WO2017150290A1

WO2017150290A1 - Surface protective film

Info

Publication number: WO2017150290A1
Application number: PCT/JP2017/006483
Authority: WO
Inventors: 浩司設樂; 創矢徐; 翔悟佐々木
Original assignee: 日東電工株式会社
Priority date: 2016-03-04
Filing date: 2017-02-22
Publication date: 2017-09-08
Also published as: CN114605931A

Abstract

Provided is a surface protective film that has ultraeasy separability, while having a low possibility of contaminating the surface of an object to which the surface protective film is bonded. A surface protective film according to the present invention has an adhesive layer; and the peel strength as measured by bonding a polyethylene terephthalate film having a thickness of 25 μm to the adhesive layer and peeling the polyethylene terephthalate film therefrom in 30 minutes at 23°C at a peeling angle of 180° and at a peeling rate of 6,000 mm/minute is 0.08 N/25 mm or less.

Description

Surface protection film

The present invention relates to a surface protective film.

In the manufacturing process of optical members and electronic members, a surface protective film is generally attached to the exposed surface in order to prevent scratches on the surface during processing, assembly, inspection, transportation, and the like. 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 electronic member to which such a surface protective film is adhered, when trying to peel off the surface protective film as described above, it is smooth only at the interface between the surface protective film and the optical member or electronic member. It is important to be able to peel off.

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 having a light releasability is obtained when the attached surface protective film is peeled off. Even if it is used, the fragile member may be damaged by the peeling force.

For this reason, a surface protective film having even lighter releasability, that is, ultra-light releasability, is required as compared with a conventional surface protective film having light releasability.

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

Also, in the manufacturing process of optical members and electronic members, the surface protective film attached to the exposed surface to prevent scratches on the surface during processing, assembly, inspection, transportation, etc., is kept attached. Often. 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.

As described above, in the manufacturing process of the optical member and the electronic member, in the surface protective film to be attached to the exposed surface in order to prevent the surface from being scratched during processing, assembly, inspection, transportation, etc. There are points to be improved, that is, imparting ultra-light release properties, reducing the contamination of the adherend surface, and suppressing heavy release over time, and the like.

Japanese Unexamined Patent Publication No. 2016-17109

An object of the present invention is to provide a surface protective film imparted with ultra-light peelability, to provide a surface protective film that can reduce the contamination of the adherend surface, and to protect the surface of the adherend from over-peeling. To provide a film.

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

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

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

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

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

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

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

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

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

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

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

In one embodiment, the fluorine-based additive is at least one selected from 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 urethane resins, acrylic resins, rubber resins, and silicone resins.

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

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

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

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

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

According to the present invention, it is possible to provide a surface protective film that has ultra-light peelability and low contamination on the adherend surface.

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

≪≪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, any appropriate release liner may be provided on the surface of the pressure-sensitive adhesive layer 2 opposite to the base material layer 1 for protection before use (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.

In one embodiment of the surface protective film of the present invention, a polyethylene terephthalate film having a thickness of 25 μm is bonded to the pressure-sensitive adhesive layer, and after 30 minutes at 23 ° C., the polyethylene terephthalate film is peeled at a peeling angle of 180 degrees and a peeling speed of 6000 mm / min. The peel force when peeled off is preferably 0.08 N / 25 mm or less, more preferably 0.075 N / 25 mm or less, still more preferably 0.07 N / 25 mm or less, and further preferably 0.065 N. / 25 mm or less, particularly preferably 0.06 N / 25 mm or less, and most preferably 0.055 N / 25 mm or less. In reality, the lower limit of the peeling force is 0.001 N / 25 mm or more. If the peeling force at a very high peeling speed of 6000 mm / min is within the above range, the surface protective film of the present invention can exhibit a very excellent ultralight peeling property. The details of the measurement of the peeling force will be described later.

In one embodiment of the surface protective film of the present invention, a polyethylene terephthalate film having a thickness of 25 μm is bonded to the pressure-sensitive adhesive layer, and after 30 minutes at 23 ° C., the polyethylene terephthalate film is peeled at a peeling angle of 180 degrees and a peeling speed of 300 mm / min. The peel force when peeled off is preferably 0.02 N / 25 mm or less, more preferably 0.018 N / 25 mm or less, still more preferably 0.015 N / 25 mm or less, and particularly preferably 0.012 N. / 25 mm or less, and most preferably 0.01 N / 25 mm or less. In reality, the lower limit of the peeling force is 0.001 N / 25 mm or more. If the said peeling force exists in the said range, the surface protection film of this invention can express ultralight peelability. The details of the measurement of the peeling force will be described later.

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

In one embodiment of the surface protective film of the present invention, a polyethylene terephthalate film having a thickness of 25 μm is bonded to the pressure-sensitive adhesive layer, and after 7 days at 80 ° C., the polyethylene terephthalate film is peeled at a peeling angle of 180 degrees and a peeling speed of 300 mm / min. The peel force when peeled off is preferably 0.07 N / 25 mm or less, more preferably 0.06 N / 25 mm or less, still more preferably 0.05 N / 25 mm or less, and particularly preferably 0.045 N. / 25 mm or less, and most preferably 0.04 N / 25 mm or less. In reality, the lower limit of the peeling force is 0.001 N / 25 mm or more. If the peeling force is within the above range, the surface protective film of the present invention can suppress heavy peeling over time. The details of the measurement of the peeling force will be described later.

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

In one embodiment of the surface protective film of the present invention, a glass plate having a thickness of 1000 μm is bonded to the adhesive layer, and after 30 minutes at 23 ° C., the glass plate is peeled off at a peeling angle of 180 degrees and a peeling speed of 300 mm / min. The peeling force is preferably 0.023 N / 25 mm or less, more preferably 0.022 N / 25 mm or less, still more preferably 0.02 N / 25 mm or less, and particularly preferably 0.015 N / 25 mm. Or less, most preferably 0.013 N / 25 mm or less. In reality, the lower limit of the peeling force is 0.001 N / 25 mm or more. If the said peeling force exists in the said range, the surface protection film of this invention can express ultralight peelability. The details of the measurement of the peeling force will be described later.

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

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

The surface protective film of the present invention has a residual adhesion rate of preferably 50% or more, more preferably 55% to 100%, still more preferably 60% to 100%, and particularly preferably 65% to 100%. %, Most preferably 70% to 100%. When the residual adhesion rate is within the above range, the surface protective film of the present invention can exhibit the effect that the adherend surface has low contamination. 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.

≪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.

≪Adhesive layer≫
The pressure-sensitive adhesive layer can be produced by any appropriate production method. Examples of such a production method include a method in which a composition that is a material for forming the pressure-sensitive adhesive layer is applied onto the base material layer, and the 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 adhesive layer is composed of an adhesive. The pressure-sensitive adhesive is formed from a pressure-sensitive adhesive composition.

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

The content of the silicone-based additive and / or fluorine-based additive in the pressure-sensitive adhesive composition is preferably 0.01 parts 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 0.02 parts by weight to 25 parts by weight, even more preferably 0.025 parts by weight to 10 parts by weight, particularly preferably 0.03 parts by weight to 5 parts by weight. And most preferably 0.05 to 3 parts by weight. If the content of the silicone-based additive and / or the fluorine-based additive in the pressure-sensitive adhesive composition is within the above range, the surface protective film of the present invention can exhibit higher ultralight release properties and can be attached. The contamination of the body surface can be made lower.

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

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

Urethane resin may contain any appropriate component as long as the effects of the present invention are not impaired. Examples of such components include resin components other than urethane 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 urethane-based resin preferably contains a deterioration preventing agent such as an antioxidant, an ultraviolet absorber, and a light stabilizer. When the urethane-based resin contains a deterioration preventing agent, the adhesive residue can be excellently prevented from remaining on the adherend even if it is stored in a heated state after being adhered to the adherend. 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.

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

1 type of polyol (A) may be sufficient, and 2 or more types may be sufficient as it.

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

Examples of the polyol (A) preferably include polyester polyol, polyether polyol, polycaprolactone polyol, polycarbonate polyol, and castor oil-based polyol. The polyol (A) 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 (A) 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. Since the wettability of the pressure-sensitive adhesive layer can be improved by adjusting the number average molecular weight Mn of the polyol (A) within the above range, the surface protective film of the present invention can be stuck without entraining bubbles. .

The polyol (A) preferably contains a polyol (A1) having three OH groups and a number average molecular weight Mn of 300 to 100,000. 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 (A) is preferably 5% by weight or more, more preferably 25% by weight to 100% by weight, and further preferably 50% by weight to 100% by weight. Since the wettability of the pressure-sensitive adhesive layer can be improved by adjusting the content ratio of the polyol (A1) in the polyol (A) within the above range, the surface protective film of the present invention is stuck without entraining bubbles. Is possible.

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. Since the wettability of the pressure-sensitive adhesive layer can be improved by adjusting the number average molecular weight Mn of the polyol (A1) within the above range, the surface protective film of the present invention can be stuck without entraining bubbles. .

The polyol (A) 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, the adhesive strength may increase with time, and excellent reworkability may not be exhibited. 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.

As the polyol (A2), a total amount of at least one of a polyol having 4 OH groups (tetraol), a polyol having 5 OH groups (pentaol), and a polyol having 6 OH groups (hexaol) is: As a content rate in a polyol (A), Preferably it is 70 weight% or less, More preferably, it is 60 weight% or less, More preferably, it is 40 weight% or less, Most preferably, it is 30 weight% or less. In the polyol (A), as the polyol (A2), at least of a polyol having 4 OH groups (tetraol), a polyol having 5 OH groups (pentaol), and a polyol having 6 OH groups (hexaol) By adjusting one type to the above range, a urethane resin excellent in transparency can be provided, and the wettability of the pressure-sensitive adhesive layer can be improved. Adhesion is possible without being involved.

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

In the polyol (A2), the content ratio of the polyol having 4 or more OH groups therein and a number average molecular weight Mn of 20000 or less is preferably less than 70% by weight, more preferably based on the whole polyol (A). Is 60% by weight or less, more preferably 50% by weight or less, particularly preferably 40% by weight or less, and most preferably 30% by weight or less. By adjusting the content ratio of the polyol having 4 or more OH groups in the polyol (A2) having a number average molecular weight Mn of 20000 or less to the above range, a urethane resin having excellent transparency can be provided. Since the wettability of the pressure-sensitive adhesive layer can be improved, the surface protective film of the present invention can be attached without entraining bubbles.

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 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. Since the wettability of the pressure-sensitive adhesive layer can be improved by adjusting the equivalent ratio of NCO group / OH group within the above range, the surface protective film of the present invention can be stuck without entraining bubbles.

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 with respect to the polyol (A). % To 27% by weight, more preferably 2.0% to 25% by weight, particularly preferably 2.3% to 23% by weight, and most preferably 2.5% to 20% by weight. It is. Since the wettability of the pressure-sensitive adhesive layer can be improved by adjusting the content ratio of the polyfunctional isocyanate compound (B) within the above range, the surface protective film of the present invention can be stuck without involving bubbles. Become.

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

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

In order to cure the composition containing the polyol (A) and the polyfunctional isocyanate compound (B), a catalyst is preferably used. Examples of such a catalyst include 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% by weight to 1.00% by weight, more preferably 0.01% by weight to 0.75% by weight, and still more preferably 0% with respect to the polyol (A). The content is 0.01% to 0.50% by weight, particularly preferably 0.01% to 0.20% by weight. Since the wettability of the pressure-sensitive adhesive layer can be improved by adjusting the amount of the catalyst within the above range, the surface protective film of the present invention can be attached without entraining bubbles.

The composition containing the polyol (A) 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.

(Urethane resin formed from a composition containing urethane prepolymer (C) and polyfunctional isocyanate compound (B))
As long as the urethane resin formed from the composition containing the urethane prepolymer (C) and the polyfunctional isocyanate compound (B) is a urethane resin obtained using a so-called “urethane prepolymer” as a raw material, any resin can be used. A suitable urethane resin can be adopted.

The urethane resin formed from the composition containing the urethane prepolymer (C) and the polyfunctional isocyanate compound (B) contains, for example, a polyurethane polyol as the urethane prepolymer (C) and the polyfunctional isocyanate compound (B). And a urethane-based resin formed from the composition. Only one type of urethane prepolymer (C) may be used, or two or more types may be used. One type of polyfunctional isocyanate compound (B) may be sufficient, and 2 or more types may be sufficient as it.

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

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

The composition containing the urethane prepolymer (C) and the polyfunctional isocyanate compound (B) may contain any appropriate other 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 producing a polyurethane resin formed from a composition containing a urethane prepolymer (C) and a polyfunctional isocyanate compound (B), a polyurethane resin is produced using a so-called “urethane prepolymer” as a raw material. Any appropriate manufacturing method may be adopted as long as it is a method.

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

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

The content ratio of the polyfunctional isocyanate compound (B) is preferably 0.01 to 30% by weight of the polyfunctional isocyanate compound (B) with respect to the urethane prepolymer (C), more preferably 0.8%. 03 wt% to 20 wt%, more preferably 0.05 wt% to 15 wt%, particularly preferably 0.075 wt% to 10 wt%, and most preferably 0.1 wt% to 8 wt%. % By weight. Since the wettability of the pressure-sensitive adhesive layer can be improved by adjusting the content ratio of the polyfunctional isocyanate compound (B) within the above range, the surface protective film of the present invention can be stuck without involving bubbles. Become.

[Acrylic resin]
As the acrylic resin, any appropriate acrylic pressure-sensitive adhesive such as a publicly known acrylic pressure-sensitive adhesive described in JP-A-2013-241606 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.

[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.

[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.

<Silicone 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 ".

<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” (manufactured by Daikin Industries, Ltd.), trade name “Megafac F-571”, “Fluonate” (manufactured 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).

<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 a fatty acid ester. 1 type of fatty acid ester may be sufficient and 2 or more types may be sufficient as it.

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

As the fatty acid ester, any appropriate fatty acid ester can be adopted as long as the effects of the present invention are not impaired. Examples of such fatty acid esters include polyoxyethylene bisphenol A laurate, butyl stearate, 2-ethylhexyl palmitate, 2-ethylhexyl stearate, monoglyceride behenate, cetyl 2-ethylhexanoate, myristic acid Isopropyl, isopropyl palmitate, cholesteryl isostearate, lauryl methacrylate, coconut fatty acid methyl, methyl laurate, methyl oleate, methyl stearate, myristyl myristate, octyldodecyl myristate, pentaerythritol monooleate, pentaerythritol monostearate , Pentaerythritol tetrapalmitate, stearyl stearate, isotridecyl stearate, 2-ethylhexanoic acid triglycera De, 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 1 to 50 parts by weight, more preferably 1.5 to 45 parts by weight with respect to 100 parts by weight of the base polymer. Parts, more preferably 2 to 40 parts by weight, particularly preferably 2.5 to 35 parts by weight, and most preferably 3 to 30 parts by weight.

The pressure-sensitive adhesive composition may 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.

Among these, 1-ethylpyridinium cation, 1-butylpyridinium cation, 1-hexylpyridinium cation, 1-ethyl-3-methylpyridinium cation, and 1 are preferable because the effects of the present invention can be further exhibited. -Pyridinium cations such as butyl-3-methylpyridinium cation, 1-hexyl-3-methylpyridinium cation, 1-butyl-4-methylpyridinium cation, 1-octyl-4-methylpyridinium cation; 1-ethyl-1- Methylpyrrolidinium cation, 1-methyl-1-propylpyrrolidinium cation, 1-methyl-1-butylpyrrolidinium cation, 1-methyl-1-pentylpyrrolidinium cation, 1-methyl-1-hexyl Pyrrolidinium cation, 1-methyl-1- 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 therefore cannot be defined unconditionally. 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.

≪≪Use≫≫
The surface protective film of the present invention has ultra-light peelability and low contamination on the adherend surface. 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 against PET at a peeling speed of 6000 mm / min (peeling force after 23 ° C. × 30 minutes and peeling force after 80 ° C. × 7 days)>
A polyethylene terephthalate film having a thickness of 25 μm was bonded to the pressure-sensitive adhesive layer, and the peeling force when the polyethylene terephthalate film was peeled off at 23 ° C., a peeling angle of 180 °, and a peeling speed of 6000 mm / min was measured as follows.
Through the double-sided adhesive tape (manufactured by Nitto Denko Corporation, trade name “No. 531”) on the entire surface opposite to the pressure-sensitive adhesive layer of the surface protective film (width 50 mm × length 140 mm) from which the separator has been peeled off, A SUS304 plate was attached using a 2 kg hand roller.
Next, a polyethylene terephthalate film (trade name “Lumirror S-10” manufactured by Toray Industries, Inc., thickness: 25 μm, width: 25 mm) was attached to the surface of the pressure-sensitive adhesive layer (temperature: 23 ° C., humidity: 65%, 2kg roller 1 round trip).
The sample for evaluation obtained as described above was measured by a tensile test. 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. After setting the sample for evaluation in a tensile tester, the sample was allowed to stand for 30 minutes at an environmental temperature of 23 ° C., or left for 7 days in a temperature environment of 80 ° C., and then the tensile test was started. The conditions of the tensile test were a peeling angle: 180 degrees and a peeling speed (tensile speed): 6000 mm / min. The load when the PET film was peeled from the surface protective film was measured, and the average load at that time was defined as the peel force of the surface protective film.

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

<Remaining adhesion rate>
A surface protection film was bonded to the entire surface of a glass plate (Matsunami Glass, 1.35 mm × 10 cm × 10 cm) with a hand roller, and stored in an atmosphere of a temperature of 23 ° C. and a humidity of 55% RH for 24 hours. The surface protective film was peeled off at a speed of 3 m / min, and a 19 mm wide No. 1 film was cut into a length of 150 mm. A 31B tape (manufactured by Nitto Denko Corporation, base material thickness: 25 μm) was attached by reciprocating 2.0 kg 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 pulling speed of 300 mm / min, and the adhesive strength was measured.
Separately, for a glass plate not subjected to the above-described treatment, a 19 mm wide No. The adhesive strength of the 31B tape was measured, and the residual adhesion rate was calculated by the following formula.
Residual adhesion rate (%) = (No. 31B adhesive strength to glass plate after surface protective film peeling / No. 31B adhesive strength to glass plate) × 100
This residual adhesion rate is an index of how much the pressure-sensitive adhesive component of the surface protective film is transferred and contaminated on the surface of the adherend. The higher the value of the residual adhesion rate, the better the surface protection film without contaminating the adherend, and the lower the value of the residual adhesion rate, the more the surface of the adherend is contaminated with the adhesive component. .

<Peeling power against glass at a peeling speed of 6000 mm / min (peeling force after 23 ° C. × 30 minutes and peeling force after 80 ° C. × 7 days)>
The surface protective film (25 mm in width × 140 mm in length) from which the separator was peeled was attached to glass (soda lime glass, manufactured by Matsunami Glass Industrial Co., Ltd.) with one reciprocation of a 2 kg hand roller.
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. After setting the sample for evaluation in a tensile tester, the sample was allowed to stand for 30 minutes at an environmental temperature of 23 ° C., or left for 7 days in a temperature environment of 80 ° C., and then the tensile test was started. The conditions of the tensile test were a peeling angle: 180 degrees and a peeling speed (tensile speed): 6000 mm / min. The load when the surface protective film was peeled from the glass was measured, and the average load at that time was defined as the peel force of the surface protective film.

<Peeling power against glass at a peeling speed of 300 mm / min (peeling force after 23 ° C. × 30 minutes and peeling force after 80 ° C. × 7 days)>
The surface protective film (25 mm in width × 140 mm in length) from which the separator was peeled was attached to glass (soda lime glass, manufactured by Matsunami Glass Industrial Co., Ltd.) with one reciprocation of a 2 kg hand roller.
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. After setting the sample for evaluation in a tensile tester, the sample was allowed to stand for 30 minutes at an environmental temperature of 23 ° C., or left for 7 days in a temperature environment of 80 ° C., and then the tensile test was started. The conditions of the tensile test were as follows: peeling angle: 180 degrees, peeling speed (pulling speed): 300 mm / min. The load when the surface protective film was peeled from the glass was measured, and the average load at that time was defined as the peel force of the surface protective film.

[Example 1]
As polyol (A), preminol S3011 (manufactured by Asahi Glass Co., Ltd., Mn = 10000) which is a polyol having 3 OH groups: 85 parts by weight, Sanniks GP-3000 (Sanyo Chemical Co., Ltd.) which is a polyol having 3 OH groups Sanix GP-1000 (manufactured by Sanyo Chemical Co., Ltd., Mn = 1000): 13 parts by weight, polyol having 3 OH groups: 2 parts by weight, polyfunctional isocyanate compound (B) Coronate HX which is a polyfunctional alicyclic isocyanate compound (manufactured by Nippon Polyurethane Industry Co., Ltd.): 18 parts by weight, catalyst (manufactured by Nippon Chemical Industry Co., Ltd., trade name: Nursem Ferric): 0.1 part by weight, fatty acid Isopropyl myristate as an ester (trade name: EXCEPARL IPM, Mn = 270, manufactured by Kao Corporation) : 20 parts by weight, 1-ethyl-3-methylimidazolium bis (fluoromethanesulfonyl) imide (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., trade name: AS110): 1.5 parts by weight, polyether-modified silicone of both ends type Oil (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KF-6004): 0.02 parts by weight, siloxane bond-containing polymer (manufactured by Kyoeisha Chemical Co., Ltd., trade name: LE-302): 0.25 parts by weight, diluent solvent Ethyl acetate was added and mixed and stirred to produce an adhesive composition (1).
The obtained pressure-sensitive adhesive composition (1) was applied to a base material “Lumirror S10” (thickness 38 μm, manufactured by Toray Industries, Inc.) made of a polyester resin so that the thickness after drying with a fountain roll would be 10 μm. It was cured and dried under conditions of 130 ° C. and a drying time of 30 seconds. Thus, the adhesive layer was produced on the base material. Next, the surface of the pressure-sensitive adhesive layer was pasted with the silicone-treated surface of a base material (separator) made of a polyester resin having a thickness of 25 μm and subjected to silicone treatment on one surface, to obtain a surface protective film with separator (1). .
The results are shown in Table 1.

[Example 2]
Without using 1-ethyl-3-methylimidazolium bis (fluoromethanesulfonyl) imide (Daiichi Kogyo Seiyaku Co., Ltd., trade name: AS110), a siloxane bond-containing polymer (Kyoeisha Chemical Co., Ltd., trade name: LE-302): A pressure-sensitive adhesive was carried out in the same manner as in Example 1 except that fluorinated polymer (manufactured by DIC, trade name: F-571): 0.50 part by weight was used instead of 0.25 part by weight. A composition (2) was produced to obtain a separator-coated surface protective film (2).
The results are shown in Table 1.

Example 3
A pressure-sensitive adhesive composition (3) was produced in the same manner as in Example 2 except that the amount of the fluorine-containing polymer (manufactured by DIC, trade name: F-571) was changed to 1.00 parts by weight. A surface protective film (3) was obtained.
The results are shown in Table 1.

Example 4
When the pressure-sensitive adhesive composition was produced, the same procedure as in Example 1 was carried out except that a fluorine-containing polymer (manufactured by DIC, trade name: F-571): 0.30 part by weight was used. 4) was produced to obtain a separator-coated surface protective film (4).
The results are shown in Table 1.

Example 5
Siloxane bond-containing polymer (manufactured by Kyoeisha Chemical Co., Ltd., trade name: LE-302): Instead of using 0.25 parts by weight, fluorine-containing polymer (manufactured by DIC, trade name: F-571): 0.30 parts by weight is used. A pressure-sensitive adhesive composition (5) was produced in the same manner as in Example 1, except that a surface protective film with a separator (5) was obtained.
The results are shown in Table 1.

Example 6
As a polyol (A), Sanix GP-3000 (manufactured by Sanyo Chemical Co., Ltd., Mn = 3000) which is a polyol having three OH groups: 100 parts by weight, a polyfunctional alicyclic system as a polyfunctional isocyanate compound (B) Coronate HX which is an isocyanate compound (manufactured by Nippon Polyurethane Industry Co., Ltd.): 18 parts by weight, catalyst (manufactured by Nippon Chemical Industry Co., Ltd., trade name: Nursem Ferric): 0.1 part by weight, hydroxyl group-containing silicone (Shin-Etsu Chemical Co., Ltd.) Product name: X-22-4015): 0.25 parts by weight, ethyl acetate was added as a diluting solvent and mixed and stirred to produce an adhesive composition (6).
Using the pressure-sensitive adhesive composition (6), the same procedure as in Example 1 was carried out to obtain a surface protective film with separator (6).
The results are shown in Table 1.

[Comparative Example 1]
As polyol (A), preminol S3011 (manufactured by Asahi Glass Co., Ltd., Mn = 10000) which is a polyol having 3 OH groups: 85 parts by weight, Sanniks GP-3000 (Sanyo Chemical Co., Ltd.) which is a polyol having 3 OH groups Sanix GP-1000 (manufactured by Sanyo Chemical Co., Ltd., Mn = 1000): 13 parts by weight, polyol having 3 OH groups: 2 parts by weight, polyfunctional isocyanate compound (B) Coronate HX which is a polyfunctional alicyclic isocyanate compound (manufactured by Nippon Polyurethane Industry Co., Ltd.): 18 parts by weight, catalyst (manufactured by Nippon Chemical Industry Co., Ltd., trade name: Nursem Ferric): 0.1 part by weight, dilution Ethyl acetate was added as a solvent and mixed and stirred to produce an adhesive composition (C1).
Using the pressure-sensitive adhesive composition (C1), the same procedure as in Example 1 was carried out to obtain a surface protective film with separator (C1).
The results are shown in Table 1.

[Comparative Example 2]
Comparative Example 1 except that a double-ended polyether-modified silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KF-6004): 0.02 parts by weight was used in the production of the pressure-sensitive adhesive composition. In the same manner as above, a pressure-sensitive adhesive composition (C2) was produced, and a surface protective film with separator (C2) was obtained.
The results are shown in Table 1.

[Comparative Example 3]
As a polyol (A), Sanix GP-3000 (manufactured by Sanyo Chemical Co., Ltd., Mn = 3000) which is a polyol having three OH groups: 100 parts by weight, a polyfunctional alicyclic system as a polyfunctional isocyanate compound (B) Coronate HX which is an isocyanate compound (manufactured by Nippon Polyurethane Industry Co., Ltd.): 18 parts by weight, catalyst (manufactured by Nippon Kagaku Sangyo Co., Ltd., trade name: Nursem Ferric): 0.1 part by weight, ethyl acetate is added as a diluent solvent The mixture was stirred and an adhesive composition (C3) was produced.
Using the pressure-sensitive adhesive composition (C3), the same procedure as in Example 1 was performed to obtain a surface protective film with separator (C3).
The results are shown in Table 1.

[Comparative Example 4]
1-ethyl-3-methylimidazolium bis (fluoromethanesulfonyl) imide (Daiichi Kogyo Seiyaku Co., Ltd., trade name: AS110) and siloxane bond-containing polymer (Kyoeisha Chemical Co., Ltd., trade name: LE-302) Except not using, it carried out similarly to Example 1 and manufactured the adhesive composition (C4), and obtained the surface protection film (C4) with a separator.
The results are shown in Table 1.

[Comparative Example 5]
Without using a siloxane bond-containing polymer, the amount of isopropyl myristate (trade name: Exepal IPM, Mn = 270, manufactured by Kao Corporation) was changed to 30 parts by weight, and both ends-type polyether-modified silicone oil (Shin-Etsu Chemical Co., Ltd.) A pressure-sensitive adhesive composition (C5) was produced in the same manner as in Example 1 except that the amount used of Co., Ltd., trade name: KF-6004) was changed to 0.01 parts by weight. (C5) was obtained.
The results are shown in Table 1.

[Comparative Example 6]
A pressure-sensitive adhesive composition was prepared in the same manner as in Comparative Example 1 except that 25 parts by weight of isopropyl myristate (trade name: Exepearl IPM, Mn = 270) manufactured by Kao Corporation was used when producing the pressure-sensitive adhesive composition. A composition (C6) was produced to obtain a surface protective film with separator (C6).
The results are shown in Table 1.

[Comparative Example 7]
Double-ended polyether-modified silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KF-6004): Instead of using 0.01 parts by weight, a silicone release agent (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KS) −776A): A pressure-sensitive adhesive composition (C7) was produced in the same manner as in Comparative Example 5 except that 0.15 part by weight was used, and a surface protective film with a separator (C7) was obtained.
The results are shown in Table 1.

Example 7
"Siavine SH-109" as urethane prepolymer (C) (solid content 54%, fatty acid ester contained, manufactured by Toyo Ink Co., Ltd.): 100 parts by weight, polyfunctional isocyanate compound (B) as polyfunctional alicyclic isocyanate compound A coronate HX (manufactured by Nippon Polyurethane Industry Co., Ltd.): 7.05 parts by weight, fluorine-containing polymer (manufactured by DIC, trade name: F-571): 1.00 parts by weight, and toluene: 208 parts by weight as a diluent solvent. The mixture was stirred with a disper to produce an adhesive composition (7).
The obtained pressure-sensitive adhesive composition (7) was applied to a base material “Lumirror S10” (thickness 38 μm, manufactured by Toray Industries, Inc.) made of a polyester resin so that the thickness after drying with a fountain roll was 10 μm. It was cured and dried under conditions of 130 ° C. and a drying time of 30 seconds. Thus, the adhesive layer was produced on the base material. Next, the surface of the pressure-sensitive adhesive layer was pasted with a silicone-treated surface of a base material (separator) made of a polyester resin having a thickness of 25 μm and subjected to silicone treatment on one surface, to obtain a surface protective film (7) with a separator. .
The results are shown in Table 2.

Example 8
A pressure-sensitive adhesive composition (8) was produced in the same manner as in Example 7 except that the amount of the fluorine-containing polymer (manufactured by DIC, trade name: F-571) was changed to 2.00 parts by weight. A surface protective film (8) was obtained.
The results are shown in Table 2.

Example 9
A pressure-sensitive adhesive composition (9) was produced in the same manner as in Example 7 except that the amount of the fluorine-containing polymer (manufactured by DIC, trade name: F-571) was changed to 3.00 parts by weight. A surface protective film (9) was obtained.
The results are shown in Table 2.

Example 10
"Siavine SH-109" as urethane prepolymer (C) (solid content 54%, fatty acid ester contained, manufactured by Toyo Ink Co., Ltd.): 100 parts by weight, polyfunctional isocyanate compound (B) as polyfunctional alicyclic isocyanate compound A coronate HX (manufactured by Nippon Polyurethane Industry Co., Ltd.): 3.6 parts by weight, fluorine-containing polymer (manufactured by DIC, trade name: F-571): 1.00 parts by weight, and toluene: 208 parts by weight as a diluent solvent The mixture was stirred with a disper to produce an adhesive composition (10).
The obtained pressure-sensitive adhesive composition (10) was applied to a base material “Lumirror S10” (thickness 38 μm, manufactured by Toray Industries, Inc.) made of a polyester resin so that the thickness after drying with a fountain roll was 50 μm, and the drying temperature It was cured and dried under conditions of 130 ° C. and a drying time of 30 seconds. Thus, the adhesive layer was produced on the base material. Next, the surface of the pressure-sensitive adhesive layer was pasted with the silicone-treated surface of a base material (separator) made of a polyester resin having a thickness of 25 μm and subjected to silicone treatment on one surface to obtain a surface protective film with separator (10). .
The results are shown in Tables 3 and 4.

Example 11
A pressure-sensitive adhesive composition (11) was produced in the same manner as in Example 10 except that the amount of the fluorine-containing polymer (manufactured by DIC, trade name: F-571) was changed to 3.00 parts by weight. A surface protective film (11) was obtained.
The results are shown in Tables 3 and 4.

Example 12
A pressure-sensitive adhesive composition (12) was produced in the same manner as in Example 10 except that the amount of the fluorine-containing polymer (manufactured by DIC, trade name: F-571) was changed to 5.00 parts by weight. A surface protective film (12) was obtained.
The results are shown in Tables 3 and 4.

[Comparative Example 8]
A pressure-sensitive adhesive composition (C8) was produced in the same manner as in Example 10 except that the fluorine-containing polymer (manufactured by DIC, trade name: F-571) was not used, and a surface protective film with a separator (C8) was obtained. It was.
The results are shown in Tables 3 and 4.

[Comparative Example 9]
The same procedure as in Example 10 was performed except that the amount of Coronate HX (manufactured by Nippon Polyurethane Industry Co., Ltd.) was replaced with 7.05 parts by weight and no fluorine-containing polymer (manufactured by DIC, trade name: F-571) was used. A pressure-sensitive adhesive composition (C9) was produced to obtain a surface protective film with separator (C9).
The results are shown in Tables 3 and 4.

Example 13
"Siavine SH-109" as urethane prepolymer (C) (solid content 54%, fatty acid ester contained, manufactured by Toyo Ink Co., Ltd.): 100 parts by weight, polyfunctional isocyanate compound (B) as polyfunctional alicyclic isocyanate compound A coronate HX (manufactured by Nippon Polyurethane Industry Co., Ltd.): 7.05 parts by weight, fluorine-containing polymer (manufactured by DIC, trade name: F-571): 1.00 parts by weight, and toluene: 208 parts by weight as a diluent solvent. The mixture was stirred with a disper to produce an adhesive composition (13).
The obtained pressure-sensitive adhesive composition (13) was applied to a base material “Lumirror S10” (thickness 38 μm, manufactured by Toray Industries, Inc.) made of a polyester resin so that the thickness after drying with a fountain roll was 50 μm, and the drying temperature It was cured and dried under conditions of 130 ° C. and a drying time of 30 seconds. Thus, the adhesive layer was produced on the base material. Next, the surface of the pressure-sensitive adhesive layer was pasted with the silicone-treated surface of a base material (separator) made of a polyester resin having a thickness of 25 μm and subjected to silicone treatment on one surface to obtain a surface protective film with separator (13). .
The results are shown in Tables 3 and 4.

Example 14
A pressure-sensitive adhesive composition (14) was produced in the same manner as in Example 13 except that the amount of the fluorine-containing polymer (manufactured by DIC, trade name: F-571) was changed to 3.00 parts by weight. A surface protective film (14) was obtained.
The results are shown in Tables 3 and 4.

Example 15
A pressure-sensitive adhesive composition (15) was produced in the same manner as in Example 13 except that the amount of the fluorine-containing polymer (manufactured by DIC, trade name: F-571) was changed to 5.00 parts by weight. A surface protective film (15) was obtained.
The results are shown in Tables 3 and 4.

[Comparative Example 10]
Example 13 is the same as Example 13 except that the fluorine-containing polymer (manufactured by DIC, trade name: F-571) is not used, and the silicone release agent (trade name: KS-776A, manufactured by Shin-Etsu Chemical Co., Ltd.): 1 part by weight is used. It carried out similarly and manufactured the adhesive composition (C10), and obtained the surface protection film (C10) with a separator.
The results are shown in Tables 3 and 4.

[Comparative Example 11]
Example 13 except that a fluorine-containing polymer (manufactured by DIC, trade name: F-571) was not used, and a silicone release agent (trade name: KS-776A, manufactured by Shin-Etsu Chemical Co., Ltd.): 3 parts by weight was used. It carried out similarly and manufactured the adhesive composition (C11), and obtained the surface protection film (C11) with a separator.
The results are shown in Tables 3 and 4.

[Comparative Example 12]
Instead of using 17.7 parts by weight of Coronate HX (manufactured by Nippon Polyurethane Industry Co., Ltd.), without using a fluorine-containing polymer (manufactured by DIC, product name: F-571), the thickness of the pressure-sensitive adhesive layer is 10 μm. Except having carried out, it carried out similarly to Example 13 and manufactured the adhesive composition (C12), and obtained the surface protection film (C12) with a separator.
The results are shown in Tables 3 and 4.

[Comparative Example 13]
Instead of using 17.7 parts by weight of Coronate HX (manufactured by Nippon Polyurethane Industry Co., Ltd.), without using a fluorine-containing polymer (manufactured by DIC, product name: F-571), the thickness of the pressure-sensitive adhesive layer is 25 μm. Except having carried out, it carried out similarly to Example 13 and manufactured the adhesive composition (C13), and obtained the surface protection film (C13) with a separator.
The results are shown in Tables 3 and 4.

Example 16
As polyol (A), preminol S3011 (manufactured by Asahi Glass Co., Ltd., Mn = 10000) which is a polyol having 3 OH groups: 85 parts by weight, Sanniks GP-3000 (Sanyo Chemical Co., Ltd.) which is a polyol having 3 OH groups Sanix GP-1000 (manufactured by Sanyo Chemical Co., Ltd., Mn = 1000): 13 parts by weight, polyol having 3 OH groups: 2 parts by weight, polyfunctional isocyanate compound (B) Coronate HX which is a polyfunctional alicyclic isocyanate compound (manufactured by Nippon Polyurethane Industry Co., Ltd.): 17.7 parts by weight, fluorine-containing polymer (manufactured by DIC, trade name: F-571): 0.3 parts by weight, diluent solvent As a mixture, 200 parts by weight of ethyl acetate was mixed and stirred with a disper to produce an adhesive composition (16).
The obtained pressure-sensitive adhesive composition (16) was applied to a base material “Lumirror S10” (thickness 38 μm, manufactured by Toray Industries, Inc.) made of a polyester resin so that the thickness after drying with a fountain roll would be 10 μm. It was cured and dried under conditions of 130 ° C. and a drying time of 30 seconds. Thus, the adhesive layer was produced on the base material. Next, the surface of the pressure-sensitive adhesive layer was pasted with the silicone-treated surface of a base material (separator) made of a polyester resin having a thickness of 25 μm and subjected to silicone treatment on one surface to obtain a surface protective film with separator (16). .
The results are shown in Tables 3 and 4.

Example 17
A pressure-sensitive adhesive composition (17) was produced in the same manner as in Example 16 except that the thickness of the pressure-sensitive adhesive layer was 25 μm, and a surface protective film with a separator (17) was obtained.
The results are shown in Tables 3 and 4.

Example 18
As polyol (A), preminol S3011 (manufactured by Asahi Glass Co., Ltd., Mn = 10000) which is a polyol having 3 OH groups: 85 parts by weight, Sanniks GP-3000 (Sanyo Chemical Co., Ltd.) which is a polyol having 3 OH groups Sanix GP-1000 (manufactured by Sanyo Chemical Co., Ltd., Mn = 1000): 13 parts by weight, polyol having 3 OH groups: 2 parts by weight, polyfunctional isocyanate compound (B) Coronate HX which is a polyfunctional alicyclic isocyanate compound (Nippon Polyurethane Industry Co., Ltd.): 17.7 parts by weight, hydroxyl group-containing silicone (Shin-Etsu Chemical Co., Ltd., trade name: X-22-4015): 0. 3 parts by weight, 200 parts by weight of ethyl acetate as a diluent solvent, and stirred with a disper, adhesive composition (18) was prepared.
The obtained pressure-sensitive adhesive composition (18) was applied to a base material “Lumirror S10” (thickness 38 μm, manufactured by Toray Industries, Inc.) made of a polyester resin so that the thickness after drying with a fountain roll would be 10 μm. It was cured and dried under conditions of 130 ° C. and a drying time of 30 seconds. Thus, the adhesive layer was produced on the base material. Next, the surface of the pressure-sensitive adhesive layer was pasted with a silicone-treated surface of a base material (separator) made of a polyester resin having a thickness of 25 μm and subjected to silicone treatment on one surface to obtain a surface protective film (18) with a separator. .
The results are shown in Tables 3 and 4.

Example 19
A pressure-sensitive adhesive composition (19) was produced in the same manner as in Example 18 except that the thickness of the pressure-sensitive adhesive layer was 25 μm, and a surface protective film with a separator (19) was obtained.
The results are shown in Tables 3 and 4.

Example 20
The separator of the surface protective film with separator (1) obtained in Example 1 was peeled off, and the pressure-sensitive adhesive layer side was adhered to a polarizing plate (product name “TEG1465DUHC” manufactured by Nitto Denko Corporation) as an optical member, An optical member having a surface protective film attached thereto was obtained.

Example 21
The separator of the surface protective film with separator (2) obtained in Example 2 was peeled off, and the pressure-sensitive adhesive layer side was attached to a polarizing plate (trade name “TEG1465DUHC” manufactured by Nitto Denko Corporation) as an optical member. An optical member having a surface protective film attached thereto was obtained.

[Example 22]
The separator of the surface protective film with separator (3) obtained in Example 3 was peeled off, and the pressure-sensitive adhesive layer side was adhered to a polarizing plate (manufactured by Nitto Denko Corporation, trade name “TEG1465DUHC”) as an optical member. An optical member having a surface protective film attached thereto was obtained.

Example 23
The separator of the surface protective film with separator (4) obtained in Example 4 was peeled off, and the pressure-sensitive adhesive layer side was adhered to a polarizing plate (trade name “TEG1465DUHC” manufactured by Nitto Denko Corporation) as an optical member. An optical member having a surface protective film attached thereto was obtained.

Example 24
The separator of the surface protective film with separator (5) obtained in Example 5 was peeled off, and the pressure-sensitive adhesive layer side was attached to a polarizing plate (trade name “TEG1465DUHC” manufactured by Nitto Denko Corporation) as an optical member. An optical member having a surface protective film attached thereto was obtained.

Example 25
The separator of the surface protective film with separator (6) obtained in Example 6 was peeled off, and the pressure-sensitive adhesive layer side was attached to a polarizing plate (trade name “TEG1465DUHC” manufactured by Nitto Denko Corporation) as an optical member. An optical member having a surface protective film attached thereto was obtained.

Example 26
The separator of the surface protective film with a separator (1) obtained in Example 1 was peeled off, and the pressure-sensitive adhesive layer side was a conductive film as an electronic member (trade name “Electrista V270L-TFMP” manufactured by Nitto Denko Corporation). An electronic member having a surface protective film attached thereto was obtained.

Example 27
The separator of the surface protective film with separator (2) obtained in Example 2 was peeled off, and the pressure-sensitive adhesive layer side was a conductive film as an electronic member (trade name “Electrista V270L-TFMP” manufactured by Nitto Denko Corporation). An electronic member having a surface protective film attached thereto was obtained.

Example 28
The separator of the surface protective film with separator (3) obtained in Example 3 was peeled off, and the pressure-sensitive adhesive layer side was a conductive film as an electronic member (trade name “Electrista V270L-TFMP” manufactured by Nitto Denko Corporation). An electronic member having a surface protective film attached thereto was obtained.

Example 29
The separator of the surface protective film with separator (4) obtained in Example 4 was peeled off, and the pressure-sensitive adhesive layer side was a conductive film as an electronic member (trade name “Electrista V270L-TFMP” manufactured by Nitto Denko Corporation). An electronic member having a surface protective film attached thereto was obtained.

Example 30
The separator of the surface protective film with separator (5) obtained in Example 5 was peeled off, and the pressure-sensitive adhesive layer side was a conductive film as an electronic member (trade name “Electrista V270L-TFMP” manufactured by Nitto Denko Corporation). An electronic member having a surface protective film attached thereto was obtained.

Example 31
The separator of the surface protective film with a separator (6) obtained in Example 6 was peeled off, and the pressure-sensitive adhesive layer side was a conductive film as an electronic member (trade name “Electrista V270L-TFMP” manufactured by Nitto Denko Corporation). An electronic member having a surface protective film attached thereto was obtained.

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

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

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

Example 35
The separator of the surface protective film with separator (16) obtained in Example 16 was peeled off, and the pressure-sensitive adhesive layer side was adhered to a polarizing plate (manufactured by Nitto Denko Corporation, trade name “TEG1465DUHC”) as an optical member. An optical member having a surface protective film attached thereto was obtained.

Example 36
The separator of the surface protective film with separator (18) obtained in Example 18 was peeled off, and the pressure-sensitive adhesive layer side was adhered to a polarizing plate (trade name “TEG1465DUHC” manufactured by Nitto Denko Corporation) as an optical member. An optical member having a surface protective film attached thereto was obtained.

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

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

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

Example 40
The separator of the surface protective film with a separator (16) obtained in Example 16 was peeled off, and the pressure-sensitive adhesive layer side was an electroconductive film as an electronic member (trade name “Electrista V270L-TFMP” manufactured by Nitto Denko Corporation). An electronic member having a surface protective film attached thereto was obtained.

Example 41
The separator of the surface protective film with separator (18) obtained in Example 18 was peeled off, and the pressure-sensitive adhesive layer side was a conductive film as an electronic member (trade name “Electrista V270L-TFMP” manufactured by Nitto Denko Corporation). An electronic member having a surface protective film attached thereto was obtained.

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

A surface protective film having an adhesive layer,
A 25 μm-thick polyethylene terephthalate film was bonded to the pressure-sensitive adhesive layer, and after 30 minutes at 23 ° C., the polyethylene terephthalate film had a peeling force of 0.08 N / min when peeled at a peeling angle of 180 degrees and a peeling speed of 6000 mm / min. 25 mm or less,
Surface protective film.
A 25 μm thick polyethylene terephthalate film was bonded to the pressure-sensitive adhesive layer, and after 30 minutes at 23 ° C., the polyethylene terephthalate film was peeled at a peeling angle of 180 degrees and a peeling speed of 300 mm / min. The surface protective film of Claim 1 which is 25 mm or less.
A surface protective film having an adhesive layer,
A polyethylene terephthalate film having a thickness of 25 μm was bonded to the pressure-sensitive adhesive layer, and after 7 days at 80 ° C., the peeling force when the polyethylene terephthalate film was peeled off at a peeling angle of 180 ° and a peeling speed of 6000 mm / min was 0.35 N / 25 mm or less,
Surface protective film.
A 25 μm-thick polyethylene terephthalate film was bonded to the pressure-sensitive adhesive layer, and after 7 days at 80 ° C., the peel strength when the polyethylene terephthalate film was peeled at a peeling angle of 180 degrees and a peeling speed of 300 mm / min was 0.07 N / The surface protection film of Claim 3 which is 25 mm or less.
A surface protective film having an adhesive layer,
A glass plate having a thickness of 1000 μm was bonded to the pressure-sensitive adhesive layer, and after 30 minutes at 23 ° C., the peeling force when peeled from the glass plate at a peeling angle of 180 degrees and a peeling speed of 6000 mm / min was 0.135 N / 25 mm or less. Is,
Surface protective film.
A glass plate having a thickness of 1000 μm was bonded to the pressure-sensitive adhesive layer, and after 30 minutes at 23 ° C., the peel force when peeled from the glass plate at a peel angle of 180 degrees and a peel speed of 300 mm / min was 0.023 N / 25 mm or less. The surface protective film according to claim 5, wherein
A surface protective film having an adhesive layer,
A glass plate having a thickness of 1000 μm was bonded to the pressure-sensitive adhesive layer, and after 7 days at 80 ° C., the peeling force when peeled from the glass plate at a peeling angle of 180 degrees and a peeling speed of 6000 mm / min was 0.35 N / 25 mm or less. Is,
Surface protective film.
A glass plate having a thickness of 1000 μm was bonded to the pressure-sensitive adhesive layer, and after 7 days at 80 ° C., the peel force when peeled from the glass plate at a peel angle of 180 degrees and a peel speed of 300 mm / min was 0.05 N / 25 mm or less. The surface protective film according to claim 7, wherein
The surface protective film according to any one of claims 1 to 8, wherein the residual adhesion rate 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 protection film according to claim 10, wherein the silicone-based 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 claim 10, wherein the fluorine-containing 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 claim 10, wherein the base polymer is at least one selected from urethane resins, acrylic resins, rubber resins, and silicone resins.
The surface protection film according to claim 13, wherein the urethane resin is a urethane resin formed from a composition containing a polyol (A) and a polyfunctional isocyanate compound (B).
The surface protection film according to claim 13, wherein the urethane resin is a urethane resin formed from a composition containing a urethane prepolymer (C) and a polyfunctional isocyanate compound (B).
The surface protective film according to any one of claims 10 to 15, wherein the pressure-sensitive adhesive composition contains a fatty acid ester.
An optical member to which the surface protective film according to any one of claims 1 to 16 is attached.
An electronic member to which the surface protective film according to any one of claims 1 to 16 is attached.