an organic compound and a silicone compound. Examples of such siloxane bond-containing polymers include commercially available products such as “LE-302” (manufactured by Kyoeisha Chemical Co., Ltd.), BYK series leveling agents (“BYK-300” manufactured by BYK Japan). ”,“ BYK-301 / 302 ”,“ BYK-306 ”,“ BYK-307 ”,“ BYK-310 ”,“ BYK-315 ”,“ BYK-313 ”,“ BYK-320 ”,“ BYK-322 ” ”,“ BYK-323 ”,“ BYK-325 ”,“ BYK-330 ”,“ BYK-331 ”,“ BYK-333 ”,“ BYK-337 ”,“ BYK-341 ”,“ BYK-344 ”, “BYK-345 / 346”, “BYK-347”, “BYK-348”, “BYK-349”, “BYK-370”, “BYK-375”, “BYK-” 77 ”,“ BYK-378 ”,“ BYK-UV3500 ”,“ BYK-UV3510 ”,“ BYK-UV3570 ”,“ BYK-3550 ”,“ BYK-SILCLEAN3700 ”,“ BYK-SILCLEAN3720 ”, etc.), Algin Chemie AC series leveling agents (“AC FS180”, “AC FS360”, “AC S20”, etc.) manufactured by Kyoeisha Chemical Co., Ltd. (“Polyflow KL-400X”, “Polyflow KL-”) 400HF "," Polyflow KL-401 "," Polyflow KL-402 "," Polyflow KL-403 "," Polyflow KL-404 ", etc.), Shin-Etsu Chemical Co., Ltd. KP series leveling agent (" KP- 323 "," KP-326 "," KP- 41 ”,“ KP-104 ”,“ KP-110 ”,“ KP-112 ”, etc.), X22 series made by Shin-Etsu Chemical Co., Ltd., KF series, etc. Leveling agents made by Toray Dow Corning (“ LP- 7001 "," LP-7002 "," 8032ADDITIVE "," 57ADDITIVE "," L-7604 "," FZ-2110 "," FZ-2105 "," 67ADDITIVE "," 8618ADDITIVE "," 3ADDITIVE "," 56ADDITIVE " Etc.).

Examples of the hydroxyl group-containing silicone compound include a polyether-modified polyorganosiloxane having a polyether group introduced into the main chain or side chain of a polyorganosiloxane skeleton (such as polydimethylsiloxane), or the main chain or side chain of the polyorganosiloxane skeleton. Polyester-modified polyorganosiloxane with a polyester group introduced into it, an organic compound-introduced polyorganosiloxane with an organic compound introduced into the main chain or side chain of the polyorganosiloxane skeleton, and a silicone-modified polyorganosiloxane introduced into a (meth) acrylic resin Examples include (meth) acrylic resins, silicone-modified organic compounds obtained by introducing polyorganosiloxane into organic compounds, and silicone-containing organic compounds obtained by copolymerizing organic compounds and silicone compounds. In these, the hydroxyl group may have a polyorganosiloxane skeleton, and may have a polyether group, a polyester group, a (meth) acryloyl group, or an organic compound. Examples of such hydroxyl group-containing silicone include commercially available products such as trade names “X-22-4015”, “X-22-4039”, “KF6000”, “KF6001”, “KF6002”, “KF6003”, “X-22-170BX”, “X-22-170DX”, “X-22-176DX”, “X-22-176F” (manufactured by Shin-Etsu Chemical Co., Ltd.), “BYK” manufactured by Big Chemie Japan Co., Ltd. -370 "," BYK-SILCLEAN3700 "," BYK-SILCLEAN3720 ", and the like.

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

<A-2-3. Fluorine-based additive>
Arbitrary appropriate fluorine-type additives can be employ | adopted for the fluorine-type additive in the range which does not impair the effect of this invention. As such a fluorine-type additive, Preferably, at least 1 sort (s) chosen from a fluorine-containing compound, a hydroxyl-containing fluorine-type compound, and a crosslinkable functional group containing fluorine-type compound is mentioned.

Only one type of fluorine-based additive may be used, or two or more types may be used.

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, fluoro t-butane, fluoropentane, and fluorohexane. It is done. Examples of such fluorine-containing compounds include commercially available Surflon series leveling agents (“S-242”, “S-243”, “S-420”, “S-420”, “AGC Seimi Chemical Co., Ltd.”). S-611 "," S-651 "," S-386 ", etc.), BYK series leveling agents (such as" BYK-340 ") manufactured by BYK Japan, Inc., AC series leveling manufactured by Algin Chemie. Agents (“AC 110a”, “AC 100a”, etc.), leveling agents (“Megafuck F-114”, “Megafuck F-410”, “Megafuck F-444” manufactured by DIC Corporation) , “Megafuck EXP TP-2066”, “Megafuck F-430”, “Megafuck F-472SF”, “Megafa "F-477", "Megafuck F-552", "Megafuck F-553", "Megafuck F-554", "Megafuck F-555", "Megafuck R-94", "Megafuck RS-" “72-K”, “Megafuck RS-75”, “Megafuck F-556”, “Megafuck EXP TF-1367”, “Megafuck EXP TF-1437”, “Megafuck F-558”, “Megafuck” EXP TF-1537, etc.), FC series leveling agents (“FC-4430”, “FC-4432”, etc.) manufactured by Sumitomo 3M Co., Ltd., leveling agents (“Futter”) manufactured by Neos Co., Ltd. "100", "100", "110", "150", "Faget" "150CH", "Factent AK", "Factent 501", "Factent 250", "Factent 251", "Factent 222F", "Factent 208G", "Factent 300", "Footer Gent 310 "," Fargent 400SW ", etc.), PF series leveling agents (" PF-136A "," PF-156A "," PF-151N "," PF-636 ") manufactured by Kitamura Chemical Industry Co., Ltd. “PF-6320”, “PF-656”, “PF-6520”, “PF-651”, “PF-652”, “PF-3320”, etc.).

As the hydroxyl group-containing fluorine-based compound, for example, a conventionally known resin can be used. For example, WO94 / 06870 pamphlet, JP-A-8-12921, JP-A-10-72569, JP-A-4-275379. And the hydroxyl group-containing fluororesins described in International Publication No. 97/11130, International Publication No. 96/26254, and the like. Examples of other hydroxyl group-containing fluororesins include fluoroolefin copolymers described in JP-A-8-231919, JP-A-10-265731, JP-A-10-204374, JP-A-8-12922, and the like. A polymer etc. are mentioned. Other examples include a copolymer of a compound having a fluorinated alkyl group with a hydroxyl group-containing compound, a fluorine-containing organic compound obtained by copolymerizing a fluorine-containing compound with a hydroxyl group-containing compound, and a fluorine-containing compound containing a hydroxyl group-containing organic compound. As such a hydroxyl group-containing fluorine-based compound, as commercial products, for example, trade name “Lumiflon” (manufactured by Asahi Glass Co., Ltd.), trade name “cefural coat” (manufactured by Central Glass Co., Ltd.), trade name “Zaflon” (Manufactured by Toa Gosei Co., Ltd.), trade name “Zeffle” (produced by Daikin Industries, Ltd.), trade name “Megafac F-571”, “Fluonate” (produced by DIC Corporation), and the like.

Examples of the crosslinkable functional group-containing fluorine-based compound include a carboxylic acid compound having a fluorinated alkyl group such as perfluorooctanoic acid, and a compound having a fluorinated alkyl group in the crosslinkable functional group-containing compound. Examples thereof include a polymer, a fluorine-containing organic compound obtained by copolymerizing a fluorine-containing compound with a crosslinkable functional group-containing compound, and a fluorine-containing compound containing a crosslinkable functional group-containing compound. As such a crosslinkable functional group-containing fluorine-based compound, commercially available products include, for example, trade names “Megafac F-570”, “Megafac RS-55”, “Megafac RS-56”, “Megafac” “RS-72-K”, “Megafuck RS-75”, “Megafuck RS-76-E”, “Megafuck RS-76-NS”, “Megafuck RS-78”, “Megafuck RS-90” (Made by DIC Corporation).

<A-2-4. Urethane resin>
Each of the urethane prepolymer and the polyol as the base polymer can be a component of a composition for forming a urethane resin in combination with the polyfunctional isocyanate compound (B). By adopting the above as a component of the composition for forming the urethane-based resin, the surface protective film of the present invention can be more easily peeled off from the adherend, resulting in heavy peeling over time. It can be more suppressed.

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

The composition for forming the urethane-based resin preferably contains a deterioration inhibitor such as an antioxidant, an ultraviolet absorber, and a light stabilizer. The composition for forming the urethane-based resin contains an anti-degradation agent, so that adhesive residue remains on the adherend even if it is stored in a heated state after the pressure-sensitive adhesive layer is applied to the adherend. It can be excellent in preventing adhesive residue, such as being difficult. Only one type of deterioration preventing agent may be used, or two or more types may be used. 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 phenolic antioxidants and amine antioxidants.

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

Examples of phenolic antioxidants include monophenolic antioxidants, bisphenolic antioxidants, and high-molecular phenolic antioxidants.

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

Examples of the bisphenol antioxidant include 2,2′-methylenebis (4-methyl-6-t-butylphenol), 2,2′-methylenebis (4-ethyl-6-t-butylphenol), 4,4 ′. -Thiobis (3-methyl-6-t-butylphenol), 4,4'-butylidenebis (3-methyl-6-t-butylphenol), 3,9-bis [1,1-dimethyl-2- [β- ( 3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl] 2,4,8,10-tetraoxaspiro [5,5] undecane.

Examples of the polymeric phenolic antioxidant include 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl-2,4, 6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, tetrakis- [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane Bis [3,3′-bis- (4′-hydroxy-3′-t-butylphenyl) butyric acid] glycol ester, 1,3,5-tris (3 ′, 5′-di-t-butyl) -4′-hydroxybenzyl) -S-triazine-2,4,6- (1H, 3H, 5H) trione, tocophenol and the like.

Examples of sulfur-based antioxidants include dilauryl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate, distearyl 3,3'-thiodipropionate.

Examples of phosphorus antioxidants include triphenyl phosphite, diphenylisodecyl phosphite, and phenyl diisodecyl phosphite.

Examples of UV absorbers include benzophenone UV absorbers, benzotriazole UV absorbers, salicylic acid UV absorbers, oxalic anilide UV absorbers, cyanoacrylate UV absorbers, and triazine UV absorbers. It is done.

Examples of the benzophenone ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2,2 ′ -Dihydroxy-4-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone, bis (2-methoxy-4-hydroxy-5-benzoylphenyl) ) Methane.

Examples of the benzotriazole ultraviolet absorber include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-5′-tert-butylphenyl) benzotriazole, 2- ( 2'-hydroxy-3 ', 5'-di-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2 -(2'-hydroxy-3 ', 5'-di-tert-butylphenyl) 5-chlorobenzotriazole, 2- (2'-hydroxy-3', 5'-di-tert-amylphenyl) benzotriazole, 2- (2′-hydroxy-4′-octoxyphenyl) benzotriazole, 2- [2′-hydroxy-3 ′-( ″, 4 ″, 5 ″, 6 ″,-tetrahydrophthalimidomethyl) -5′-methylphenyl] benzotriazole, 2,2′methylenebis [4- (1,1,3,3-tetramethylbutyl) ) -6- (2H-benzotriazol-2-yl) phenol], 2- (2′-hydroxy-5′-methacryloxyphenyl) -2H-benzotriazole and the like.

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

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

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

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

Examples of the ultraviolet stabilizer include nickel bis (octylphenyl) sulfide, [2,2′-thiobis (4-tert-octylphenolate)]-n-butylamine nickel, nickel complex-3,5-di-tert- Examples thereof include butyl-4-hydroxybenzyl-phosphate monoethylate, nickel-dibutyldithiocarbamate, benzoate type quencher, and nickel-dibutyldithiocarbamate.

[A-2-4-a. Urethane 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) is formed from, for example, a composition containing the polyurethane polyol as the urethane prepolymer and the polyfunctional isocyanate compound (B). Urethane resin.

Only one type of urethane prepolymer may be used, or two or more types may be used.

1 type of polyfunctional isocyanate compounds (B) may be sufficient, and 2 or more types may be sufficient as them.

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

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, 2,4,4 Examples include 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, Examples include hydrogenated tolylene diisocyanate and hydrogenated tetramethylxylylene diisocyanate.

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

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

The composition containing the urethane prepolymer and the polyfunctional isocyanate compound (B) may contain any appropriate other component as long as the effects of the present invention are not impaired. Examples of such other components include resin components other than polyurethane resins, tackifiers, inorganic fillers, organic fillers, metal powders, pigments, foils, softeners, anti-aging agents, conductive agents, Examples include ultraviolet absorbers, antioxidants, light stabilizers, surface lubricants, leveling agents, corrosion inhibitors, heat stabilizers, polymerization inhibitors, lubricants, solvents, and catalysts.

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

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

In the urethane prepolymer and the polyfunctional isocyanate compound (B), the equivalent ratio of NCO group to OH group is preferably 5.0 or less, more preferably 0.01 to 4.75 as NCO group / OH group. More preferably 0.02 to 4.5, particularly preferably 0.03 to 4.25, and most preferably 0.05 to 4.0. If the equivalent ratio of NCO group / OH group is within the above range, the surface protective film of the present invention can be more easily removed from the adherend, and the heavy peeling over time can be further suppressed.

The content ratio of the polyfunctional isocyanate compound (B) is preferably 0.01% by weight to 30% by weight and more preferably 0.05% by weight with respect to the urethane prepolymer. 25 wt%, more preferably 0.1 wt% to 20 wt%, particularly preferably 0.5 wt% to 17.5 wt%, most preferably 1 wt% to 15 wt%. is there. If the content rate of a polyfunctional isocyanate compound (B) exists in the said range, the surface protection film of this invention will become difficult to peel from an adherend more easily, and the heavy peeling over time may be suppressed more.

[A-2-4-b. Urethane resin formed from composition containing polyol and polyfunctional isocyanate compound (B)]
Specifically, the urethane resin formed from the composition containing the polyol and the polyfunctional isocyanate compound (B) is preferably obtained by curing the composition containing the polyol and the polyfunctional isocyanate compound (B). Urethane resin.

Only one type of polyol may be used, or two or more types may be used.

1 type of polyfunctional isocyanate compounds (B) may be sufficient, and 2 or more types may be sufficient as them.

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

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, as NCO groups / OH groups. More preferably, it is 0.2 to 2.5, particularly preferably 0.3 to 2.25, and most preferably 0.5 to 2.0. If the equivalent ratio of NCO group / OH group is within the above range, the surface protective film of the present invention can be more easily removed from the adherend, and the heavy peeling over time can be further suppressed.

The content ratio of the polyfunctional isocyanate compound (B) is preferably 1.0% by weight to 30% by weight, more preferably 1.5% by weight to 27% by weight of the polyfunctional isocyanate compound (B) with respect to the polyol. % By weight, more preferably 2.0% by weight to 25% by weight, particularly preferably 2.3% by weight to 23% by weight, and most preferably 2.5% by weight to 20% by weight. If the content rate of a polyfunctional isocyanate compound (B) exists in the said range, the surface protection film of this invention will become difficult to peel from an adherend more easily, and the heavy peeling over time may be suppressed more.

Specifically, the polyurethane-based resin is preferably formed by curing a composition containing a polyol and a polyfunctional isocyanate compound (B). The method of curing a composition containing a polyol and a polyfunctional isocyanate compound (B) to form a urethane resin does not impair the effects of the present invention, such as a urethanization reaction method using bulk polymerization or solution polymerization. Any suitable method can be adopted in the range.

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

Examples of the organometallic compounds include iron compounds, tin compounds, titanium compounds, zirconium compounds, lead compounds, cobalt compounds, zinc compounds, and the like. 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 iron-based compounds include iron acetylacetonate and iron 2-ethylhexanoate.

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

Examples of titanium compounds include dibutyltitanium dichloride, tetrabutyltitanate, butoxytitanium trichloride, and the like.

Examples of zirconium compounds include zirconium naphthenate and zirconium acetylacetonate.

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

Examples of cobalt compounds include cobalt 2-ethylhexanoate and cobalt benzoate.

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

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

The catalyst may be only one kind or two or more kinds. A catalyst and a crosslinking retarder 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, and still more preferably 0.01% by weight based on the polyol. % To 0.50% by weight, particularly preferably 0.01% to 0.20% by weight. If the amount of the catalyst is within the above range, the surface protective film of the present invention can be more easily peeled off from the adherend, and the heavy peeling over time can be further suppressed.

The composition containing the polyol and the polyfunctional isocyanate compound (B) may contain any appropriate other component as long as the effects of the present invention are not impaired. Examples of such other components include resin components other than polyurethane resins, tackifiers, inorganic fillers, organic fillers, metal powders, pigments, foils, softeners, anti-aging agents, conductive agents, Examples include ultraviolet absorbers, antioxidants, light stabilizers, surface lubricants, leveling agents, corrosion inhibitors, heat stabilizers, polymerization inhibitors, lubricants, solvents, and catalysts.

<A-2-5. Fatty acid ester>
The pressure-sensitive adhesive composition preferably contains a fatty acid ester. 1 type of fatty acid ester may be sufficient and 2 or more types may be sufficient as it. If the pressure-sensitive adhesive composition contains a fatty acid ester, the surface protective film of the present invention can be more easily peeled off from the adherend, and can be prevented from being heavily peeled over time, and can be attached to the adherend. The effect that the contamination property of the adherend surface is low can be further exhibited.

The number average molecular weight Mn of the fatty acid ester is preferably from 100 to 800, more preferably from 150 to 750, even more preferably from 200 to 700, particularly preferably from 200 to 650, most preferably from 200 to 600. It is. If the number average molecular weight Mn of the fatty acid ester is within the above range, the surface protective film of the present invention can be more easily peeled off from the adherend, and the heavy release over time can be further suppressed. The effect that the contamination of the adherend surface due to the sticking is low can be further exhibited.

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

When the pressure-sensitive adhesive composition contains a fatty acid ester, the content of the fatty acid ester is preferably 0.01 parts by weight to 50 parts by weight, more preferably 0.05 parts by weight to 100 parts by weight of the base polymer. 45 parts by weight, more preferably 0.1 parts by weight to 40 parts by weight, further preferably 0.3 parts by weight to 35 parts by weight, and further preferably 0.5 parts by weight to 30 parts by weight. Particularly preferred is 0.5 to 25 parts by weight, and most preferred is 0.5 to 20 parts by weight. If 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 be more easily peeled off from the adherend, and the heavy peeling over time is further suppressed. Thus, the effect that the adherend surface is less contaminated by being attached to the adherend can be further exhibited.

<A-2-6. Other ingredients>
The pressure-sensitive adhesive composition can contain any appropriate other component as long as the effects of the present invention are not impaired. Examples of such other components include other resin components, tackifiers, inorganic fillers, organic fillers, metal powders, pigments, foils, softeners, anti-aging agents, conductive agents, and ultraviolet absorbers. , Antioxidants, light stabilizers, surface lubricants, leveling agents, corrosion inhibitors, heat stabilizers, polymerization inhibitors, lubricants, solvents, catalysts, and the like.

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

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

As the ionic liquid, any appropriate ionic liquid can be adopted as long as it does not impair the effects of the present invention as long as it is an ionic liquid containing a fluoro organic anion. Such an ionic liquid is preferably an ionic liquid composed of a fluoroorganic anion and an onium cation. By adopting an ionic liquid composed of a fluoro organic anion and an onium cation as the ionic liquid, it is possible to provide a pressure-sensitive adhesive composition having extremely excellent antistatic properties.

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

The onium cation capable of constituting the ionic liquid is preferably at least one selected from cations having a structure represented by the general formulas (1) to (5).

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

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

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

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

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

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

Specific examples of the cation represented by the general formula (1) include, for example, 1-ethylpyridinium cation, 1-butylpyridinium cation, 1-hexylpyridinium cation, 1-ethyl-3-methylpyridinium cation, 1-butyl -3-methylpyridinium cation, 1-hexyl-3-methylpyridinium cation, 1-butyl-4-methylpyridinium cation, 1-octyl-4-methylpyridinium cation, 1-butyl-3,4-dimethylpyridinium cation, Pyridinium cations such as 1,1-dimethylpyrrolidinium cation; 1-ethyl-1-methylpyrrolidinium cation, 1-methyl-1-propylpyrrolidinium cation, 1-methyl-1-butylpyrrolidinium cation, 1-methyl-1-pentylpyrrolidi Cation, 1-methyl-1-hexylpyrrolidinium cation, 1-methyl-1-heptylpyrrolidinium cation, 1-ethyl-1-propylpyrrolidinium cation, 1-ethyl-1-butylpyrrolidinium cation 1-ethyl-1-pentylpyrrolidinium cation, 1-ethyl-1-hexylpyrrolidinium cation, 1-ethyl-1-heptylpyrrolidinium cation, 1,1-dipropylpyrrolidinium cation, Pyrrolidinium cations such as 1-propyl-1-butylpyrrolidinium cation and 1,1-dibutylpyrrolidinium cation; 1-propylpiperidinium cation, 1-pentylpiperidinium cation, 1-methyl-1- Ethylpiperidinium cation, 1-methyl-1-propylpiperidinium cut 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, -Ethyl-1-heptylpiperidinium cation, 1-propyl-1-butylpiperidinium cation, 1,1-dimethylpiperidinium cation, 1,1-dipropylpiperidinium cation, 1,1-dibutyl Piperidinium cations such as piperidinium cations; 2-methyl-1-pyrroline cations; 1- And ethyl-2-phenylindole cation; 1,2-dimethylindole cation; 1-ethylcarbazole cation; and the like.

Of these, 1-ethylpyridinium cation, 1-butylpyridinium cation, 1-hexylpyridinium cation, 1-ethyl-3-methylpyridinium cation, -Pyridinium cations such as butyl-3-methylpyridinium cation, 1-hexyl-3-methylpyridinium cation, 1-butyl-4-methylpyridinium cation, 1-octyl-4-methylpyridinium cation; 1-ethyl-1- Methylpyrrolidinium cation, 1-methyl-1-propylpyrrolidinium cation, 1-methyl-1-butylpyrrolidinium cation, 1-methyl-1-pentylpyrrolidinium cation, 1-methyl-1-hexyl Pyrrolidinium cation, 1-methyl-1- Ptylpyrrolidinium cation, 1-ethyl-1-propylpyrrolidinium cation, 1-ethyl-1-butylpyrrolidinium cation, 1-ethyl-1-pentylpyrrolidinium cation, 1-ethyl-1-hexyl Pyrrolidinium cations such as pyrrolidinium cation and 1-ethyl-1-heptylpyrrolidinium cation; 1-methyl-1-ethylpiperidinium cation, 1-methyl-1-propylpiperidinium cation, 1- Methyl-1-butylpiperidinium cation, 1-methyl-1-pentylpiperidinium cation, 1-methyl-1-hexylpiperidinium cation, 1-methyl-1-heptylpiperidinium cation, 1-ethyl 1-propylpiperidinium cation, 1-ethyl-1-butylpiperidinium ON, 1-ethyl-1-pentylpiperidinium cation, 1-ethyl-1-hexylpiperidinium cation, 1-ethyl-1-heptylpiperidinium cation, 1-propyl-1-butylpiperidinium cation And more preferably, 1-hexylpyridinium cation, 1-ethyl-3-methylpyridinium cation, 1-butyl-3-methylpyridinium cation, 1-octyl-4-methyl, and the like. Pyridinium 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 tetrahydropyrimidinium cation, and a dihydropyrimidinium cation.

Specific examples of the cation represented by the general formula (2) include, for example, 1,3-dimethylimidazolium cation, 1,3-diethylimidazolium cation, 1-ethyl-3-methylimidazolium cation, and 1-butyl. -3-methylimidazolium cation, 1-hexyl-3-methylimidazolium cation, 1-octyl-3-methylimidazolium cation, 1-decyl-3-methylimidazolium cation, 1-dodecyl-3-methylimidazole Cation, 1-tetradecyl-3-methylimidazolium, 1,2-dimethyl-3-propylimidazolium cation, 1-ethyl-2,3-dimethylimidazolium cation, 1-butyl-2,3-dimethylimidazole Lithium cation, 1-hexyl-2,3-dimethylimida An imidazolium cation such as a lithium cation; 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, etc. Tetrahydropyrimidinium cation; 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- , 4-dihydropyrimidinium cation, 1,2,3,4-tetramethyl-1,6-dihydropyrimidinium dihydropyrimidinium cation, such as cations; and the like.

Among these, the 1,3-dimethylimidazolium cation, the 1,3-diethylimidazolium cation, the 1-ethyl-3-methylimidazolium cation, -Butyl-3-methylimidazolium cation, 1-hexyl-3-methylimidazolium cation, 1-octyl-3-methylimidazolium cation, 1-decyl-3-methylimidazolium cation, 1-dodecyl-3- An imidazolium cation such as a methylimidazolium cation or 1-tetradecyl-3-methylimidazolium cation, more preferably a 1-ethyl-3-methylimidazolium cation or 1-hexyl-3-methylimidazolium cation; is there.

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

Specific examples of the cation represented by the general formula (3) include, for example, 1-methylpyrazolium cation, 3-methylpyrazolium cation, 1-ethyl-2-methylpyrazolinium cation, 1-ethyl- Pyrazolium cations such as 2,3,5-trimethylpyrazolium cation, 1-propyl-2,3,5-trimethylpyrazolium cation, 1-butyl-2,3,5-trimethylpyrazolium cation; 1-ethyl-2,3,5-trimethylpyrazolinium cation, 1-propyl-2,3,5-trimethylpyrazolinium cation, 1-butyl-2,3,5-trimethylpyrazolinium cation, etc. Zolinium cation; and the like.

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

Specific examples of the cation represented by the general formula (4) include, for example, tetramethylammonium cation, tetraethylammonium cation, tetrabutylammonium cation, tetrapentylammonium cation, tetrahexylammonium cation, tetraheptylammonium cation, and triethylmethylammonium. Cation, tributylethylammonium cation, trimethylpropylammonium cation, trimethyldecylammonium cation, N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium cation, glycidyltrimethylammonium cation, trimethylsulfonium cation, triethylsulfonium cation , Tributylsulfonium cation, trihexylsulfonium cati , Diethylmethylsulfonium cation, dibutylethylsulfonium cation, dimethyldecylsulfonium cation, tetramethylphosphonium cation, tetraethylphosphonium cation, tetrabutylphosphonium cation, tetrahexylphosphonium cation, tetraoctylphosphonium cation, triethylmethylphosphonium cation, tributylethylphosphonium cation , Trimethyldecylphosphonium cation, diallyldimethylammonium cation and the like.

Among these, the triethylmethyl ammonium cation, tributyl ethyl ammonium cation, trimethyl decyl ammonium cation, diethyl methyl sulfonium cation, dibutyl ethyl sulfonium cation, dimethyl decyl sulfonium cation, Asymmetric tetraalkylammonium cations such as triethylmethylphosphonium cation, tributylethylphosphonium cation, trimethyldecylphosphonium cation, trialkylsulfonium cation, tetraalkylphosphonium cation, N, N-diethyl-N-methyl-N- (2-methoxy Ethyl) ammonium cation, glycidyl trimethyl ammonium cation, diallyl dimethyl ammonium Cation, N, N-dimethyl-N-ethyl-N-propylammonium cation, N, N-dimethyl-N-ethyl-N-butylammonium cation, N, N-dimethyl-N-ethyl-N-pentylammonium cation, N, N-dimethyl-N-ethyl-N-hexylammonium cation, N, N-dimethyl-N-ethyl-N-heptylammonium cation, N, N-dimethyl-N-ethyl-N-nonylammonium cation, N, N-dimethyl-N, N-dipropylammonium cation, N, N-diethyl-N-propyl-N-butylammonium cation, N, N-dimethyl-N-propyl-N-pentylammonium cation, N, N-dimethyl -N-propyl-N-hexylammonium cation, N, N-dimethyl N-propyl-N-heptylammonium cation, N, N-dimethyl-N-butyl-N-hexylammonium cation, N, N-diethyl-N-butyl-N-heptylammonium cation, N, N-dimethyl-N- Pentyl-N-hexylammonium cation, N, N-dimethyl-N, N-dihexylammonium cation, trimethylheptylammonium cation, N, N-diethyl-N-methyl-N-propylammonium cation, N, N-diethyl-N -Methyl-N-pentylammonium cation, N, N-diethyl-N-methyl-N-heptylammonium cation, N, N-diethyl-N-propyl-N-pentylammonium cation, triethylpropylammonium cation, triethylpentylammonium Cation, triethylheptylammonium cation, N, N-dipropyl-N-methyl-N-ethylammonium cation, N, N-dipropyl-N-methyl-N-pentylammonium cation, N, N-dipropyl-N-butyl-N -Hexylammonium cation, N, N-dipropyl-N, N-dihexylammonium cation, N, N-dibutyl-N-methyl-N-pentylammonium cation, N, N-dibutyl-N-methyl-N-hexylammonium cation , Trioctylmethylammonium cation, N-methyl-N-ethyl-N-propyl-N-pentylammonium cation, and the like, more preferably trimethylpropylammonium cation.

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

Examples of such fluoroorganic anions include fluorinated aryl sulfonates, perfluoroalkane sulfonates, bis (fluorosulfonyl) imides, bis (perfluoroalkanesulfonyl) imides, cyanoperfluoroalkanesulfonylamides, and bis (cyano). Perfluoroalkanesulfonylmethide, cyano-bis- (perfluoroalkanesulfonyl) methide, tris (perfluoroalkanesulfonyl) methide, trifluoroacetate, perfluoroalkylate, tris (perfluoroalkanesulfonyl) methide, (perfluoroalkane) Sulfonyl) trifluoroacetamide and the like.

Among these fluoro organic anions, more preferred are perfluoroalkylsulfonate, bis (fluorosulfonyl) imide, bis (perfluoroalkanesulfonyl) imide, and more specifically, for example, trifluoromethanesulfonate, pentafluoroethane. Sulfonate, heptafluoropropane sulfonate, nonafluorobutane sulfonate, bis (fluorosulfonyl) imide, bis (trifluoromethanesulfonyl) imide.

Specific examples of the ionic liquid may be appropriately selected from a combination of the cation component and the anion component. Specific examples of such ionic liquids include, for example, 1-hexylpyridinium bis (fluorosulfonyl) imide, 1-ethyl-3-methylpyridinium trifluoromethanesulfonate, 1-ethyl-3-methylpyridinium pentafluoroethanesulfonate, 1-ethyl-3-methylpyridinium heptafluoropropane sulfonate, 1-ethyl-3-methylpyridinium nonafluorobutane sulfonate, 1-butyl-3-methylpyridinium trifluoromethanesulfonate, 1-butyl-3-methylpyridinium bis (trifluoromethane Sulfonyl) imide, 1-butyl-3-methylpyridinium bis (pentafluoroethanesulfonyl) imide, 1-octyl-4-methylpyridinium bis (fluorosulfonyl) imi 1,1-dimethylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-ethylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-propylpyrrolidinium bis (trifluoromethanesulfonyl) ) Imide, 1-methyl-1-propylpyrrolidinium bis (fluorosulfonyl) imide, 1-methyl-1-butylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-pentylpyrrolidinium bis ( Trifluoromethanesulfonyl) imide, 1-methyl-1-hexylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-heptylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-ethyl-1- Propyl pyro Dinium bis (trifluoromethanesulfonyl) imide, 1-ethyl-1-butylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-ethyl-1-pentylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-ethyl-1- Hexylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-ethyl-1-heptylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1,1-dipropylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1 -Propyl-1-butylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1,1-dibutylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-propylpiperidinium bis (trifluoromethanesulfonyl) Nyl) imide, 1-pentylpiperidinium bis (trifluoromethanesulfonyl) imide, 1,1-dimethylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-ethylpiperidinium bis (trifluoromethanesulfonyl) Imido, 1-methyl-1-propylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-propylpiperidinium bis (fluorosulfonyl) imide, 1-methyl-1-butylpiperidinium bis (trifluoro) Romethanesulfonyl) imide, 1-methyl-1-pentylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-hexylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-heptylpiperi Dinium bis (trifluoromethanesulfonyl) imide, 1-ethyl-1-propylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-ethyl-1-butylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-ethyl-1- Pentylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-ethyl-1-hexylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-ethyl-1-heptylpiperidinium bis (trifluoromethanesulfonyl) imide, 1,1-dipropylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-propyl-1-butylpiperidinium bis (trifluoromethanesulfonyl) imide, 1,1-dibutylpiperidinium bis (trifluoro Tansulfonyl) imide, 1,1-dimethylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-ethylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-propylpyrrolidi Nitrobis (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 ( Pentafluoroethane Sulfonyl) imide, 1-ethyl-1-butylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-pentylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-hexyl Pyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-heptylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1,1-dipropylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-propyl-1-butylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1,1-dibutylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-propylpiperidinium bis (pentafluoroethanesulfonyl) imide , 1- Pentylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1,1-dimethylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-ethylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1 -Methyl-1-propylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-butylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-pentylpiperidinium bis (penta Fluoroethanesulfonyl) imide, 1-methyl-1-hexylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-heptylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl- 1-propi Piperidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-butylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-pentylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-hexylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-heptylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1,1-dipropylpiperidinium bis (Pentafluoroethanesulfonyl) imide, 1-propyl-1-butylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1,1-dibutylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-3- Methyl imidazoli Mutrifluoroacetate, 1-ethyl-3-methylimidazolium heptafluorobutyrate, 1-ethyl-3-methylimidazolium trifluoromethanesulfonate, 1-ethyl-3-methylimidazolium heptafluoropropanesulfonate, 1-ethyl-3 -Methylimidazolium nonafluorobutanesulfonate, 1-ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide, 1-ethyl-3-methylimidazolium bis (fluorosulfonyl) imide, 1-ethyl-3-methylimidazole Rium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-3-methylimidazolium tris (trifluoromethanesulfonyl) methide, 1-butyl-3-methylimidazolium trifluoroacetate 1-butyl-3-methylimidazolium heptafluorobutyrate, 1-butyl-3-methylimidazolium trifluoromethanesulfonate, 1-butyl-3-methylimidazolium perfluorobutanesulfonate, 1-butyl-3-methyl Imidazolium bis (trifluoromethanesulfonyl) imide, 1-hexyl-3-methylimidazolium trifluoromethanesulfonate, 1-hexyl-3-methylimidazolium bis (fluorosulfonyl) imide, 1,2-dimethyl-3-propylimidazo Bis (trifluoromethanesulfonyl) imide, 1-ethyl-2,3,5-trimethylpyrazolium bis (trifluoromethanesulfonyl) imide, 1-propyl-2,3,5-trimethylpyrazolium bis (trifluoro) Methanesulfonyl) imide, 1-butyl-2,3,5-trimethylpyrazolium bis (trifluoromethanesulfonyl) imide, 1-ethyl-2,3,5-trimethylpyrazolium bis (pentafluoroethanesulfonyl) imide, 1-propyl-2,3,5-trimethylpyrazolium bis (pentafluoroethanesulfonyl) imide, 1-butyl-2,3,5-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 (trifluoro Tansulfonyl) trifluoroacetamide, trimethylpropylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-ethyl-N-propylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-ethyl- N-butylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-ethyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-ethyl-N-hexylammonium bis ( Trifluoromethanesulfonyl) imide, N, N-dimethyl-N-ethyl-N-heptylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-ethyl-N-nonylammonium bis (tri Fluoromethanesulfonyl) imide, N, N-dimethyl-N, N-dipropylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-propyl-N-butylammonium bis (trifluoromethanesulfonyl) imide, N , N-dimethyl-N-propyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-propyl-N-hexylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N -Propyl-N-heptylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-butyl-N-hexylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-butyl-N-heptyla Monium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-pentyl-N-hexylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N, N-dihexylammonium bis (trifluoromethanesulfonyl) imide, Trimethylheptylammonium bis (trifluoromethanesulfonyl) imide, N, N-diethyl-N-methyl-N-propylammonium bis (trifluoromethanesulfonyl) imide, N, N-diethyl-N-methyl-N-pentylammonium bis (trifluoro) Romethanesulfonyl) imide, N, N-diethyl-N-methyl-N, N-heptylammonium bis (trifluoromethanesulfonyl) imide, N, N-diethyl-N-propyl-N-pentylan Ni-bis (trifluoromethanesulfonyl) imide, triethylpropylammonium bis (trifluoromethanesulfonyl) imide, triethylpentylammonium bis (trifluoromethanesulfonyl) imide, triethylheptylammonium bis (trifluoromethanesulfonyl) imide, N, N-dipropyl-N-methyl -N-ethylammonium bis (trifluoromethanesulfonyl) imide, N, N-dipropyl-N-methyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, N, N-dipropyl-N-butyl-N-hexylammonium bis (Trifluoromethanesulfonyl) imide, N, N-dipropyl-N, N-dihexylammonium bis (trifluoromethanesulfonyl) imide, N , N-dibutyl-N-methyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, N, N-dibutyl-N-methyl-N-hexylammonium bis (trifluoromethanesulfonyl) imide, trioctylmethylammonium bis ( Trifluoromethanesulfonyl) imide, N-methyl-N-ethyl-N-propyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, 1-butylpyridinium (trifluoromethanesulfonyl) trifluoroacetamide, 1-butyl-3-methyl Pyridinium (trifluoromethanesulfonyl) trifluoroacetamide, 1-ethyl-3-methylimidazolium (trifluoromethanesulfonyl) trifluoroacetamide, tetrahexylammonium (Trifluoromethanesulfonyl) imide, diallyldimethylammonium trifluoromethanesulfonate, diallyldimethylammonium bis (trifluoromethanesulfonyl) imide, diallyldimethylammonium bis (pentafluoroethanesulfonyl) imide, N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium trifluoromethanesulfonate, N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium bis (trifluoromethanesulfonyl) imide, N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium bis (pentafluoroethanesulfonyl) imide, glycidyltrimethylammonium trifluoromethanesulfonate, glycidyltrimethylammonium Umbis (trifluoromethanesulfonyl) imide, glycidyltrimethylammonium bis (pentafluoroethanesulfonyl) imide, diallyldimethylammonium bis (trifluoromethanesulfonyl) imide, diallyldimethylbis (pentafluoroethanetanesulfonyl) imide, lithium bis (trifluoromethanesulfonyl) Examples thereof include imide and lithium bis (fluorosulfonyl) imide.

Among these ionic liquids, 1-hexylpyridinium bis (fluorosulfonyl) imide, 1-ethyl-3-methylpyridinium trifluoromethanesulfonate, 1-ethyl-3-methylpyridinium pentafluoroethanesulfonate, Ethyl-3-methylpyridinium heptafluoropropane sulfonate, 1-ethyl-3-methylpyridinium nonafluorobutane sulfonate, 1-butyl-3-methylpyridinium trifluoromethanesulfonate, 1-butyl-3-methylpyridinium bis (trifluoromethanesulfonyl) Imido, 1-octyl-4-methylpyridinium bis (fluorosulfonyl) imide, 1-methyl-1-propylpyrrolidinium bis (trifluoromethanesulfonyl) i 1-methyl-1-propylpyrrolidinium bis (fluorosulfonyl) imide, 1-methyl-1-propylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-propylpiperidinium bis (fluoro Sulfonyl) 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 (trifluoromethanesulfonyl) imide, lithium bis (fluorosulfonyl) imide.

The commercially available ionic liquid may be used, but it can also be synthesized as follows. The method of synthesizing the ionic liquid is not particularly limited as long as the desired ionic liquid can be obtained. In general, the document “ionic liquids—the forefront and future of development” (CMC Publishing Co., Ltd.) The halide method, the hydroxide method, the acid ester method, the complex formation method, the neutralization method, and the like are used.

The synthesis method for the halide method, hydroxide method, acid ester method, complex formation method, and neutralization method will be described below using nitrogen-containing onium salts as examples. Other sulfur-containing onium salts and phosphorus-containing onium salts Other ionic liquids can be obtained by the same method.

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

An acid (HA) or salt having an anion structure (A ⁻ ) of a target ionic liquid for the obtained halide (MA and M are cations that form a salt with the target anion such as ammonium, lithium, sodium, potassium, etc.) ) To obtain the desired ionic liquid (R ₄ NA).

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

By using the reaction of the reaction formulas (7) to (8) for the obtained hydroxide in the same manner as in the halogenation method, the target ionic liquid (R ₄ NA) can be obtained.

The acid ester method is a method carried out by reactions as shown in reaction formulas (9) to (11). First, a tertiary amine (R ₃ N) is reacted with an acid ester to obtain an acid ester product (Reaction Formula (9)). As the acid ester, inorganic acids such as sulfuric acid, sulfurous acid, phosphoric acid, phosphorous acid, and carbonic acid are used. And esters of organic acids such as esters, methanesulfonic acid, methylphosphonic acid, formic acid, etc.).

By using the reaction of the reaction formulas (10) to (11) in the same manner as the halogenation method for the obtained acid ester, the desired ionic liquid (R ₄ NA) can be obtained. Further, by using methyl trifluoromethanesulfonate, methyl trifluoroacetate or the like as the acid ester, an ionic liquid can be directly obtained.

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

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

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

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

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

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

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

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

≪≪B. Application >>>>
The surface protective film of the present invention can be easily peeled off from the adherend, can prevent heavy peeling over time, and has an effect that the adherend surface is less contaminated by being attached to the adherend. It can be expressed. For this reason, it can use suitably for the surface protection of an optical member or an electronic member. The optical member of the present invention has the surface protective film of the present invention attached thereto. The electronic member of the present invention is obtained by attaching the surface protective film of the present invention.

Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to these examples. In addition, the test and evaluation method in an Example etc. are as follows. Note that “parts” means “parts by weight” unless otherwise noted, and “%” means “% by weight” unless otherwise noted.

<Peeling force A from glass plate (after leaving at a temperature of 23 ° C. for 30 minutes)>
The pressure-sensitive adhesive layer side of the surface protective film (25 mm wide × 140 mm long) with the separator peeled off is pasted to a glass plate (soda lime glass, manufactured by Matsunami Glass Industrial Co., Ltd.) with one reciprocating 2 kg hand roller, and the environment at 23 ° C. It was left under temperature for 30 minutes.
The sample for evaluation obtained as described above was measured with a tensile tester. As a tensile tester, a trade name “Autograph AG-Xplus HS 6000 mm / min high-speed model (AG-50NX plus)” manufactured by Shimadzu Corporation was used. A sample for evaluation was set in a tensile tester, and a tensile test was started. Specifically, the load when the surface protective film was peeled from the glass plate was measured, and the average load at that time was defined as the peel force A from the glass plate of the surface protective film. The tensile test conditions were as follows: test environment temperature: 23 ° C., peel angle: 180 degrees, peel speed (tensile 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 of the surface protective film (25 mm in width × 140 mm in length) from which the separator has been peeled off is bonded to a glass plate (soda lime glass, manufactured by Matsunami Glass Industrial Co., Ltd.) in a single reciprocation of a 2 kg hand roller, and a temperature of 100 ° C. Left in the environment for 2 days.
The sample for evaluation obtained as described above was measured with a tensile tester. As a tensile tester, a trade name “Autograph AG-Xplus HS 6000 mm / min high-speed model (AG-50NX plus)” manufactured by Shimadzu Corporation was used. A sample for evaluation was set in a tensile tester, and a tensile test was started. Specifically, the load when the surface protective film was peeled from the glass plate was measured, and the average load at that time was defined as the peel force B from the glass plate of the surface protective film. The tensile test conditions were as follows: test environment temperature: 23 ° C., peel angle: 180 degrees, peel speed (tensile 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 of the surface protective film (25 mm in width × 140 mm in length) from which the separator has been peeled off is pasted onto a glass plate (soda lime glass, manufactured by Matsunami Glass Industrial Co., Ltd.) with one reciprocating 2 kg hand roller, and a temperature of 23 ° C. Left in the environment for 7 days.
The sample for evaluation obtained as described above was measured with a tensile tester. As a tensile tester, a trade name “Autograph AG-Xplus HS 6000 mm / min high-speed model (AG-50NX plus)” manufactured by Shimadzu Corporation was used. A sample for evaluation was set in a tensile tester, and a tensile test was started. Specifically, the load when the surface protective film was peeled from the glass plate was measured, and the average load at that time was defined as the peel force C from the glass plate of the surface protective film. The tensile test conditions were as follows: test environment temperature: 23 ° C., peel angle: 180 degrees, peel speed (tensile speed): 300 mm / min.

<Residual adhesion to glass plate at 23 ° C.>
The pressure-sensitive adhesive layer side of the surface protective film from which the separator has been peeled off is pasted on the entire surface of a glass plate (made by Matsunami Glass, 1.35 mm x 10 cm x 10 cm) with a 2 kg hand roller reciprocation, temperature 23 ° C, humidity 55% RH Then, after storing for 24 hours, the surface protective film was peeled off at a rate of 0.3 m / min to prepare a treated glass plate.
Subsequently, a 19 mm wide No. 1 cut to a length of 150 mm was formed on the surface of the treated glass plate from which the surface protective film was peeled off. A 31B tape (manufactured by Nitto Denko Corporation, base material thickness: 25 μm) was attached by reciprocation of a 2 kg hand roller in an atmosphere of a temperature of 23 ° C. and a humidity of 55% RH. Tensile tester (trade name “Autograph AG-Xplus HS 6000 mm / min high-speed model (AG-50NX plus) manufactured by Shimadzu Corporation)” after curing for 30 minutes in an atmosphere of temperature 23 ° C. and humidity 55% RH) Was peeled at a peeling angle of 180 degrees and a peeling speed of 300 mm / min, and the adhesive strength a was measured.
Separately, on a glass plate (made by Matsunami Glass, 1.35 mm × 10 cm × 10 cm) that has not been bonded and peeled off as described above, a 19 mm wide No. The adhesive strength b of the 31B tape was measured.
The residual adhesion rate was calculated by the following formula.
Residual adhesion rate (%) = (adhesive strength a / adhesive strength b) × 100
This residual adhesion rate is an index of how much the components of the pressure-sensitive adhesive layer of the surface protective film are transferred and contaminated with respect to the adherend. The higher the residual adhesion value, the less the surface of the adherend is contaminated with the adhesive layer components, and the lower the residual adhesion value, the more the surface of the adherend becomes the component of the adhesive layer. It is a surface protective film that easily contaminates.

[Production Example 1]
1L round bottom separable flask, separable cover, separatory funnel, thermometer, nitrogen inlet tube, Liebig condenser, vacuum seal, stirring rod, stirring wing equipped with polymerization glycol, polypropylene glycol (product name “ Sannics PP-2000 ”(manufactured by Sanyo Chemical Co., Ltd.): 150 g, polyester polyol (product name“ Kuraray Polyol P-2010 ”, manufactured by Kuraray Co., Ltd.): 150 g, toluene (manufactured by Tosoh Corp.): 110 g, dilauric acid as catalyst Dibutyltin (IV) (manufactured by Wako Pure Chemical Industries, Ltd.): 0.041 g was added, and nitrogen substitution was performed at room temperature for 1 hour while stirring. Thereafter, 33.5 g of hexamethylene diisocyanate (product name “HDI”, manufactured by Tosoh Corporation): 33.5 g was added while stirring under nitrogen flow so that the solution temperature in the experimental apparatus was 90 ± 2 ° C. in a water bath. After maintaining for 4 hours while controlling, 74.9 g of polypropylene glycol (product name “GP1000”, manufactured by Sanyo Chemical Co., Ltd.) is added, and the solution temperature in the experimental apparatus is 90 ± 2 ° C. in a water bath. After maintaining for 2 hours while controlling, 25.4 g of hexamethylene diisocyanate (product name “HDI”, manufactured by Tosoh Corporation): 25.4 g is added, and the solution temperature in the experimental apparatus is 90 ± 2 ° C. in a water bath. While being controlled, this was held for 2 hours to obtain a urethane prepolymer solution A. In the middle of the polymerization, toluene was appropriately added dropwise in order to control the temperature during the polymerization and to prevent the stirring property from being lowered due to an increase in viscosity. The total amount of toluene dropped was 320 g. The solid content concentration of the urethane prepolymer solution A was 50% by weight.

[Example 1]
As shown in Table 1, 100 parts by weight of the urethane prepolymer solution A obtained in Production Example 1 was converted into solid polymer content and an isocyanate-based crosslinking agent (trade name “Coronate HL”, manufactured by Nippon Polyurethane Co., Ltd.). 5.2 parts by weight, 0.5 parts by weight of heat stabilizer (trade name “Irganox 1010”, manufactured by BASF), and fluorine-containing polymer (trade name “F-571”, DIC) Co., Ltd.) in terms of solid content and 0.01 part by weight of fatty acid ester (trade name “Saracos 816”, Nisshin Oilio Co., Ltd.) in terms of solid content are blended to obtain a total solid content. Was diluted with ethyl acetate so as to be 45% by weight to obtain a pressure-sensitive adhesive composition (1).
The obtained pressure-sensitive adhesive composition (1) was applied to a base material made of polyester resin (trade name “T100-75S”, thickness 75 μm, manufactured by Mitsubishi Plastics Co., Ltd.) so that the thickness after drying was 75 μm, and dried. It was cured by drying at a temperature of 130 ° C. and a drying time of 3 minutes. Thus, the adhesive layer (1) formed from an adhesive composition (1) was produced on the base material.
Next, a silicone of a separator (trade name “MRF25”, thickness 25 μm, manufactured by Mitsubishi Chemical Corporation) made of a polyester resin with a thickness of 25 μm, on which the surface of the obtained pressure-sensitive adhesive layer (1) is subjected to silicone treatment on one surface. The treated surfaces were bonded together to obtain a surface protective film (1).
The obtained surface protective 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]
As shown in Table 1, the same procedure as in Example 1 was carried out except that the amount of fatty acid ester (trade name “Saracos 816”, manufactured by Nisshin Oilio Co., Ltd.) was changed to 5 parts by weight in terms of solid content. A pressure-sensitive adhesive layer (2) formed from the agent composition (2) was produced to obtain a surface protective film (2). The results are shown in Table 2.

Example 3
As shown in Table 1, the same procedure as in Example 1 was carried out except that the amount of fatty acid ester (trade name “Saracos 816”, manufactured by Nisshin Oilio Co., Ltd.) was changed to 15 parts by weight in terms of solid content. A pressure-sensitive adhesive layer (3) formed from the agent composition (3) was produced to obtain a surface protective film (3). The results are shown in Table 2.

Example 4
As shown in Table 1, the same procedure as in Example 1 was conducted except that the blending amount of the fluorine-containing polymer (trade name “F-571”, manufactured by DIC Corporation) was changed to 0.05 parts by weight in terms of solid content. A pressure-sensitive adhesive layer (4) formed from the pressure-sensitive adhesive composition (4) was produced to obtain a surface protective film (4). The results are shown in Table 2.

Example 5
As shown in Table 1, the amount of the fluorine-containing polymer (trade name “F-571”, manufactured by DIC Corporation) is 0.05 parts by weight in terms of solid content, and a fatty acid ester (trade name “Saracos 816”). , Manufactured by Nisshin Oilio Co., Ltd.) except that the blending amount was changed to 5 parts by weight in terms of solid content, and the pressure-sensitive adhesive layer (5) formed from the pressure-sensitive adhesive composition (5) was carried out in the same manner as in Example 1. And a surface protective film (5) was obtained. The results are shown in Table 2.

Example 6
As shown in Table 1, the amount of the fluorine-containing polymer (trade name “F-571”, manufactured by DIC Corporation) is 0.05 parts by weight in terms of solid content, and a fatty acid ester (trade name “Saracos 816”). The pressure-sensitive adhesive layer (6) formed from the pressure-sensitive adhesive composition (6) is the same as that of Example 1 except that the blending amount of Nisshin Oilio Co., Ltd. is changed to 15 parts by weight in terms of solid content. And a surface protective film (6) was obtained. The results are shown in Table 2.

Example 7
As shown in Table 1, the amount of the isocyanate-based crosslinking agent (trade name “Coronate HL”, manufactured by Nippon Polyurethane Co., Ltd.) is 3.9 parts by weight in terms of solid content, and a fatty acid ester (trade name “Saracos 816”). The pressure-sensitive adhesive layer (7) formed from the pressure-sensitive adhesive composition (7) was prepared in the same manner as in Example 1 except that the blending amount of Nisshin Oilio Co., Ltd. was changed to 5 parts by weight in terms of solid content. ) To obtain a surface protective film (7). The results are shown in Table 2.

Example 8
As shown in Table 1, the amount of the isocyanate-based crosslinking agent (trade name “Coronate HL”, manufactured by Nippon Polyurethane Co., Ltd.) is 3.9 parts by weight in terms of solid content, and a fluorine-containing polymer (trade name “F-571”). ”, Manufactured by DIC Corporation) in an amount of 0.05 parts by weight in terms of solids, and 5 parts by weight in terms of solids in terms of the amount of a fatty acid ester (trade name“ Saracos 816 ”, manufactured by Nisshin Oilio Co., Ltd.). Except having changed into the weight part, it carried out like Example 1 and produced the adhesive layer (8) formed from an adhesive composition (8), and obtained the surface protection film (8). The results are shown in Table 2.

Example 9
As shown in Table 1, the amount of the isocyanate-based crosslinking agent (trade name “Coronate HL”, manufactured by Nippon Polyurethane Co., Ltd.) is 2.6 parts by weight in terms of solid content, and a fluorine-containing polymer (trade name “F-571”). ", DIC Co., Ltd.) in an amount of 0.10 parts by weight in terms of solids, and fatty acid ester (trade name" Saracos 816 ", Nisshin Oilio Co., Ltd.) in an amount of 5 in terms of solids. Except having changed into the weight part, it carried out like Example 1 and produced the adhesive layer (9) formed from an adhesive composition (9), and obtained the surface protection film (9). The results are shown in Table 2.

Example 10
As shown in Table 1, the amount of the isocyanate-based crosslinking agent (trade name “Coronate HL”, manufactured by Nippon Polyurethane Co., Ltd.) is 2.6 parts by weight in terms of solid content, and a fluorine-containing polymer (trade name “F-571”). ”, Manufactured by DIC Corporation) is 0.20 parts by weight in terms of solid content, and the amount of fatty acid ester (trade name“ Saracos 816 ”, manufactured by Nisshin Oilio Co., Ltd.) is 5 in terms of solid content. Except having changed into the weight part, it carried out like Example 1 and produced the adhesive layer (10) formed from an adhesive composition (10), and obtained the surface protection film (10). The results are shown in Table 2.

Example 11
As shown in Table 1, as in Example 1, except that the amount of the isocyanate-based crosslinking agent (trade name “Coronate HL”, manufactured by Nippon Polyurethane Co., Ltd.) was changed to 9.5 parts by weight in terms of solid content. It performed, the adhesive layer (11) formed from an adhesive composition (11) was produced, and the surface protection film (11) was obtained. The results are shown in Table 2.

Example 12
As shown in Table 1, as in Example 1, except that the amount of the isocyanate-based crosslinking agent (trade name “Coronate HL”, manufactured by Nippon Polyurethane Co., Ltd.) was changed to 12.7 parts by weight in terms of solid content. It performed, the adhesive layer (12) formed from an adhesive composition (12) was produced, and the surface protection film (12) was obtained. The results are shown in Table 2.

Example 13
As shown in Table 1, instead of using a fluorine-containing polymer (trade name “F-571”, manufactured by DIC Corporation), a hydroxyl group-containing silicone (trade name “X-22-4015”, manufactured by Shin-Etsu Chemical Co., Ltd.) Except for changing the amount of fatty acid ester (trade name “Saracos 816”, manufactured by Nisshin Oillio Co., Ltd.) to 5 parts by weight in terms of solids, using 0.05 parts by weight in terms of solids It carried out similarly to Example 1 and produced the adhesive layer (13) formed from an adhesive composition (13), and obtained the surface protection film (13). The results are shown in Table 2.

Example 14
As shown in Table 1, instead of using an isocyanate-based crosslinking agent (trade name “Coronate HL”, manufactured by Nippon Polyurethane Co., Ltd.), an isocyanate-based crosslinking agent (trade name “Coronate HX”, manufactured by Nippon Polyurethane Co., Ltd.) is solid. Using 3.2 parts by weight in terms of a fraction, the blending amount of a fluorine-containing polymer (trade name “F-571”, manufactured by DIC Corporation) is 0.05 parts by weight in terms of solids, and a fatty acid ester (trade name) A pressure-sensitive adhesive formed from the pressure-sensitive adhesive composition (14) in the same manner as in Example 1 except that the blending amount of “Saracos 816” (manufactured by Nisshin Oillio Co., Ltd.) is changed to 5 parts by weight in terms of solid content. A layer (14) was produced to obtain a surface protective film (14). The results are shown in Table 2.

Example 15
As shown in Table 1, instead of using an isocyanate-based crosslinking agent (trade name “Coronate HL”, manufactured by Nippon Polyurethane Co., Ltd.), an isocyanate-based crosslinking agent (trade name “Coronate HX”, manufactured by Nippon Polyurethane Co., Ltd.) is solid. Example 1 except that 5.6 parts by weight in terms of minutes were used and the blending amount of the fatty acid ester (trade name “Saracos 816”, manufactured by Nisshin Oilio Co., Ltd.) was changed to 5 parts by weight in terms of solids. In the same manner as described above, a pressure-sensitive adhesive layer (15) formed from the pressure-sensitive adhesive composition (15) was produced, and a surface protective film (15) was obtained. The results are shown in Table 2.

[Comparative Example 1]
As shown in Table 1, the amount of isocyanate-based crosslinking agent (trade name “Coronate HL”, manufactured by Nippon Polyurethane Co., Ltd.) was changed to 3.9 parts by weight in terms of solid content, and a fluorine-containing polymer (trade name “F” -571 ", manufactured by DIC Corporation) and a fatty acid ester (trade name" Saracos 816 ", manufactured by Nisshin Oilio Co., Ltd.). A pressure-sensitive adhesive layer (C1) formed from the above was prepared to obtain a surface protective film (C1). The results are shown in Table 2.

[Comparative Example 2]
As shown in Table 1, except that a fluorine-containing polymer (trade name “F-571”, manufactured by DIC Corporation) and a fatty acid ester (trade name “Saracos 816”, manufactured by Nisshin Oilio Co., Ltd.) are not used. It carried out similarly to Example 1 and produced the adhesive layer formed from an adhesive composition (C2), and obtained the surface protection film (C2). The results are shown in Table 2.

[Comparative Example 3]
As shown in Table 1, the blending amount of the fluorine-containing polymer (trade name “F-571”, manufactured by DIC Corporation) was changed to 0.05 parts by weight in terms of solid content, and a fatty acid ester (trade name “Saracos” 816 ", manufactured by Nisshin Oillio Co., Ltd.), except that the pressure-sensitive adhesive layer (C3) formed from the pressure-sensitive adhesive composition (C3) was prepared, and the surface protective film (C3) was used. ) The results are shown in Table 2.

[Comparative Example 4]
As shown in Table 1, the fatty acid ester (trade name “Saracos 816”, manufactured by Nisshin Oilio Co., Ltd.) was changed to 5 parts by weight in terms of solid content, and a fluorine-containing polymer (trade name “F-571”), Except not using DIC Corporation), it carried out similarly to Example 1, the adhesive layer which consists of an adhesive composition (C4) was produced, and the surface protection film (C4) was obtained. The results are shown in Table 2.

[Comparative Example 5]
As shown in Table 1, instead of using a fluorine-containing polymer (trade name “F-571”, manufactured by DIC Corporation), a silicone release agent (trade name “KS-776A”, manufactured by Shin-Etsu Chemical Co., Ltd.) was solidified. A pressure-sensitive adhesive composition (C5) was prepared in the same manner as in Example 1 except that 1.0 part by weight was used and a fatty acid ester (trade name “Saracos 816”, manufactured by Nisshin Oilio Co., Ltd.) was not used. ) To form a pressure-sensitive adhesive layer (C5) to obtain a surface protective film (C5). The results are shown in Table 2.

[Comparative Example 6]
As shown in Table 1, instead of using the urethane prepolymer solution A obtained in Production Example 1, a commercially available urethane prepolymer solution (trade name “Siavine SH-109”, manufactured by Toyochem Co., Ltd.) was converted into solid content. Using 100 parts by weight, instead of using an isocyanate crosslinking agent (trade name “Coronate HL”, manufactured by Nippon Polyurethane Co., Ltd.), an isocyanate crosslinking agent (trade name “Coronate HX”, manufactured by Nippon Polyurethane Co., Ltd.) is used as a solid content. Using 3.6 parts by weight in terms of conversion, the blending amount of the fluorine-containing polymer (trade name “F-571”, manufactured by DIC Corporation) was changed to 1 part by weight in terms of solid content, and a fatty acid ester (trade name “ An adhesive layer (C6) formed from the adhesive composition (C6), except that SARACOS 816 "and Nisshin Oilio Co., Ltd.) are not used. ) Was prepared, and a surface protecting film was obtained (C6). The results are shown in Table 2.

[Examples 16 to 30]
For each of the surface protective films (1) to (15) obtained in Examples 1 to 15, the separator was peeled off, and the pressure-sensitive adhesive layer side was a polarizing plate (manufactured by Nitto Denko Corporation, trade name “ TEG1465DUHC ") to obtain an optical member having a surface protective film attached thereto.

[Examples 31 to 45]
For each of the surface protective films (1) to (15) obtained in Examples 1 to 15, the separator was peeled off, and the adhesive layer side was electrically conductive film (Nitto Denko Corporation, trade name) It was attached to “Electrista V270L-TFMP”) to obtain an electronic member to which a surface protective film was attached.

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

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

Claims (10)

A surface protective film having an adhesive layer,
The pressure-sensitive adhesive layer of the surface protective film was bonded to a glass plate and allowed to stand at a temperature of 23 ° C. for 30 minutes, and then the surface protective film was peeled from the glass plate at a temperature of 23 ° C. at a peeling angle of 180 degrees and a peeling speed of 300 mm / min. The peel force A when peeled off is 0.024 N / 25 mm to 0.50 N / 25 mm,
The pressure-sensitive adhesive layer of the surface protective film was bonded to a glass plate and allowed to stand at a temperature of 100 ° C. for 2 days, and then the surface protective film was peeled from the glass plate at a temperature of 23 ° C. at a peeling angle of 180 degrees and a peeling speed of 300 mm / min. When the peel force at the time of peeling is B, the rate of increase in peel force with time calculated by (B / A) × 100 is 1000% or less.
Surface protective film. The pressure-sensitive adhesive layer of the surface protective film was bonded to a glass plate and allowed to stand at 23 ° C. for 7 days, and then the surface protective film was peeled off from the glass plate at a temperature of 23 ° C. at a peeling angle of 180 degrees and a peeling speed of 300 mm / min. The surface protective film according to claim 1, wherein the rate of increase in peel force with time calculated by (C / A) × 100 is 160% or less, where C is the peel force at the time. The surface protective film according to claim 1 or 2, wherein the residual adhesion rate to the glass plate at 23 ° C is 50% or more. The pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer is formed from a pressure-sensitive adhesive composition, and the pressure-sensitive adhesive composition includes a base polymer, a silicone-based additive and / or a fluorine-based additive. The surface protection film in any one of. The surface protective film according to claim 4, wherein the pressure-sensitive adhesive composition contains a fatty acid ester. The surface protective film according to claim 4 or 5, wherein the silicone additive is at least one selected from a siloxane bond-containing compound, a hydroxyl group-containing silicone compound, and a crosslinkable functional group-containing silicone compound. The surface protective film according to any one of claims 4 to 6, wherein the fluorine-based additive is at least one selected from a fluorine-containing compound, a hydroxyl group-containing fluorine-based compound, and a crosslinkable functional group-containing fluorine-based compound. The surface protective film according to any one of claims 4 to 7, wherein the base polymer is at least one selected from a urethane prepolymer, a polyol, an acrylic resin, a rubber resin, and a silicone resin. An optical member to which the surface protective film according to any one of claims 1 to 8 is attached. An electronic member to which the surface protective film according to claim 1 is attached.

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