CN114605931A

CN114605931A - Surface protective film

Info

Publication number: CN114605931A
Application number: CN202210203146.0A
Authority: CN
Inventors: 设乐浩司; 徐创矢; 佐佐木翔悟
Original assignee: Nitto Denko Corp
Current assignee: Nitto Denko Corp
Priority date: 2016-03-04
Filing date: 2017-02-22
Publication date: 2022-06-10
Also published as: WO2017150290A1

Abstract

The invention provides a surface protective film which has ultra-light peeling performance and low contamination of the surface of an adhered object. The surface protection film of the invention has an adhesive layer, wherein a polyethylene terephthalate film with a thickness of 25 μm is bonded to the adhesive layer, and after 30 minutes at 23 ℃, when the polyethylene terephthalate film is peeled at a peeling angle of 180 degrees and a peeling speed of 6000 mm/min, the peeling force is less than 0.08N/25 mm.

Description

Surface protective film

The present application is a divisional application of an application having an application date of 2017, 2/22, an application number of 201780015170.9, and an invention name of "surface protective film".

Technical Field

The present invention relates to a surface protective film.

Background

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

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

However, in the case where the optical member or the electronic member includes a fragile member such as a thin glass, if it is desired to peel off the attached surface protective film, the fragile member may be damaged by a peeling force even when a conventional surface protective film having a light peeling property is used.

Therefore, a surface protective film having a further light peelability, that is, an ultra light peelability, is required as compared with a conventional surface protective film having a light peelability.

Here, in order to reduce the peeling force, when a conventional peeling agent is contained in a large amount in the pressure-sensitive adhesive layer of the surface protective film, a certain degree of super light peelability may be exhibited. However, such a method has the following problems: after the surface protective film is peeled off, the surface of the adherend is contaminated with the release agent to a large extent, and when it is desired to stick the surface protective film again, the surface protective film becomes difficult to stick due to contamination of the surface of the adherend.

In the manufacturing process of optical members and electronic members, a surface protective film attached to an exposed surface is generally stored in an attached state in order to prevent the surface from being damaged during processing, assembly, inspection, transportation, and the like. In this case, when the conventional surface protective film is stored in a bonded state, there is a problem that the adhesive strength increases with time and the peeling is heavy.

As described above, in the production process of optical members and electronic members, there are some aspects to be improved that a surface protective film attached to an exposed surface in order to prevent the surface from being damaged during processing, assembly, inspection, transportation, and the like, that is, there are aspects to be improved that an ultra-light peelability is imparted, the staining property of the surface of an adherend can be reduced, and heavy peeling over time can be suppressed.

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open No. 2016 & 17109

Disclosure of Invention

Problems to be solved by the invention

The invention provides a surface protective film with ultra-light stripping property, a surface protective film capable of reducing the pollution of the surface of an adhered object, and a surface protective film capable of inhibiting the heavy stripping with time.

Means for solving the problems

The surface protective film of the present invention has an adhesive layer in which,

a polyethylene terephthalate film having a thickness of 25 μm is bonded to the pressure-sensitive adhesive layer, and after 30 minutes at 23 ℃, the peel force is 0.08N/25mm or less when the polyethylene terephthalate film is peeled at a peel angle of 180 degrees and a peel speed of 6000 mm/min.

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 ℃, when the polyethylene terephthalate film is peeled at a peeling angle of 180 degrees and a peeling speed of 300 mm/min, the peeling force is 0.02N/25mm or less.

a polyethylene terephthalate film having a thickness of 25 μm is bonded to the pressure-sensitive adhesive layer, and after 7 days at 80 ℃, the peel force is 0.35N/25mm or less when the polyethylene terephthalate film is peeled at a peel angle of 180 degrees and a peel speed of 6000 mm/min.

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

a glass plate having a thickness of 1000 μm was bonded to the adhesive layer, and when the glass plate was peeled from the adhesive layer at a peeling angle of 180 degrees and a peeling speed of 6000 mm/min after 30 minutes at 23 ℃, the peeling force was 0.135N/25mm or less.

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

a glass plate having a thickness of 1000 μm was bonded to the adhesive layer, and when the glass plate was peeled from the adhesive layer at a peeling angle of 180 degrees and a peeling speed of 6000 mm/min after 7 days at 80 ℃, the peeling force was 0.35N/25mm or less.

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

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

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

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

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

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

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

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

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

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

The electronic component of the present invention is bonded with the surface protective film of the present invention.

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, a surface protective film having ultra-light peelability and low staining property on the surface of an adherend can be provided.

Drawings

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

Description of the symbols

1 base material layer

2 adhesive layer

10 surface protective film

Detailed Description

Surface protection film

The surface protective film of the present invention has an adhesive layer. When the surface protective film of the present invention has an adhesive layer, any other suitable member may be provided within a range not impairing the effects of the present invention. 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 an embodiment of the present invention. In fig. 1, the surface protection film 10 includes a base layer 1 and a pressure-sensitive adhesive layer 2. In fig. 1, a base material layer 1 and an adhesive layer 2 are directly laminated.

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

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

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

In one embodiment of the surface protective film of the present invention, when a polyethylene terephthalate film having a thickness of 25 μm is bonded to an adhesive layer and the polyethylene terephthalate film is peeled at a peeling angle of 180 degrees and a peeling speed of 6000 mm/min at 23 ℃ for 30 minutes, the peeling force is preferably 0.08N/25mm or less, more preferably 0.075N/25mm or less, still more preferably 0.07N/25mm or less, still more preferably 0.065N/25mm or less, particularly preferably 0.06N/25mm or less, and most preferably 0.055N/25mm or less. The lower limit of the peeling force is substantially 0.001N/25mm or more. The surface protective film of the present invention can exhibit very excellent ultra-light peelability if the above-mentioned peeling force at a very high peeling speed, such as a peeling speed of 6000 mm/min, is in the above-mentioned range. 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, when a polyethylene terephthalate film having a thickness of 25 μm is bonded to an adhesive layer and the polyethylene terephthalate film is peeled at a peeling angle of 180 degrees and a peeling speed of 300 mm/min after 30 minutes at 23 ℃, the peeling force is preferably 0.02N/25mm or less, more preferably 0.018N/25mm or less, still more preferably 0.015N/25mm or less, particularly preferably 0.012N/25mm or less, and most preferably 0.01N/25mm or less. The lower limit of the peeling force is substantially 0.001N/25mm or more. When the above peeling force is within the above range, the surface protective film of the present invention can exhibit ultra light peelability. The details of the measurement of the peeling force will be described later.

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

In one embodiment of the surface protection film of the present invention, when a polyethylene terephthalate film having a thickness of 25 μm is bonded to a pressure-sensitive adhesive layer and peeled at a peeling angle of 180 degrees and a peeling speed of 300 mm/min at 80 ℃ for 7 days, the peeling force is preferably 0.07N/25mm or less, more preferably 0.06N/25mm or less, still more preferably 0.05N/25mm or less, particularly preferably 0.045N/25mm or less, and most preferably 0.04N/25mm or less. The lower limit of the peeling force is substantially 0.001N/25mm or more. When the peeling force is within the above range, the surface protective film of the present invention can suppress re-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, when a glass plate having a thickness of 1000 μm is bonded to an adhesive layer and peeled from the glass plate at a peeling angle of 180 degrees and a peeling speed of 6000 mm/min after 30 minutes at 23 ℃, the peeling force is preferably 0.135N/25mm or less, more preferably 0.1N/25mm or less, still more preferably 0.07N/25mm or less, still more preferably 0.065N/25mm or less, particularly preferably 0.06N/25mm or less, and most preferably 0.055N/25mm or less. The lower limit of the peeling force is substantially 0.001N/25mm or more. When the above-mentioned peeling force is within the above-mentioned range at a very high peeling speed of 6000 mm/min, the surface protective film of the present invention can exhibit very excellent ultra-light peelability. The details of the measurement of the peeling force will be described later.

In one embodiment of the surface protective film of the present invention, when a glass plate having a thickness of 1000 μm is bonded to an adhesive layer and peeled from the glass plate at a peeling angle of 180 degrees and a peeling speed of 300 mm/min at 23 ℃ for 30 minutes, the peeling force is preferably 0.023N/25mm or less, more preferably 0.022N/25mm or less, still more preferably 0.02N/25mm or less, particularly preferably 0.015N/25mm or less, and most preferably 0.013N/25mm or less. The lower limit of the peeling force is substantially 0.001N/25mm or more. When the above peeling force is within the above range, the surface protective film of the present invention can exhibit ultra light peelability. The details of the measurement of the peeling force will be described later.

In one embodiment of the surface protective film of the present invention, when a glass plate having a thickness of 1000 μm is bonded to an adhesive layer and peeled from the glass plate at a peeling angle of 180 degrees and a peeling speed of 6000 mm/min after 7 days at 80 ℃, the peeling force is preferably 0.35N/25mm or less, more preferably 0.3N/25mm or less, still more preferably 0.25N/25mm or less, still more preferably 0.2N/25mm or less, particularly preferably 0.15N/25mm or less, and most preferably 0.1N/25mm or less. The lower limit of the peeling force is substantially 0.001N/25mm or more. When the peeling force after 7 days at 80 ℃ is within the above range, the surface protective film of the present invention can sufficiently suppress the re-peeling with 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, when a glass plate having a thickness of 1000 μm is bonded to an adhesive layer and peeled from the glass plate at a peeling angle of 180 degrees and a peeling speed of 300 mm/min after 7 days at 80 ℃, the peeling force is preferably 0.05N/25mm or less, more preferably 0.045N/25mm or less, still more preferably 0.04N/25mm or less, particularly preferably 0.035N/25mm or less, and most preferably 0.03N/25mm or less. The lower limit of the peeling force is substantially 0.001N/25mm or more. When the peeling force is within the above range, the surface protective film of the present invention can suppress re-peeling over time. The details of the measurement of the peeling force will be described later.

The residual adhesion ratio of the surface protective film of the present invention is preferably 50% or more, more preferably 55% to 100%, further preferably 60% to 100%, particularly preferably 65% to 100%, most preferably 70% to 100%. When the residual adhesion ratio is within the above range, the surface protective film of the present invention can exhibit an effect of reducing staining of the adherend surface. The details of the measurement of the residual adhesion ratio will be described later.

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

(1) a method of coating a solution or a hot melt of a material for forming an adhesive layer on a base material layer;

(2) a method of transferring a pressure-sensitive adhesive layer formed by applying a solution or a hot-melt of a material for forming a pressure-sensitive adhesive layer on a separator onto a base material layer;

(3) a method of forming a material for forming an adhesive layer by extrusion coating onto a base material layer;

(4) a method of extruding the substrate layer and the adhesive layer in the form of a double layer or a multilayer;

(5) a method of laminating an adhesive layer on a substrate layer in a single layer or a method of laminating an adhesive layer and a laminate layer in a double layer;

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

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

Substrate layer

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

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

For example, a surface of the base material layer on which the pressure-sensitive adhesive layer is not provided may be subjected to a release treatment by adding a fatty amide, polyethyleneimine, a long-chain alkyl additive, or the like to the base material layer, or may be provided with a coating layer containing any suitable release agent such as silicone, long-chain alkyl, or fluorine, in order to form a wound body or the like which can be easily unwound.

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

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

The base layer may contain any suitable additive as required. Examples of additives that can be contained in the base layer include: antioxidants, ultraviolet absorbers, light stabilizers, antistatic agents, fillers, pigments, and the like. The kind and amount of the additive that the base material layer may contain may be appropriately set according to the purpose. Particularly, when the material of the base material layer is plastic, it is preferable to contain a plurality of the above additives in order to prevent deterioration. From the viewpoint of improving weather resistance and the like, preferable examples of the additive include: antioxidants, ultraviolet absorbers, light stabilizers, fillers.

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

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

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

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

In addition, as the additive, in order to impart antistatic properties, preferable examples include: surfactants, inorganic salts, polyols, metal compounds, inorganic, low molecular weight and high molecular weight antistatic agents such as carbon. In particular, from the viewpoint of contamination and adhesion retention, a high molecular weight antistatic agent and carbon are preferable.

Adhesive layer

The adhesive layer may be manufactured by any suitable manufacturing method. Examples of such a production method include the following methods: the composition as a pressure-sensitive adhesive layer-forming material is applied to a base layer, and a pressure-sensitive adhesive layer is formed on the base layer. Examples of such a coating method 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 to 150. mu.m, more preferably 2 to 140. mu.m, still more preferably 3 to 130. mu.m, yet more preferably 4 to 120. mu.m, yet more preferably 5 to 100. mu.m, yet more preferably 10 to 90. mu.m, particularly preferably 20 to 85 μm, most preferably 30 to 80 μm.

The adhesive layer is composed of an adhesive. The adhesive is formed from an adhesive composition.

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

The content of the silicone additive and/or the fluorine additive in the adhesive composition is preferably 0.01 to 50 parts by weight, more preferably 0.02 to 25 parts by weight, further preferably 0.025 to 10 parts by weight, particularly preferably 0.03 to 5 parts by weight, and most preferably 0.05 to 3 parts by weight, based on 100 parts by weight of the base polymer, in total of the silicone additive and the fluorine additive. When the content of the silicone-based additive and/or the fluorine-based additive in the pressure-sensitive adhesive composition is within the above range, the surface protective film of the present invention can exhibit not only higher super-light releasability but also further reduced staining of the adherend surface.

< basic Polymer >

The base polymer is preferably at least one selected from the group consisting of urethane resins, acrylic resins, rubber resins, and silicone resins. The base polymer is more preferably a urethane resin or an acrylic resin from the viewpoint of further exhibiting the effects of the present invention.

[ urethane resin ]

As the urethane resin, any suitable urethane resin may be used within a range not impairing the effects of the present invention. The urethane resin is preferably a urethane resin formed from a composition containing a polyol (a) and a polyfunctional isocyanate compound (B), or a urethane resin formed from a composition containing a urethane prepolymer (C) and a polyfunctional isocyanate compound (B). Since the wettability of the pressure-sensitive adhesive layer can be improved by using the resin as described above as the urethane resin, the surface protective film of the present invention can be attached without sandwiching air bubbles.

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

The urethane resin preferably contains a deterioration inhibitor such as an antioxidant, an ultraviolet absorber, a light stabilizer, or the like. By incorporating a deterioration inhibitor into the urethane resin, the adhesive does not easily form a residue or the like on an adherend even when stored in a heated state after being adhered to the adherend, and the adhesive residue prevention property can be improved. The number of the deterioration inhibitors may be only 1, or may be 2 or more. As the deterioration inhibitor, an antioxidant is particularly preferable.

Examples of the antioxidant include: radical chain inhibitors, peroxide decomposers, and the like.

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

Examples of the peroxide decomposer include: sulfur-based antioxidants, phosphorus-based antioxidants, and the like.

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

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

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

Examples of the high molecular weight phenol antioxidant include: 1,1, 3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 1,3, 5-trimethyl-2, 4, 6-tris (3, 5-di-t-butyl-4-hydroxybenzyl) benzene, tetrakis [ methylene-3- (3 ', 5 ' -di-t-butyl-4 ' -hydroxyphenyl) propionate ] methane, ethylene glycol bis [3,3 ' -bis- (4 ' -hydroxy-3 ' -t-butylphenyl) butyrate ], 1,3, 5-tris (3 ', 5 ' -di-t-butyl-4 ' -hydroxybenzyl) -S-triazine-2, 4,6- (1H,3H,5H) trione, tocopherol, and the like.

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

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

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

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

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

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

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

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

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

Examples of the ultraviolet stabilizer include: bis (octylphenyl) nickel sulfide, [2, 2' -thiobis (4-tert-octylphenol) ] n-butylamine nickel, 3, 5-di-tert-butyl-4-hydroxybenzyl-phosphoric acid monoethyl ester nickel complex, dibutyl dithiocarbamate nickel, benzoate type quencher (quencher), dibutyl dithiocarbamate nickel, and the like.

(urethane resin formed from a composition containing a polyol (A) and a polyfunctional isocyanate compound (B))

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

The number of the polyol (A) may be only 1, or may be 2 or more.

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

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

The polyester polyol is obtained, for example, by esterification of a polyol component with an acid component.

Examples of the polyol component include: ethylene glycol, diethylene glycol, 1, 3-butanediol, 1, 4-butanediol, neopentyl glycol, 3-methyl-1, 5-pentanediol, 2-butyl-2-ethyl-1, 3-propanediol, 2, 4-diethyl-1, 5-pentanediol, 1, 2-hexanediol, 1, 6-hexanediol, 1, 8-octanediol, 1, 9-nonanediol, 2-methyl-1, 8-octanediol, 1, 8-decanediol, octadecanediol, glycerol, trimethylolpropane, pentaerythritol, hexanetriol, polypropylene glycol, and the like. Examples of the acid component include: succinic acid, methylsuccinic acid, adipic acid, pimelic acid, azelaic acid, sebacic acid, 1, 12-dodecanedioic acid, 1, 14-tetradecanedioic acid, dimer acid, 2-methyl-1, 4-cyclohexanedicarboxylic acid, 2-ethyl-1, 4-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, isophthalic acid, terephthalic acid, 1, 4-naphthalenedicarboxylic acid, 4' -biphenyldicarboxylic acid, anhydrides thereof, and the like.

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

Examples of the polycaprolactone polyol include caprolactone polyesterdiols obtained by ring-opening polymerization of cyclic ester monomers such as e-caprolactone and e-valerolactone.

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

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

The number average molecular weight Mn of the polyol (A) is preferably 300 to 100000, more preferably 400 to 75000, still more preferably 450 to 50000, and particularly preferably 500 to 30000. By adjusting the number average molecular weight Mn of the polyol (a) to be within the above range, the wettability of the pressure-sensitive adhesive layer can be improved, and therefore the surface protective film of the present invention can be attached without sandwiching air bubbles.

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

The content of the polyol (a1) in the polyol (a) is preferably 5% by weight or more, more preferably 25% by weight to 100% by weight, and still more preferably 50% by weight to 100% by weight. By adjusting the content of the polyol (a1) in the polyol (a) to be within the above range, the wettability of the pressure-sensitive adhesive layer can be improved, and therefore the surface protective film of the present invention can be attached without sandwiching air bubbles.

The number average molecular weight Mn of the polyol (A1) is preferably 1000 to 100000, more preferably 1200 to 80000, still more preferably 1500 to 70000, still more preferably 1750 to 50000, particularly preferably 1500 to 40000, and most preferably 2000 to 30000. By adjusting the number average molecular weight Mn of the polyol (a1) to be within the above range, the wettability of the pressure-sensitive adhesive layer can be improved, and therefore the surface protective film of the present invention can be attached without sandwiching air 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 number of the polyhydric alcohols (a2) may be only 1, or may be 2 or more. The number average molecular weight Mn of the polyol (A2) is preferably 100 to 20000, more preferably 150 to 10000, still more preferably 200 to 7500, particularly preferably 300 to 6000, most preferably 300 to 5000. If the number average molecular weight Mn of the polyol (a2) is outside the above range, there is a concern that the adhesive force is particularly increased with the lapse of time, and there is a concern that excellent reworkability cannot be exhibited. Preferred examples of the polyol (a2) include: polyols having 3 OH groups (triols), polyols having 4 OH groups (tetraols), polyols having 5 OH groups (pentaols), polyols having 6 OH groups (hexaols).

The total amount of at least 1 of the polyol (a2) having 4 OH groups (tetraol), the polyol (pentaol) having 5 OH groups, and the polyol (hexaol) having 6 OH groups is preferably 70 wt% or less, more preferably 60 wt% or less, still more preferably 40 wt% or less, and particularly preferably 30 wt% or less, based on the content ratio in the polyol (a). By adjusting at least 1 of the polyol (a2) which is a polyol (a2) and has 4 OH groups (tetraol), 5 OH groups (pentaol), and 6 OH groups (hexaol) to the above range, a urethane resin having excellent transparency can be provided, and the wettability of the pressure-sensitive adhesive layer can be improved.

The content of the polyol (a2) in the polyol (a) is preferably 95% by weight or less, and more preferably 0% by weight to 75% by weight. By adjusting the content of the polyol (a2) in the polyol (a) to be within the above range, the wettability of the pressure-sensitive adhesive layer can be improved, and therefore the surface protective film of the present invention can be attached without sandwiching air bubbles.

The content of the polyol (a2) having 4 or more OH groups and a number average molecular weight Mn of 20000 or less is preferably less than 70% by weight, more preferably 60% by weight or less, still more preferably 50% by weight or less, particularly preferably 40% by weight or less, and most preferably 30% by weight or less, based on the total amount of the polyol (a). By adjusting the content ratio of the polyol having 4 or more OH groups and a number average molecular weight Mn of 20000 or less in the polyol (a2) to the above range, a urethane resin having excellent transparency can be provided and the wettability of the pressure-sensitive adhesive layer can be improved, so that the surface protective film of the present invention can be attached without sandwiching air bubbles.

As the polyfunctional isocyanate compound (B), any suitable polyfunctional isocyanate compound that can be used for the urethanization reaction can be used. Examples of such a polyfunctional isocyanate compound (B) include: polyfunctional aliphatic isocyanate compounds, polyfunctional alicyclic isocyanates, 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 isocyanate, dodecamethylene diisocyanate, 2,4, 4-trimethylhexamethylene diisocyanate, and the like.

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

Examples of the polyfunctional aromatic diisocyanate compound include: benzene diisocyanate, 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, 2 '-diphenylmethane diisocyanate, 4' -toluidine diisocyanate, 4 '-diphenyl ether diisocyanate, 4' -biphenyl diisocyanate, 1, 5-naphthalene diisocyanate, xylylene diisocyanate, and the like.

As the polyfunctional isocyanate compound (B), there can be also mentioned: trimethylolpropane adducts of the above-mentioned various polyfunctional isocyanate compounds, biuret products obtained by reaction with water, trimer having an isocyanurate ring, and the like. In addition, the above compounds may also 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, further preferably 0.2 to 2.5, particularly preferably 0.3 to 2.25, and most preferably 0.5 to 2.0 in terms of NCO groups/OH groups. By adjusting the equivalent ratio of NCO groups/OH groups to be within the above range, the wettability of the pressure-sensitive adhesive layer can be improved, and therefore the surface protective film of the present invention can be attached without sandwiching air bubbles.

The content of the polyfunctional isocyanate compound (B) is preferably 1.0 to 30% by weight, more preferably 1.5 to 27% by weight, still more preferably 2.0 to 25% by weight, particularly preferably 2.3 to 23% by weight, and most preferably 2.5 to 20% by weight, based on the polyol (a). By adjusting the content ratio of the polyfunctional isocyanate compound (B) within the above range, the wettability of the pressure-sensitive adhesive layer can be improved, and therefore the surface protective film of the present invention can be attached without sandwiching air bubbles.

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

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

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

Examples of the organometallic compound include: iron-based compounds, tin-based compounds, titanium-based compounds, zirconium-based compounds, lead-based compounds, cobalt-based compounds, zinc-based compounds, and the like. Among them, from the viewpoints of reaction rate and pot life of the pressure-sensitive adhesive layer, an iron-based compound and a tin-based compound are preferable.

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

Examples of the tin compound include: dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin maleate, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin sulfide, tributylmethoxytin, tributyltin acetate, triethylethoxytin, tributylethoxytin, dioctyltin oxide, dioctyltin dilaurate, tributyltin chloride, tributyltin trichloroacetate, tin 2-ethylhexanoate, and the like.

Examples of the titanium-based compound include: dibutyltitanium dichloride, tetrabutyltitanate, butoxytitanium trichloride, and the like.

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

Examples of the lead-based compound include: lead oleate, lead 2-ethylhexoate, lead benzoate, lead naphthenate, and the like.

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

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

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

The number of the catalyst may be only 1, or may be 2 or more. In addition, a catalyst may be used in combination with a crosslinking retarder or the like. The amount of the catalyst is preferably 0.005 to 1.00% by weight, more preferably 0.01 to 0.75% by weight, much more preferably 0.01 to 0.50% by weight, particularly preferably 0.01 to 0.20% by weight, based on the polyol (A). By adjusting the amount of the catalyst within the above range, the wettability of the adhesive layer can be improved, and therefore the surface protective film of the present invention can be attached without sandwiching air bubbles.

The composition containing the polyol (A) and the polyfunctional isocyanate compound (B) may contain any suitable other components within a range not impairing the effects of the present invention. Examples of such other components include: resin components other than polyurethane resins, tackifiers, inorganic fillers, organic fillers, metal powders, pigments, foils, softeners, antiaging agents, conductive agents, ultraviolet absorbers, antioxidants, light stabilizers, surface lubricants, leveling agents, resists, heat stabilizers, polymerization inhibitors, lubricants, solvents, catalysts, and the like.

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

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

Examples of the urethane resin formed from the composition containing the urethane prepolymer (C) and the polyfunctional isocyanate compound (B) include urethane resins formed from a composition containing a urethane polyol as the urethane prepolymer (C) and the polyfunctional isocyanate compound (B). The number of the urethane prepolymer (C) may be only 1, or may be 2 or more. The number of the polyfunctional isocyanate compounds (B) may be only 1, or may be 2 or more.

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

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

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

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

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

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

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

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

Examples of the aromatic polyisocyanate include: 1, 3-phenylene diisocyanate, 4 ' -biphenyl diisocyanate, 1, 4-phenylene diisocyanate, 4 ' -diphenylmethane diisocyanate, 2, 4-tolylene diisocyanate, 2, 6-tolylene diisocyanate, 4 ' -toluidine diisocyanate, 2,4, 6-triisocyanatotoluene, 1,3, 5-triisocyanatobenzene, dianisidine diisocyanate (dianisidine diisocyanate), 4 ' -diphenylether diisocyanate, 4 ' -triphenylmethane triisocyanate, and the like.

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

Examples of the araliphatic polyisocyanate include: omega, omega '-diisocyanate-1, 3-dimethylbenzene, omega' -diisocyanate-1, 4-diethylbenzene, 1, 4-tetramethylxylylene diisocyanate, 1, 3-tetramethylxylylene diisocyanate, and the like.

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

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

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

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

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

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

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

When a catalyst is used for obtaining a polyurethane polyol, in a system in which two polyols, i.e., a polyester polyol and a polyether polyol, are present, there is a problem that gelation and turbidity of a reaction solution easily occur in a single catalyst system due to a difference in reactivity between the two polyols. Therefore, by using 2 catalysts when obtaining a polyurethane polyol, the reaction rate and the selectivity of the catalyst can be easily controlled, and these problems can be solved. Examples of the combination of 2 catalysts include: tertiary amines/organic metals, tin/non-tin, tin/tin, preferably tin/tin, more preferably a combination of dibutyltin dilaurate and tin 2-ethylhexanoate. The mixing ratio of the tin 2-ethylhexanoate/dibutyltin dilaurate is preferably less than 1, and more preferably 0.2 to 0.6 in terms of weight ratio. When the mixing ratio is 1 or more, there is a risk that gelation is likely to occur due to the balance of the catalytic activity.

When a catalyst is used to obtain the polyurethane polyol, the amount of the catalyst used is preferably 0.01 to 1.0% by weight based on the total amount of the polyester polyol (a1), the polyether polyol (a2), and the organic polyisocyanate compound (a 3).

In the case of using a catalyst in obtaining the polyurethane polyol, the reaction temperature is preferably less than 100 ℃, more preferably from 85 ℃ to 95 ℃. At temperatures above 100 ℃, there is a risk that the reaction rate and the crosslinked structure are difficult to control, and there is a risk that a polyurethane polyol having a given molecular weight is difficult to obtain.

In obtaining the polyurethane polyol, a catalyst may not be used. In this case, the reaction temperature is preferably 100 ℃ or higher, more preferably 110 ℃ or higher. When the polyurethane polyol is obtained without a catalyst, the reaction is preferably carried out for 3 hours or more.

Examples of the method for obtaining the polyurethane polyol include: 1) a method in which the polyester polyol, the polyether polyol, the catalyst and the organic polyisocyanate are all added to the flask; 2) a method in which a polyester polyol, a polyether polyol and a catalyst are added to a flask and an organic polyisocyanate is added dropwise. The method for obtaining the polyurethane polyol is preferably the method 2) from the viewpoint of controlling the reaction.

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

As the polyfunctional isocyanate compound (B), the polyfunctional isocyanate compounds described above can be applied.

In the composition containing the urethane prepolymer (C) and the polyfunctional isocyanate compound (B), any appropriate other component may be contained within a range not impairing the effect of the present invention. Examples of such other components include: resin components other than polyurethane resins, tackifiers, inorganic fillers, organic fillers, metal powders, pigments, foils, softeners, antiaging agents, conductive agents, ultraviolet absorbers, antioxidants, light stabilizers, surface lubricants, leveling agents, resists, heat stabilizers, polymerization inhibitors, lubricants, solvents, catalysts, and the like.

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

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

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 3.0, further preferably 0.02 to 2.5, particularly preferably 0.03 to 2.25, and most preferably 0.05 to 2.0 in terms of NCO groups/OH groups. By adjusting the equivalent ratio of NCO groups/OH groups to be within the above range, the wettability of the pressure-sensitive adhesive layer can be improved, and therefore the surface protective film of the present invention can be attached without sandwiching air bubbles.

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

[ acrylic resin ]

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

The acrylic resin may contain any appropriate component within a range not impairing the effects of the present invention. Examples of such components include: a resin component other than acrylic resin, a tackifier, an inorganic filler, an organic filler, a metal powder, a pigment, a foil, a softening agent, an antiaging agent, a conductive agent, an ultraviolet absorber, an antioxidant, a light stabilizer, a surface lubricant, a leveling agent, a resist, a heat stabilizer, a polymerization inhibitor, a lubricant, a solvent, a catalyst, and the like.

[ rubber-based resin ]

As the rubber-based resin, any suitable rubber-based adhesive such as a known rubber-based adhesive described in japanese patent laid-open No. 2015-074771 and the like can be used within a range not impairing the effect of the present invention. These resins may be 1 kind or 2 or more kinds.

The rubber-based resin may contain any appropriate component within a range not impairing the effects of the present invention. Examples of such components include: a resin component other than the rubber-based resin, a tackifier, an inorganic filler, an organic filler, a metal powder, a pigment, a foil, a softening agent, an antiaging agent, a conductive agent, an ultraviolet absorber, an antioxidant, a light stabilizer, a surface lubricant, a leveling agent, a resist, a heat stabilizer, a polymerization inhibitor, a lubricant, a solvent, a catalyst, and the like.

[ Silicone resin ]

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

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

< organosilicon additives >

The silicone additive may be any suitable silicone additive within a range not impairing the effects of the present invention. The silicone additive is preferably at least one member selected from the group consisting of a silicone bond-containing compound, a hydroxyl group-containing silicone compound, and a crosslinkable functional group-containing silicone compound.

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

Examples of the compound having a siloxane bond include: polyether-modified polyorganosiloxanes obtained by introducing polyether groups into the main chain or side chain of a polyorganosiloxane skeleton (such as polydimethylsiloxane), polyester-modified polyorganosiloxanes obtained by introducing polyester groups into the main chain or side chain of a polyorganosiloxane skeleton, organic compound-introduced polyorganosiloxanes obtained by introducing organic compounds into the main chain or side chain of a polyorganosiloxane skeleton, silicone-modified (meth) acrylic resins obtained by introducing polyorganosiloxanes into (meth) acrylic resins, silicone-modified organic compounds obtained by introducing polyorganosiloxanes into organic compounds, silicone-containing organic compounds obtained by copolymerizing organic compounds and organosilicon compounds, and the like. Examples of commercially available products of such siloxane bond-containing polymers include: "LE-302" (manufactured by Kyoeisha chemical Co., Ltd.), a leveling agent of BYK series manufactured by BYK-Chemie Japan (BYK-300 "," BYK-301/302 "," BYK-306 "," BYK-307 "," BYK-310 "," BYK-315 "," BYK-313 "," BYK-320 "," BYK-322 "," BYK-323 "," BYK-325 "," BYK-330 "," BYK-331 "," BYK-333 "," BYK-337 "," BYK-341 "," BYK-344 "," BYK-345/346 "," BYK-347 "," BYK-348 "," BYK-349 "," BYK-370 "," BYK-375 "," BYK-377 "," BYK-378 "," BYK-UV3500 ", a, "BYK-UV 3510", "BYK-UV 3570", "BYK-3550", "BYK-SILCLEAN 3700", "BYK-SILCLEAN 3720", etc.), AC series leveling agents manufactured by Algin Chemie (AC FS180 "," AC FS360 "," AC S20 ", etc.), Polyflow series leveling agents manufactured by Kyowa chemical Co., Ltd (Polyflow KL-400X", "Polyflow KL-400 HF", "Polyflow KL-401", "Polyflow KL-402", "Polyflow KL-403", "Polyflow KL-404", etc.), KP series leveling agents manufactured by shin-Etsu chemical Co., Ltd (KP-323 "," KP-326 "," KP-341 "," KP-104 "," KP-110 "," KF-112 ", etc.), X22 series, Dow series, etc. manufactured by shin chemical industry Co., Corp, "LP-7002", "8032 ADDITIVE", "57 ADDITIVE", "L-7604", "FZ-2110", "FZ-2105", "67 ADDITIVE", "8618 ADDITIVE", "3 ADDITIVE", "56 ADDITIVE", etc.), etc.

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

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

< fluorine-based additive >

The fluorine-based additive may be any suitable fluorine-based additive within a range not impairing the effects of the present invention. The fluorine-containing additive is preferably at least one selected from the group consisting of fluorine-containing compounds, hydroxyl group-containing fluorine-containing compounds, and fluorine-containing compounds having a crosslinkable functional group.

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

Examples of the fluorine-containing compound include: a compound having a fluorinated aliphatic hydrocarbon skeleton, a fluorine-containing organic compound obtained by copolymerizing an organic compound with a fluorine compound, a fluorine-containing compound containing an organic compound, and the like. Examples of the fluorinated aliphatic hydrocarbon skeleton include: fluorinated C1-C10 alkanes such as fluoromethane, fluoroethane, fluoropropane, fluoroisopropane, fluorobutane, fluoroisobutane, fluorot-butane, fluoropentane and fluorohexane, and the like. Examples of such a fluorinated compound include commercially available products such as: surflon-series leveling agents manufactured by AGC Seimi Chemical company ("S-242", "S-243", "S-420", "S-611", "S-651", "S-386", and the like), BYK-series leveling agents manufactured by BYK-Chemie Japan company ("BYK-340", and the like), AC-series leveling agents manufactured by Algin Chemie company ("AC 110 a", "AC 100 a", and the like), MEGAFAC-series leveling agents manufactured by DIC company ("MEGAFAC F-114", "MEGAFAC F-410", "MEGAFAC F-444", "MEGAFAC EXP TP-2066", "MEGAFAC F-430", "GAFAC F-472", "SF" MEGAFAC F-477 "," MEGAFAC F-552 "," MEGAFAC F-553 "," MEGAFAC F-554 "," MEGAFAC F-555 " "MEGAFAC R-94", "MEGAFAC RS-72-K", "MEGAFAC RS-75", "MEGAFAC F-556", "MEGAFAC EXP TF-1367", "MEGAFAC EXP TF-1437", "MEGAFAC F-558", "MEGAFAC EXP TF-1537", etc.), FC series leveling agents ("FC-4430", "FC-4432", etc.) manufactured by Sumitomo 3M, FTERGENT series leveling agents ("FTERGENT 100", "FTERGENT 100C", "FTERGENT 110", "FTERGENT 150 CH", "FTERGENT A-K", "FTERGENT 501", "FTERGENT 250", "FTERGENT 251", "FTERGENT 222F", "FTERGENT 208G", "FTERGENT 300", "FTERGENT 310", "FTERGENT 400", etc.), and FTIFF-PF series leveling agents ("PF-136A" "manufactured by Beijing chemical industries, Inc, "PF-156A", "PF-151N", "PF-636", "PF-6320", "PF-656", "PF-6520", "PF-651", "PF-652", "PF-3320", etc.), etc.

Examples of the hydroxyl group-containing fluorine-based compound include conventionally known resins, and examples thereof include hydroxyl group-containing fluororesins described in, for example, pamphlet of International publication No. 94/06870, Japanese patent application laid-open No. 8-12921, Japanese patent application laid-open No. 10-72569, Japanese patent application laid-open No. 4-275379, International publication No. 97/11130, and International publication No. 96/26254. Examples of the other hydroxyl-containing fluororesins include fluoroolefin copolymers described in, for example, Japanese patent application laid-open Nos. 8-231919, 10-265731, 10-204374 and 8-12922. Further, there can be enumerated: a copolymer of a compound having a fluorinated alkyl group in the hydroxyl group-containing compound, a fluorine-containing organic compound obtained by copolymerizing a fluorine-containing compound and a hydroxyl group-containing compound, a fluorine-containing compound containing a hydroxyl group-containing organic compound, and the like. Examples of commercially available products of such a hydroxyl group-containing fluorine-based compound include: trade name "Lumiflon" (manufactured by Asahi Glass Co., Ltd.), trade name "Central Coat" (manufactured by Central Glass Co., Ltd.), trade name "Zaffron" (manufactured by east Asia synthetic Co., Ltd.), trade name "Zeffle" (manufactured by Daikin Industries Co., Ltd.), trade name "MEGAFAC F-571" and "Fluonate" (manufactured by DIC Co., Ltd.), 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, a copolymer of a compound having a fluorinated alkyl group among crosslinkable functional group-containing compounds, a fluorine-containing organic compound obtained by copolymerizing a fluorine-containing compound with a crosslinkable functional group-containing compound, a fluorine-containing compound containing a crosslinkable functional group-containing compound, and the like. Examples of commercially available fluorine-based compounds having such a crosslinkable functional group include: trade names such as "MEGAFAC F-570", "MEGAFAC RS-55", "MEGAFAC RS-56", "MEGAFAC RS-72-K", "MEGAFAC RS-75", "MEGAFAC RS-76-E", "MEGAFAC RS-76-NS", "MEGAFAC RS-78", "MEGAFAC RS-90" (manufactured by DIC).

< other ingredients >

The adhesive composition may contain any suitable other components within a range not impairing the effects of the present invention. Examples of such other components include: other resin components, a tackifier, an inorganic filler, an organic filler, metal powder, a pigment, a foil, a softener, an antiaging agent, a conductive agent, an ultraviolet absorber, an antioxidant, a light stabilizer, a surface lubricant, a leveling agent, a resist, a heat stabilizer, a polymerization inhibitor, a lubricant, a solvent, a catalyst, and the like.

The adhesive composition may also comprise a fatty acid ester. The number of the fatty acid esters may be only 1, or may be 2 or more.

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

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

When the adhesive composition contains the 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, still 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, based on 100 parts by weight of the base polymer.

The adhesive composition may also contain an ionic liquid comprising a fluorinated organic anion. By making the adhesive composition contain an ionic liquid containing a fluorinated organic anion, an adhesive composition having very excellent antistatic properties can be provided. Such ionic liquids may be only 1 type, or may be 2 or more types.

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

As the ionic liquid, any appropriate ionic liquid may be used as long as it contains a fluorinated organic anion, and the effects of the present invention are not impaired. The ionic liquid is preferably a mixture of a fluorinated organic anion and

ionic liquid composed of cations. By using a fluorinated organic anion and

the ionic liquid composed of cations can provide a pressure-sensitive adhesive composition having extremely excellent antistatic properties.

As capable of constituting ionic liquids

The cation may be any suitable one within the range not impairing the effects of the present invention

A cation. As such

Cations, preferably selected from nitrogen

Cationic, sulfur-containing

Cationic, phosphorus-containing

At least one of cations. By selecting these

The cationic binder can provide a binder composition having extremely excellent antistatic properties.

As capable of constituting ionic liquids

The cation is preferably at least one selected from the group consisting of cations having structures represented by general formulae (1) to (5).

[ chemical formula 1]

In the general formula (1), Ra represents a hydrocarbon group having 4 to 20 carbon atoms and optionally includes a heteroatom, and Rb and Rc are the same or different and represent hydrogen or a hydrocarbon group having 1 to 16 carbon atoms and optionally includes a heteroatom. Wherein, in the case where the nitrogen atom contains a double bond, there is no Rc.

In the general formula (2), Rd represents a hydrocarbon group having 2 to 20 carbon atoms and optionally contains a heteroatom, and Re, Rf and Rg are the same or different and represent hydrogen or a hydrocarbon group having 1 to 16 carbon atoms and optionally contains a heteroatom.

In the general formula (3), Rh represents a hydrocarbon group having 2 to 20 carbon atoms and optionally contains a heteroatom, and Ri, Rj and Rk are the same or different and represent hydrogen or a hydrocarbon group having 1 to 16 carbon atoms and optionally contains a heteroatom.

In the general formula (4), Z represents a nitrogen atom, a sulfur atom or a phosphorus atom, and Rl, Rm, Rn and Ro are the same or different and represent a hydrocarbon group having 1 to 20 carbon atoms, and optionally contain a hetero atom. Wherein, when Z is a sulfur atom, Ro is absent.

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

Examples of the cation represented by the general formula (1) include: pyridine compound

Cation, pyrrolidine

Cation, piperidine

A cation, a cation having a pyrroline skeleton, a cation having an azole skeleton, and the like.

Specific examples of the cation represented by the general formula (1) include: 1-ethylpyridines

Cationic, 1-butylpyridines

Cationic, 1-hexylpyridines

Cationic, 1-ethyl-3-methylpyridine

Cationic, 1-butyl-3-methylpyridine

Cationic, 1-hexyl-3-methylpyridine

Cationic, 1-butyl-4-methylpyridine

Cationic, 1-octyl-4-methylpyridine

Cationic, 1-butyl-3, 4-dimethylpyridine

Cationic, 1-dimethylpyrrolidine

Pyridines such as cations

A cation; 1-ethyl-1-methylpyrrolidine

Cationic, 1-methyl-1-propylpyrrolidine

Cationic, 1-methyl-1-butylpyrrolidine

Cationic, 1-methyl-1-pentylpyrrolidines

Cationic, 1-methyl-1-hexylpyrrolidine

Cationic, 1-methyl-1-heptyl pyrrolidines

Cationic, 1-ethyl-1-propylpyrrolidine

Cationic, 1-ethyl-1-butylpyrrolidine

Cationic, 1-ethyl-1-pentylpyrrolidine

Cationic, 1-ethyl-1-hexylpyrrolidine

Cationic, 1-ethyl-1-heptyl pyrrolidines

Cationic, 1-dipropylpyrrolidine

Cationic, 1-propyl-1-butylpyrrolidine

Cationic, 1-dibutylpyrrolidine

Cationic and like pyrrolidines

A cation; 1-Propylpiperidine

Cationic, 1-pentylpiperidines

Cationic, 1-methyl-1-ethylpiperidine

Cationic, 1-methyl-1-propylpiperidines

Cationic, 1-methyl-1-butylpiperidine

Cationic, 1-methyl-1-pentylpiperidines

Cationic, 1-methyl-1-hexylpiperidine

Cationic, 1-methyl-1-heptylpiperidines

Cationic, 1-ethyl-1-propylpiperidines

Cationic, 1-ethyl-1-butylpiperidine

Cationic, 1-ethyl-1-pentylpiperidines

Cationic, 1-ethyl-1-hexylpiperidine

Cationic, 1-ethyl-1-heptylpiperidines

Cationic, 1-propyl-1-butylpiperidine

Cationic, 1-dimethylpiperidine

Cationic polymerZizi, 1-dipropylpiperidine

Cationic, 1-dibutylpiperidine

Cationic isopiperidine

A cation; 2-methyl-1-pyrroline cation; 1-ethyl-2-phenylindole cation; 1, 2-dimethylindole cation; 1-ethylcarbazole cation, and the like.

Among them, from the viewpoint of further exhibiting the effects of the present invention, preferred are: 1-ethylpyridines

Cationic, 1-butylpyridines

Cationic, 1-hexylpyridines

Cationic, 1-ethyl-3-methylpyridine

Cationic, 1-butyl-3-methylpyridine

Cationic, 1-hexyl-3-methylpyridine

Cationic, 1-butyl-4-methylpyridine

Cationic, 1-octyl-4-methylpyridine

Pyridines such as cations

A cation; 1-ethyl-1-methylpyrrolidine

Cationic, 1-methyl-1-propylpyrrolidine

Cationic, 1-methyl-1-butylpyrrolidine

Cationic, 1-methyl-1-pentylpyrrolidines

Cationic, 1-methyl-1-hexylpyrrolidine

Cationic, 1-methyl-1-heptyl pyrrolidines

Cationic, 1-ethyl-1-propylpyrrolidine

Cationic, 1-ethyl-1-butylpyrrolidine

Cationic, 1-ethyl-1-pentylpyrrolidines

Cationic, 1-ethyl-1-hexylpyrrolidine

Cationic, 1-ethyl-1-heptyl pyrrolidines

Cationic and like pyrrolidines

A cation; 1-methyl-1-ethylpiperidine

Cationic, 1-methyl-1-propylpiperidines

Cationic, 1-methyl-1-butylpiperidine

Cationic, 1-methyl-1-pentylpiperidines

Cationic, 1-methyl-1-hexylpiperidines

Cationic, 1-methyl-1-heptylpiperidines

Cationic, 1-ethyl-1-propylpiperidines

Cationic, 1-ethyl-1-butylpiperidine

Cationic, 1-ethyl-1-pentylpiperidines

Cationic, 1-ethyl-1-hexylpiperidine

Cationic, 1-ethyl-1-heptylpiperidines

Cationic, 1-propyl-1-butylpiperidine

Cationic isopiperidines

A cation; etc., more preferably 1-hexylpyridine

Cationic, 1-ethyl-3-methylpyridine

Cationic, 1-butyl-3-methylpyridine

Cationic, 1-octyl-4-methylpyridine

Cationic, 1-methyl-1-propylpyrrolidine

Cationic, 1-methyl-1-propylpiperidines

A cation.

Examples of the cation represented by the general formula (2) include: imidazole

Cationic, tetrahydropyrimidines

Cationic dihydropyrimidines

Cations, and the like.

Specific examples of the cation represented by the general formula (2) include: 1, 3-dimethylimidazole

Cation(s)1, 3-diethylimidazole

Cationic, 1-ethyl-3-methylimidazole

Cationic, 1-butyl-3-methylimidazole

Cationic, 1-hexyl-3-methylimidazole

Cationic, 1-octyl-3-methylimidazole

Cationic, 1-decyl-3-methylimidazole

Cationic, 1-dodecyl-3-methylimidazole

Cationic, 1-tetradecyl-3-methylimidazole

Cationic, 1, 2-dimethyl-3-propylimidazoles

Cationic, 1-ethyl-2, 3-dimethylimidazole

Cationic, 1-butyl-2, 3-dimethylimidazole

Cationic, 1-hexyl-2, 3-dimethylimidazole

Imidazole such as cation

A cation; 1, 3-dimethyl-1, 4,5, 6-tetrahydropyrimidine

Cationic, 1,2, 3-trimethyl-1, 4,5, 6-tetrahydropyrimidine

Cationic, 1,2,3, 4-tetramethyl-1, 4,5, 6-tetrahydropyrimidine

Cationic, 1,2,3, 5-tetramethyl-1, 4,5, 6-tetrahydropyrimidine

Cationic isotetrahydropyrimidines

A cation; 1, 3-dimethyl-1, 4-dihydropyrimidines

Cationic, 1, 3-dimethyl-1, 6-dihydropyrimidines

Cationic, 1,2, 3-trimethyl-1, 4-dihydropyrimidines

Cationic, 1,2, 3-trimethyl-1, 6-dihydropyrimidines

Cationic, 1,2,3, 4-tetramethyl-1, 4-dihydropyrimidines

Cationic, 1,2,3, 4-tetramethyl-1, 6-dihydropyrimidines

Cationic isodihydropyrimidines

A cation; and the like.

Among these, 1, 3-dimethylimidazole is preferable from the viewpoint of further exhibiting the effects of the present invention

Cationic, 1, 3-diethylimidazoles

Cationic, 1-ethyl-3-methylimidazole

Cationic, 1-butyl-3-methylimidazole

Cationic, 1-hexyl-3-methylimidazole

Cationic, 1-octyl-3-methylimidazole

Cationic, 1-decyl-3-methylimidazole

Cationic, 1-dodecyl-3-methylimidazole

Cationic, 1-tetradecyl-3-methylimidazole

Imidazole of cation etc

Cation, more preferably 1-ethyl-3-methylimidazole

Cationic, 1-hexyl-3-methylimidazole

A cation.

Examples of the cation represented by the general formula (3) include: pyrazoles

Cationic pyrazolines

Cations, and the like.

Specific examples of the cation represented by the general formula (3) include: 1-methylpyrazole

Cationic, 3-methylpyrazole

Cationic, 1-ethyl-2-methylpyrazoline

Cationic, 1-ethyl-2, 3, 5-trimethylpyrazoles

Cationic, 1-propyl-2, 3, 5-trimethylpyrazoles

Cationic, 1-butyl-2, 3, 5-trimethylpyrazoles

Cationic isopyrazoles

A cation; 1-ethyl-2, 3, 5-trimethylpyrazoline

Cationic, 1-propyl-2, 3, 5-trimethylpyrazoline

Cationic, 1-butyl-2, 3, 5-trimethylpyrazoline

Pyrazolines such as cations

A cation; and the like.

Examples of the cation represented by the general formula (4) include: tetraalkylammonium cations, trialkylsulfonium cations, tetraalkyl radicals

Cations obtained by substituting a part of the alkyl group with an alkenyl group, an alkoxy group, or an epoxy group, and the like.

Specific examples of the cation represented by the general formula (4) include: tetramethylammonium cation, tetraethylammonium cation, tetrabutylammonium cation, tetrapentylammonium cation, tetrahexylammonium cation, tetraheptylammonium cation, triethylmethylammonium cation, tributylethylammonium cation, trimethylpropylammonium cation, trimethyldecylammonium cation, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium cation, glycidyltrimethylammonium cation, trimethylsulfonium cation, triethylsulfonium cation, tributylsulfonium cation, trihexylsulfonium cation, diethylmethylsulfinium cation, dibutylethylsulfonium cation, dimethyldecylsulfonium cation, tetramethylammonium cation

Cationic, tetraethyl radical

Cationic, tetrabutyl

Cation(s)Tetra-hexyl

Cationic, tetraoctyl

Cation, triethyl methyl

Cationic, tributylethyl

Cationic, trimethyldecyl

Cations, diallyldimethylammonium cations, and the like.

Among them, from the viewpoint of further exhibiting the effects of the present invention, preferred are: triethylmethylammonium cation, tributylethylammonium cation, trimethyldecylammonium cation, diethylmethylsulfonium cation, dibutylethylsulfonium cation, dimethyldecylsulfonium cation, triethylmethyl

Cationic, tributylethyl

Cationic, trimethyldecyl

Cation-like asymmetric tetraalkylammonium cation, trialkylsulfonium cation, tetraalkyl

Cation, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium cation, glycidyltrimethylammonium cation, diallyldimethylammonium cation, N-dimethyl-N-ethyl-N-propylammonium cation, N-dimethyl-N-ethyl-N-butylammonium cation, N-A dimethyl-N-ethyl-N-pentylammonium cation, an N, N-dimethyl-N-ethyl-N-hexylammonium cation, an N, N-dimethyl-N-ethyl-N-heptylammonium cation, an N, N-dimethyl-N-ethyl-N-nonylammonium cation, an N, N-dimethyl-N, N-dipropylammonium cation, an N, N-diethyl-N-propyl-N-butylammonium cation, an N, N-dimethyl-N-propyl-N-pentylammonium cation, an N, N-dimethyl-N-propyl-N-hexylammonium cation, an N, N-dimethyl-N-propyl-N-heptylammonium cation, a N, N-dimethyl-N-propyl-N-hexylammonium cation, a N-heptylammonium cation, a N-hexylammonium cation, a, N, N-dimethyl-N-butyl-N-hexylammonium cation, N-diethyl-N-butyl-N-heptylammonium cation, N-dimethyl-N-pentyl-N-hexylammonium cation, N-dimethyl-N, N-dihexylammonium cation, trimethylheptylammonium cation, N-diethyl-N-methyl-N-propylammonium cation, N-diethyl-N-methyl-N-pentylammonium cation, N-diethyl-N-methyl-N-heptylammonium cation, N-diethyl-N-propyl-N-pentylammonium cation, N-diethyl-N-pentyl-ammonium cation, N-diethyl-N-pentyl-N-hexylammonium cation, N-diethyl-N-hexylammonium cation, N-diethyl-butyl-N-heptylammonium cation, N-pentyl-ammonium cation, N-pentyl-cation, N-pentyl-cation, N-pentyl-cation, N-pentyl-alkyl-ammonium cation, N, triethylpropylammonium cation, triethylpentylammonium cation, triethylheptylammonium cation, N-dipropyl-N-methyl-N-ethylammonium cation, N-dipropyl-N-methyl-N-pentylammonium cation, N-dipropyl-N-butyl-N-hexylammonium cation, N-dipropyl-N, N-dihexylammonium cation, N-dibutyl-N-methyl-N-pentylammonium cation, N-dibutyl-N-methyl-N-hexylammonium cation, trioctylmethylammonium cation, N-methyl-N-ethyl-N-propyl-N-pentylammonium cation, and the like, more preferably a trimethylpropylammonium cation.

As the fluorinated organic anion capable of constituting the ionic liquid, any suitable fluorinated organic anion may be used within a range not impairing the effects of the present invention. Such fluorinated organic anions may be fully fluorinated (perfluorinated) or partially fluorinated.

Examples of such fluorinated organic anions include: fluorinated arylsulfonates, perfluoroalkanesulfonates, bis (fluorosulfonyl) imides, bis (perfluoroalkanesulfonyl) imides, cyanoperfluoroalkanesulfonamides, bis (cyano) perfluoroalkanesulfonylmethides, cyanobis (perfluoroalkanesulfonyl) methides, tris (perfluoroalkanesulfonyl) methides, trifluoroacetates, perfluoroalkanes, tris (perfluoroalkanesulfonyl) methides, (perfluoroalkanesulfonyl) trifluoroacetates, and the like.

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

As a specific example of the ionic liquid, a combination of the above-mentioned cationic component and the above-mentioned anionic component can be appropriately selected. Specific examples of such ionic liquids include: 1-hexyl pyridine

Bis (fluorosulfonyl) imide, 1-ethyl-3-methylpyridine

Triflate, 1-ethyl-3-methylpyridine

Pentafluoroethanesulfonate, 1-ethyl-3-methylpyridine

Heptafluoropropanesulfonate salt, 1-ethyl-3-methylpyridine

Nonafluorobutanesulfonate, 1-butyl-3-methylpyridine

Triflate, 1-butyl-3-methylpyridine

Bis (trifluoromethanesulfonyl) imide, 1-butyl-3-methylpyridine

Bis (pentafluoroethanesulfonyl) imide, 1-octyl-4-methylpyridine

Bis (fluorosulfonyl) imide, 1-dimethylpyrrolidine

Bis (trifluoromethanesulfonyl) imide, 1-methyl-1-ethylpyrrolidine

Bis (trifluoromethanesulfonyl) imide, 1-methyl-1-propylpyrrolidine

Bis (trifluoromethanesulfonyl) imide, 1-methyl-1-propylpyrrolidine

Bis (fluorosulfonyl) imide, 1-methyl-1-butylpyrrolidine

Bis (trifluoromethanesulfonyl) imide, 1-methyl-1-pentylpyrrolidine

Bis (trifluoromethanesulfonyl) imide, 1-methyl-1-hexylpyrrolidine

Bis (trifluoromethanesulfonyl) imide, 1-methyl-1-heptylpyrrolidine

Bis (trifluoromethanesulfonyl) imide, 1-ethyl-1-propylpyrrolidine

Bis (trifluoromethanesulfonyl) imide, 1-ethyl-1-butylpyrrolidine

Bis (trifluoromethanesulfonyl) imide, 1-ethyl-1-pentylpyrrolidine

Bis (trifluoromethanesulfonyl) imide, 1-ethyl-1-hexylpyrrolidine

Bis (trifluoromethanesulfonyl) imide, 1-ethyl-1-heptylpyrrolidine

Bis (trifluoromethanesulfonyl) imide, 1-dipropylpyrrolidine

Bis (trifluoromethanesulfonyl) imide, 1-propyl-1-butylpyrrolidine

Bis (trifluoromethanesulfonyl) imide, 1-dibutylpyrrolidine

Bis (trifluoromethanesulfonyl) imide, 1-propylpiperidine

Bis (trifluoromethanesulfonyl) imide, 1-pentylpiperidine

Bis (trifluoromethanesulfonyl) imide, 1-dimethylpiperidine

Bis (trifluoromethanesulfonyl) imide, 1-methyl-1-ethylpiperidine

Bis (trifluoromethanesulfonyl) imide, 1-methyl-1-propylpiperidine

Bis (trifluoromethanesulfonyl) imide, 1-methyl-1-propylpiperidine

Bis (fluorosulfonic acid)Imide), 1-methyl-1-butylpiperidine

Bis (trifluoromethanesulfonyl) imide, 1-methyl-1-pentylpiperidine

Bis (trifluoromethanesulfonyl) imide, 1-methyl-1-hexylpiperidine

Bis (trifluoromethanesulfonyl) imide, 1-methyl-1-heptylpiperidine

Bis (trifluoromethanesulfonyl) imide, 1-ethyl-1-propylpiperidine

Bis (trifluoromethanesulfonyl) imide, 1-ethyl-1-butylpiperidine

Bis (trifluoromethanesulfonyl) imide, 1-ethyl-1-pentylpiperidine

Bis (trifluoromethanesulfonyl) imide, 1-ethyl-1-hexylpiperidine

Bis (trifluoromethanesulfonyl) imide, 1-ethyl-1-heptylpiperidine

Bis (trifluoromethanesulfonyl) imide, 1-dipropylpiperidine

Bis (trifluoromethanesulfonyl) imide, 1-propyl-1-butylpiperidine

Bis (trifluoromethanesulfonyl) imide, 1-dibutylpiperidine

Bis (trifluoromethanesulfonyl) imide, 1-dimethylpyrrolidine

Bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-ethylpyrrolidine

Bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-propylpyrrolidine

Bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-butylpyrrolidine

Bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-pentylpyrrolidine

Bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-hexylpyrrolidine

Bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-heptylpyrrolidine

Bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-propylpyrrolidine

Bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-butylpyrrolidine

Bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-pentylpyrrolidine

Bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-hexylpyrroleAlkane (I) and its preparation method

Bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-heptylpyrrolidine

Bis (pentafluoroethanesulfonyl) imide, 1-dipropylpyrrolidine

Bis (pentafluoroethanesulfonyl) imide, 1-propyl-1-butylpyrrolidine

Bis (pentafluoroethanesulfonyl) imide, 1-dibutylpyrrolidine

Bis (pentafluoroethanesulfonyl) imide, 1-propylpiperidine

Bis (pentafluoroethanesulfonyl) imide, 1-pentylpiperidine

Bis (pentafluoroethanesulfonyl) imide, 1-dimethylpiperidine

Bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-ethylpiperidine

Bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-propylpiperidine

Bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-butylpiperidine

Bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-pentylpiperidine

Bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-hexylpiperidine

Bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-heptylpiperidine

Bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-propylpiperidine

Bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-butylpiperidine

Bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-pentylpiperidine

Bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-hexylpiperidine

Bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-heptylpiperidine

Bis (pentafluoroethanesulfonyl) imide, 1-dipropylpiperidine

Bis (pentafluoroethanesulfonyl) imide, 1-propyl-1-butylpiperidine

Bis (pentafluoroethanesulfonyl) imide, 1-dibutylpiperidine

Bis (pentafluoroethanesulfonyl) imide, 1-ethyl-3-methylimidazole

Trifluoroacetate salt, 1-ethyl-3-methylimidazole

Heptafluorobutanoate, 1-ethyl-3-methylimidazole

Triflate, 1-ethyl-3-methylimidazole

Heptafluoropropanesulfonate, 1-ethyl-3-methylimidazole

Nonafluorobutanesulfonate, 1-ethyl-3-methylimidazole

Bis (trifluoromethanesulfonyl) imide, 1-ethyl-3-methylimidazole

Bis (fluorosulfonyl) imide, 1-ethyl-3-methylimidazole

Bis (pentafluoroethanesulfonyl) imide, 1-ethyl-3-methylimidazole

Tris (trifluoromethanesulfonyl) methide, 1-butyl-3-methylimidazole

Trifluoroacetate salt, 1-butyl-3-methylimidazole

Heptafluorobutyric acid salt, 1-butyl-3-methylimidazole

Triflate, 1-butyl-3-methylImidazole base

Perfluorobutanesulfonate, 1-butyl-3-methylimidazole

Bis (trifluoromethanesulfonyl) imide, 1-hexyl-3-methylimidazole

Triflate, 1-hexyl-3-methylimidazole

Bis (fluorosulfonyl) imide, 1, 2-dimethyl-3-propylimidazole

Bis (trifluoromethanesulfonyl) imide, 1-ethyl-2, 3, 5-trimethylpyrazole

Bis (trifluoromethanesulfonyl) imide, 1-propyl-2, 3, 5-trimethylpyrazole

Bis (trifluoromethanesulfonyl) imide, 1-butyl-2, 3, 5-trimethylpyrazole

Bis (trifluoromethanesulfonyl) imide, 1-ethyl-2, 3, 5-trimethylpyrazole

Bis (pentafluoroethanesulfonyl) imide, 1-propyl-2, 3, 5-trimethylpyrazole

Bis (pentafluoroethanesulfonyl) imide, 1-butyl-2, 3, 5-trimethylpyrazole

Bis (pentafluoroethanesulfonyl) imide, 1-ethyl-2, 3,5-Trimethylpyrazole

(Trifluoromethanesulfonyl) trifluoroacetamide, 1-propyl-2, 3, 5-trimethylpyrazole

(Trifluoromethanesulfonyl) trifluoroacetamide, 1-butyl-2, 3, 5-trimethylpyrazole

(trifluoromethanesulfonyl) trifluoroacetamide, trimethylpropylammonium bis (trifluoromethanesulfonyl) imide, N-dimethyl-N-ethyl-N-propylammonium bis (trifluoromethanesulfonyl) imide, N-dimethyl-N-ethyl-N-butylammonium bis (trifluoromethanesulfonyl) imide, N-dimethyl-N-ethyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, N-dimethyl-N-ethyl-N-hexylammonium bis (trifluoromethanesulfonyl) imide, N-dimethyl-N-ethyl-N-heptylammonium bis (trifluoromethanesulfonyl) imide, N-dimethyl-N-ethyl-N-nonylammonium bis (trifluoromethanesulfonyl) imide, N-dimethyl-N-ethyl-nonylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N, N-dipropylammonium bis (trifluoromethanesulfonyl) imide, N-dimethyl-N-propyl-N-butylammonium bis (trifluoromethanesulfonyl) imide, N-dimethyl-N-propyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, N-dimethyl-N-propyl-N-hexylammonium bis (trifluoromethanesulfonyl) imide, N-dimethyl-N-propyl-N-heptylammonium bis (trifluoromethanesulfonyl) imide, N-dimethyl-N-butyl-N-hexylammonium bis (trifluoromethanesulfonyl) imide, N-dimethyl-N-butyl-N-heptylammonium bis (trifluoromethanesulfonyl) imide, N-dimethyl-N-N-heptylammonium bis (trifluoromethanesulfonyl) imide, N-propyl-N-hexylammonium bis (trifluoromethanesulfonyl) imide, N-propyl-N-hexylammonium bis (trifluoromethanesulfonyl) imide, N-hexylammonium, N-amide, N-dimethyl-N-propyl-N-hexylammonium bis (trifluoromethanesulfonyl) imide, N-propyl-N-hexylammonium bis (trifluoromethanesulfonyl) imide, N-methyl-N-butyl-N-hexylammonium bis (trifluoromethanesulfonyl-N-yl-N-m-N-m-N-m-N-m-N-m-N-m, N, N-dimethyl-N-pentyl-N-hexylammonium bis (trifluoromethanesulfonyl) imide, N-dimethyl-N, N-dihexylammonium bis (trifluoromethanesulfonyl) imide, trimethylheptylammonium bis (trifluoromethanesulfonyl) imide, N-diethyl-N-methyl-N-propylammonium bis (trifluoromethanesulfonyl) imide, N-diethyl-N-methyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, N-diethyl-N-methyl-N, N-heptylammonium bis (trifluoromethanesulfonyl) imide, N-diethyl-N-propyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, triethylpropylammonium bis (trifluoromethanesulfonyl) imide, Triethylpentylammonium bis (trifluoromethanesulfonyl) imide, triethylheptylammonium bis (trifluoromethanesulfonyl) imide, N-dipropyl-N-methyl-N-ethylammonium bis (trifluoromethanesulfonyl) imideSulfonyl) imide, N-dipropyl-N-methyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, N-dipropyl-N-butyl-N-hexylammonium bis (trifluoromethanesulfonyl) imide, N-dipropyl-N, N-dihexylammonium bis (trifluoromethanesulfonyl) imide, N-dibutyl-N-methyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, N-dibutyl-N-methyl-N-hexylammonium bis (trifluoromethanesulfonyl) imide, trioctylmethylammonium bis (trifluoromethanesulfonyl) imide, N-methyl-N-ethyl-N-propyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, N-dipropyl-N-methyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, N-dipropyl-N-hexylammonium bis (trifluoromethanesulfonyl) imide, N-dihexylammonium bis (trifluoromethanesulfonyl) imide, 1-butylpyridines

(Trifluoromethanesulfonyl) trifluoroacetamide, 1-butyl-3-methylpyridine

(Trifluoromethanesulfonyl) trifluoroacetamide, 1-ethyl-3-methylimidazole

(trifluoromethanesulfonyl) trifluoroacetamide, tetrahexylammonium bis (trifluoromethanesulfonyl) imide, diallyldimethylammonium trifluoromethanesulfonate, diallyldimethylammonium bis (trifluoromethanesulfonyl) imide, diallyldimethylammonium bis (pentafluoroethanesulfonyl) imide, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium trifluoromethanesulfonate, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium bis (trifluoromethanesulfonyl) imide, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium bis (pentafluoroethanesulfonyl) imide, glycidyltrimethylammonium trifluoromethanesulfonate, glycidyltrimethylammonium bis (trifluoromethanesulfonyl) imide, ammonium sulfate, and ammonium sulfate, and ammonium sulfate, Glycidyl trimethyl ammonium bis (pentafluoroethanesulfonyl) imide, diallyl dimethyl ammonium bis (trifluoromethanesulfonyl) imide, diallyl dimethyl bis (pentafluoroethanesulfonyl) imide, lithium bis (trifluoromethanesulfonyl) imide, lithium bis (fluorosulfonyl) imide, and the like.

Of these ionic liquids, 1-hexylpyridine is more preferable

Bis (fluorosulfonyl) imide, 1-ethyl-3-methylpyridine

Triflate, 1-ethyl-3-methylpyridine

Pentafluoroethanesulfonate, 1-ethyl-3-methylpyridine

Heptafluoropropanesulfonate salt, 1-ethyl-3-methylpyridine

Nonafluorobutanesulfonate, 1-butyl-3-methylpyridine

Triflate, 1-butyl-3-methylpyridine

Bis (trifluoromethanesulfonyl) imide, 1-octyl-4-methylpyridine

Bis (fluorosulfonyl) imide, 1-methyl-1-propylpyrrolidine

Bis (trifluoromethanesulfonyl) imide, 1-methyl-1-propylpyrrolidine

Bis (fluorosulfonyl) imide, 1-methyl-1-propylpiperidine

Bis (trifluoromethanesulfonyl) imide, 1-methyl-1-propylpiperidine

Bis (fluorosulfonyl) imide, 1-ethyl-3-methylimidazole

Triflate, 1-ethyl-3-methylimidazole

Heptafluoropropanesulfonate, 1-ethyl-3-methylimidazole

Bis (trifluoromethanesulfonyl) imide, 1-ethyl-3-methylimidazole

Bis (fluorosulfonyl) imide, 1-hexyl-3-methylimidazole

Bis (fluorosulfonyl) imide, trimethylpropylammonium bis (trifluoromethanesulfonyl) imide, lithium bis (fluorosulfonyl) imide.

The ionic liquid may be commercially available, or may be synthesized in the following manner. As a method for synthesizing an ionic liquid, there is no particular limitation as long as a target ionic liquid can be obtained, and generally, there can be used a halide method, a hydroxide method, an acid ester method, a complex formation method, an intermediate and other methods described in the literature "ionic liquid-the most advanced and future" (published by CMC corporation) (the "イオン liquid-the most advanced and open development" the と future "(published by the laid シーエムシー)).

Hereinafter, the halide method, the hydroxide method, the acid ester method, the complex formation method and the neutralization method are described by using nitrogen

Salts are exemplified for their synthesis, others containing sulfur

Salts, containing phosphorus

Other ionic liquids such as salts can also be obtained by the same method.

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

The obtained halide is reacted with an anion having the target ionic liquid (A)^-) The acid (HA) or salt (MA, M is cation of salt formed by ammonium, lithium, sodium, potassium and the like and target anion) to obtain target ionic liquid (R)₄NA)。

[ chemical formula 2]

(1)R₃N+RX→R₄NX(X：Cl，Br，I)

(2)R₄NX+HA→R₄NA+HX

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

The hydroxide method is a method performed by reactions represented by the reaction formulas (4) to (8). First, electrolysis (reaction formula (4)), an OH-type ion exchange resin method (reaction formula (5)), or silver oxide (Ag) is performed by an ion exchange membrane method₂O) (reaction formula (6)), from a halide (R)₄NX) to give the hydroxide (R)₄NOH) (as halogen, chlorine, bromine, iodine were used).

The obtained hydroxide was subjected to reactions using reaction formulas (7) to (8) in the same manner as in the halogenation method described above to obtain the target ionic liquid (R)₄NA)。

[ chemical formula 3]

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

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

(6)R₄NX+1/2Ag₂O+1/2H₂O→R₄NOH+AgX

(7)R₄NOH+HA→R₄NA+H₂O

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

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

The obtained acid ester compound was subjected to the reactions of the reaction formulae (10) to (11) in the same manner as in the halogenation method described above to obtain the target ionic liquid (R)₄NA). In addition, an ionic liquid can also be obtained directly by using methyl trifluoromethanesulfonate, methyl trifluoroacetate, or the like as an acid ester.

[ chemical formula 4]

(9)R₃N+ROY→R₄NOY

(OY：

Etc.)

(10)R₄NOY+HA→R₄NA+HOY

(OY：

In the case of (1), R₄N

)

(11)R₄NOY+MA→R₄NA+MOY(M：NH₄Li, Na, K, Ag, etc.)

The neutralization method is a method performed by a reaction represented by the reaction formula (12). By reacting tertiary amines with CF₃COOH、CF₃SO₃H、(CF₃SO₂)₂NH、(CF₃SO₂)₃CH、(C₂F₅SO₂)₂NH, etc.

[ chemical formula 5]

(12)R₃N+HZ→R₃HN+Z^-

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

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

The amount of the ionic liquid to be blended varies depending on the compatibility between the polymer to be used and the ionic liquid, and therefore, in general, is preferably 0.001 to 50 parts by weight, more preferably 0.01 to 40 parts by weight, further preferably 0.01 to 30 parts by weight, particularly preferably 0.01 to 20 parts by weight, and most preferably 0.01 to 10 parts by weight, based on 100 parts by weight of the base polymer. By adjusting the amount of the ionic liquid to be blended within the above range, a pressure-sensitive adhesive composition having very excellent antistatic properties can be provided. When 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 added exceeds 50 parts by weight, contamination of the adherend tends to increase.

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

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

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

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

Examples of the polyether-modified silicone oil include: side chain type polyether-modified silicone oil, both terminal type polyether-modified silicone oil, and the like. Among these, from the viewpoint of sufficiently effectively exhibiting the antistatic property, both-terminal type polyether-modified silicone oils are preferable.

< < < use > >)

The surface protective film of the present invention has ultra-light peelability and is low in staining property on the surface of an adherend. Therefore, the resin composition can be preferably used for surface protection of optical members and electronic members. The surface protective film of the present invention is attached to the optical member of the present invention. The electronic component of the present invention is bonded with the surface protective film of the present invention.

Examples

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

< peeling speed 6000 mm/time-division peeling force (peeling force after 23 ℃ C.. times.30 minutes and peeling force after 80 ℃ C.. times.7 days) for PET >

A polyethylene terephthalate film having a thickness of 25 μm was bonded to the pressure-sensitive adhesive layer, and the polyethylene terephthalate film was peeled off at 23 ℃ at a peel angle of 180 degrees and at a peel speed of 6000 mm/min, and the peel force at the time of peeling was measured in the following manner.

The SUS304 plate was adhered to the entire surface of the surface protective film (50 mm in width. times.140 mm in length) from which the separator was peeled, on the side opposite to the pressure-sensitive adhesive layer, with a double-sided tape (product name "No. 531" manufactured by Nindon electric Co., Ltd.) by using a 2kg hand roll.

Next, a polyethylene terephthalate film (trade name "Lumiror S-10" manufactured by Toray corporation, thickness: 25 μm, width: 25mm) (temperature: 23 ℃, humidity: 65%, 2kg roller was reciprocated 1 time) was bonded to the surface of the pressure-sensitive adhesive layer.

The evaluation sample obtained as described above was measured by a tensile test. As the tensile testing machine, a product name "Autograph AG-Xplus HS6000 mm/min high speed model (AG-50NX plus)" manufactured by Shimadzu corporation was used. After the test piece for evaluation was set in a tensile testing machine, the test piece was left at an ambient temperature of 23 ℃ for 30 minutes or at a temperature of 80 ℃ for 7 days, and then the tensile test was started. The conditions for the tensile test were set as peel angle: 180 degrees, peeling speed (stretching 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 taken as the peeling force of the surface protective film.

< peeling speed 300 mm/time peeling force (peeling force after 23 ℃ C.. times.30 minutes and peeling force after 80 ℃ C.. times.7 days) for PET >

A polyethylene terephthalate film having a thickness of 25 μm was bonded to the pressure-sensitive adhesive layer, and the polyethylene terephthalate film was peeled off at 23 ℃ at a peeling angle of 180 degrees and a peeling speed of 300 mm/min, and the peeling force at the time of peeling was measured in the following manner.

The SUS304 plate was adhered to the entire surface of the surface protective film (width 50 mm. times. length 140mm) from which the separator was peeled, on the side opposite to the pressure-sensitive adhesive layer, with a double-sided adhesive tape (product name "No. 531" manufactured by Nindon electric Co., Ltd.) by using a 2kg hand roll.

The evaluation sample obtained as described above was subjected to a tensile test. As the tensile testing machine, a product name "Autograph AG-Xplus HS6000 mm/min high speed model (AG-50NX plus)" manufactured by Shimadzu corporation was used. The test piece for evaluation was set in a tensile tester, and then left at an ambient temperature of 23 ℃ for 30 minutes or at a temperature of 80 ℃ for 7 days, after which the tensile test was started. The conditions for the tensile test were set as peel angle: 180 degrees, peeling speed (stretching 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 taken as the peeling force of the surface protective film.

< residual adhesion ratio >

A surface protective film was bonded to the entire surface of a glass plate (1.35 mm. times.10 cm, manufactured by Sonlang Nitri K.K.) using a hand-press roller, the glass plate was stored at 23 ℃ and 55% RH for 24 hours, then the surface protective film was peeled off at a speed of 0.3 m/min, and a 2.0kg roller was reciprocated 1 time at 23 ℃ and 55% RH to attach a No.31B tape (manufactured by Ninto Denko K.K., substrate thickness: 25 μm) cut into a length of 150mm and a width of 19 mm. The sheet was aged at 23 ℃ and 55% RH for 30 minutes, and then peeled off at a peeling angle of 180 ℃ and a drawing speed of 300 mm/min using a tensile tester (trade name "Autograph AG-Xplus HS6000 mm/min high speed model (AG-50NX plus) manufactured by Shimadzu corporation), and the adhesive force was measured.

The adhesive force of No.31B tape having a width of 19mm was measured in the same manner for a glass plate which had not been subjected to the above-mentioned treatment, and the residual adhesion rate was calculated from the following equation.

Residual adhesion ratio (%) × 100 (adhesive force of No.31B to glass plate after peeling of surface protective film/adhesive force of No.31B to glass plate) × 100

The residual adhesion rate is an index of how much the adhesive component of the surface protective film transfers to the adherend and contaminates the surface. It is considered that the higher the value of the residual adhesion ratio, the more favorable the surface protective film which does not contaminate the adherend, and the lower the value of the residual adhesion ratio, the more contaminated the surface of the adherend is with the adhesive component or the like.

< peeling speed 6000 mm/min peeling force (peeling force after 23 ℃ C.. times.30 minutes and peeling force after 80 ℃ C.. times.7 days) for glass

A surface protective film (25 mm in width. times.140 mm in length) from which a separator was peeled was attached to glass (soda-lime glass, manufactured by Sonlang Nitri industries, Ltd.) by reciprocating a 2kg hand roller once.

The evaluation sample obtained as described above was measured by a tensile tester. As the tensile testing machine, a product name "Autograph AG-Xplus HS6000 mm/min high speed model (AG-50NX plus)" manufactured by Shimadzu corporation was used. After the test piece for evaluation was set in a tensile testing machine, the test piece was left at an ambient temperature of 23 ℃ for 30 minutes or at a temperature of 80 ℃ for 7 days, and then the tensile test was started. The conditions for the tensile test were set as peel angle: 180 degrees, peeling speed (stretching speed): 6000 mm/min. The load at the time of peeling the surface protective film from the glass was measured, and the average load at this time was taken as the peeling force of the surface protective film.

< peeling speed 300 mm/min peeling force (peeling force after 23 ℃ C.. times.30 minutes and peeling force after 80 ℃ C.. times.7 days) for glass >

The evaluation sample obtained as described above was measured with a tensile tester. As the tensile testing machine, a product name "Autograph AG-Xplus HS6000 mm/min high speed model (AG-50NX plus)" manufactured by Shimadzu corporation was used. After the test piece for evaluation was set in a tensile testing machine, the test piece was left at an ambient temperature of 23 ℃ for 30 minutes or at a temperature of 80 ℃ for 7 days, and then the tensile test was started. The conditions for the tensile test were set as peel angle: 180 degrees, peeling speed (stretching speed): 300 mm/min. The load at the time of peeling the surface protective film from the glass was measured, and the average load at this time was taken as the peeling force of the surface protective film.

[ example 1]

Polyol PREMINOL S3011 (manufactured by Asahi glass company, Ltd., Mn: 10000) having 3 OH groups, polyol SANNIX GP-3000 (manufactured by Sanyo chemical Co., Ltd., Mn: 3000) having 3 OH groups, and polyol SA having 3 OH groups were added as polyol (A)NNIX GP-1000 (manufactured by Sanyo chemical Co., Ltd., Mn 1000)2 parts by weight, a polyfunctional alicyclic isocyanate compound Coronate HX (manufactured by Nippon Polyurethane Industry Co., Ltd.) 18 parts by weight as the polyfunctional isocyanate compound (B), a catalyst (manufactured by Nippon chemical Industry Co., Ltd., trade name: Nacem Ferric Iron)0.1 part by weight, isopropyl myristate (manufactured by Kao corporation, trade name: EXCEPARL IPM, Mn 270)20 parts by weight as the fatty acid ester, 1-ethyl-3-methylimidazole

1.5 parts by weight of bis (fluoromethanesulfonyl) imide (trade name: AS110, manufactured by first Industrial pharmaceutical Co., Ltd.), 0.02 part by weight of both-terminal polyether-modified silicone oil (trade name: KF-6004, manufactured by shin-Etsu chemical Co., Ltd.), 0.25 part by weight of a polymer having siloxane bonds (trade name: LE-302, manufactured by Kyoho chemical Co., Ltd.), and ethyl acetate AS a diluting solvent were mixed and stirred to prepare a pressure-sensitive adhesive composition (1).

The obtained adhesive composition (1) was applied to a substrate "lumiror S10" (thickness 38 μm, manufactured by Toray corporation) made of a polyester resin by using a dipping roll (fountain roll) so that the thickness after drying was 10 μm, and cured (cure) and dried under the conditions of a drying temperature of 130 ℃ and a drying time of 30 seconds. Thereby, an adhesive layer was produced on the substrate. Next, the silicone-treated surface of the base material (separator) having a thickness of 25 μm, one surface of which was silicone-treated, was bonded to the surface of the pressure-sensitive adhesive layer, thereby obtaining a surface protective film (1) with a separator.

The results are shown in Table 1.

[ example 2]

Without using 1-ethyl-3-methylimidazole

Bis (fluoromethanesulfonyl) imide (trade name: AS110, manufactured by first Industrial pharmaceutical Co., Ltd.) and 0.50 part by weight of a fluoropolymer (trade name: F-571, manufactured by DIC) were used in place of the siloxane bond-containing polymer (Kyowa Kagaku K.K.)Manufactured by Kagaku corporation, trade name: LE-302) was carried out in the same manner as in example 1 except that the amount of the adhesive composition (2) was changed to 0.25 parts by weight, to obtain a surface protective film (2) with a separator.

The results are shown in Table 1.

[ example 3]

An adhesive composition (3) was produced in the same manner as in example 2 except that the amount of the fluoropolymer (product name: F-571, manufactured by DIC) used was changed to 1.00 part by weight, to obtain a surface protective film (3) with a separator.

The results are shown in Table 1.

[ example 4]

An adhesive composition (4) was produced in the same manner as in example 1 except that 0.30 parts by weight of a fluoropolymer (trade name: F-571, manufactured by DIC) was further used in the production of the adhesive composition, to obtain a surface protective film (4) with a separator.

The results are shown in Table 1.

[ example 5]

An adhesive composition (5) was prepared in the same manner as in example 1 except that 0.30 parts by weight of a fluoropolymer (trade name: F-571, manufactured by DIC) was used in place of 0.25 parts by weight of a polymer having a siloxane bond (trade name: LE-302, manufactured by Kyoritsu chemical Co., Ltd.), and a surface protective film (5) with a separator was obtained.

The results are shown in Table 1.

[ example 6]

An adhesive composition (6) was prepared by adding 100 parts by weight of polyol SANNIX GP-3000 (Mn. about.3000, manufactured by Sanyo chemical Co., Ltd.) having 3 OH groups as polyol (A), 18 parts by weight of polyfunctional alicyclic isocyanate compound Coronate HX (manufactured by Nippon Polyurethane Industry Co., Ltd.) as polyfunctional isocyanate compound (B), 0.1 part by weight of catalyst (manufactured by Nippon chemical Industry Co., Ltd., trade name: Nacem Ferric Iron), 0.25 part by weight of hydroxyl-containing silicone (manufactured by shin-Etsu chemical Industry Co., Ltd., trade name: X-22-4015) and ethyl acetate as a diluting solvent to the above-mentioned components and mixing them.

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

The results are shown in Table 1.

Comparative example 1

Polyol PREMINOL S3011 (manufactured by asahi glass co., ltd., Mn: 10000) having 3 OH groups as polyol (a), polyol sannari GP-3000 (manufactured by sanyo chemical co., ltd., Mn: 3000) having 3 OH groups as polyol (a), polyol sannari GP-1000 (manufactured by sannari chemical co., ltd., Mn: 1000) having 3 OH groups as polyol (B), polyfunctional alicyclic isocyanate compound Coronate HX (manufactured by Nippon Polyurethane Industry) 18 parts by weight as polyfunctional isocyanate compound (B), catalyst (manufactured by japan chemical co., ltd., trade name: Nacem ferro Iron)0.1 part by weight as catalyst, and ethyl acetate as a diluting solvent were added and mixed and stirred to produce adhesive composition (C1).

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

The results are shown in Table 1.

Comparative example 2

An adhesive composition (C2) was prepared in the same manner as in comparative example 1 except that 0.02 part by weight of a both-terminal polyether-modified silicone oil (trade name: KF-6004, manufactured by shin-Etsu chemical Co., Ltd.) was further used in the preparation of the adhesive composition, and a surface protective film with a separator (C2) was obtained.

The results are shown in Table 1.

Comparative example 3

100 parts by weight of polyol SANNIX GP-3000 (Mn. about.3000, manufactured by Sanyo chemical Co., Ltd.) having 3 OH groups as polyol (A), 18 parts by weight of polyfunctional alicyclic isocyanate compound Coronate HX (manufactured by Nippon Polyurethane Industry Co., Ltd.) as polyfunctional isocyanate compound (B), 0.1 part by weight of catalyst (manufactured by Nippon chemical Industry Co., Ltd., trade name: Nacem ferromagnetic Iron) and ethyl acetate as a diluting solvent were added to the mixture and mixed, thereby producing adhesive composition (C3).

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

The results are shown in Table 1.

Comparative example 4

Without using 1-ethyl-3-methylimidazole

An adhesive composition (C4) was prepared in the same manner AS in example 1 except that bis (fluoromethanesulfonyl) imide (trade name: AS110, manufactured by Kasei corporation) and a siloxane bond-containing polymer (trade name: LE-302, manufactured by Kyoeisha chemical Co., Ltd.) were used, to obtain a surface protective film with a separator (C4).

The results are shown in Table 1.

Comparative example 5

An adhesive composition (C5) was produced in the same manner as in example 1 except that the amount of isopropyl myristate (trade name: EXCEPARL IPM, Mn: 270, manufactured by kao corporation) was changed to 30 parts by weight and the amount of both-end polyether-modified silicone oil (trade name: KF-6004, manufactured by shin-Etsu chemical Co., Ltd.) was changed to 0.01 part by weight without using a siloxane bond-containing polymer, to obtain a surface protective film with a separator (C5).

The results are shown in Table 1.

Comparative example 6

An adhesive composition (C6) was produced in the same manner as in comparative example 1 except that 25 parts by weight of isopropyl myristate (trade name: EXCEPARL IPM, Mn: 270, manufactured by kao corporation) was further used in the production of the adhesive composition, and a surface protective film with a separator (C6) was obtained.

The results are shown in Table 1.

Comparative example 7

An adhesive composition (C7) was produced in the same manner as in comparative example 5 except that 0.15 part by weight of a silicone release agent (trade name: KS-776A, manufactured by shin-Etsu chemical Co., Ltd.) was used in place of 0.01 part by weight of a both-end type polyether modified silicone oil (trade name: KF-6004, manufactured by shin-Etsu chemical Co., Ltd.), and a surface protective film (C7) with a separator was obtained.

The results are shown in Table 1.

[ example 7]

An adhesive composition (7) was prepared by mixing 100 parts by weight of "CYABINE SH-109" (54% solid content, fatty acid ester-containing product, manufactured by Toyo Ink Co.), 7.05 parts by weight of a polyfunctional alicyclic isocyanate compound Coronate HX (manufactured by Nippon Polyurethane Industry Co.), 1.00 part by weight of a fluorine-containing polymer (manufactured by DIC Co., Ltd., trade name: F-571), and 208 parts by weight of toluene as a diluting solvent with stirring using a disperser as a urethane prepolymer (C).

The obtained adhesive composition (7) was applied to a substrate "lumiror S10" (thickness 38 μm, manufactured by Toray corporation) made of a polyester resin by using a dip roll so as to be cured and dried at a drying temperature of 130 ℃ for a drying time of 30 seconds, with the dried thickness being 10 μm. Thereby, an adhesive layer was produced on the substrate. Next, a silicone-treated surface of a 25 μm thick polyester resin substrate (separator) having one surface subjected to silicone treatment was bonded to the surface of the pressure-sensitive adhesive layer, thereby obtaining a surface protective film (7) with a separator.

The results are shown in Table 2.

[ example 8]

An adhesive composition (8) was prepared in the same manner as in example 7 except that the amount of the fluoropolymer (trade name: F-571, manufactured by DIC) used was changed to 2.00 parts by weight, to obtain a surface protective film (8) with a separator.

The results are shown in Table 2.

[ example 9]

An adhesive composition (9) was prepared in the same manner as in example 7 except that the amount of the fluoropolymer (trade name: F-571, manufactured by DIC) used was changed to 3.00 parts by weight, to obtain a surface protective film (9) with a separator.

The results are shown in Table 2.

[ Table 2]

[ example 10]

An adhesive composition (10) was prepared by mixing 100 parts by weight of "CYABINE SH-109" (54% solid content, fatty acid ester-containing product, manufactured by Toyo Ink Co.), 3.6 parts by weight of a polyfunctional alicyclic isocyanate compound Coronate HX (manufactured by Nippon Polyurethane Industry Co.), 1.00 part by weight of a fluorine-containing polymer (manufactured by DIC Co., Ltd., trade name: F-571), and 208 parts by weight of toluene as a diluting solvent with stirring using a disperser as a urethane prepolymer (C).

The obtained adhesive composition (10) was applied to a substrate "lumiror S10" (thickness 38 μm, manufactured by Toray corporation) made of a polyester resin by using a dip roll so as to be cured and dried at a drying temperature of 130 ℃ for a drying time of 30 seconds, with the dried thickness being 50 μm. Thereby, an adhesive layer was produced on the substrate. Subsequently, the silicone-treated surface of the base material (separator) having a thickness of 25 μm, one surface of which was silicone-treated, was bonded to the surface of the pressure-sensitive adhesive layer, thereby obtaining a surface protective film (10) with a separator.

The results are shown in tables 3 and 4.

[ example 11]

An adhesive composition (11) was produced in the same manner as in example 10 except that the amount of the fluoropolymer (trade name: F-571, manufactured by DIC) used was changed to 3.00 parts by weight, to obtain a surface protective film (11) with a separator.

The results are shown in tables 3 and 4.

[ example 12]

An adhesive composition (12) was produced in the same manner as in example 10 except that the amount of the fluoropolymer (trade name: F-571, manufactured by DIC) used was changed to 5.00 parts by weight, to obtain a surface protective film (12) with a separator.

The results are shown in tables 3 and 4.

Comparative example 8

An adhesive composition (C8) was prepared in the same manner as in example 10 except that a fluoropolymer (trade name: F-571, manufactured by DIC) was not used, and a surface protective film with a separator (C8) was obtained.

The results are shown in tables 3 and 4.

Comparative example 9

An adhesive composition (C9) was prepared in the same manner as in example 10 except that the amount of Coronate HX (manufactured by Nippon Polyurethane Industry Co.) was changed to 7.05 parts by weight and a fluoropolymer (manufactured by DIC Co., Ltd., trade name: F-571) was not used, to obtain a surface protective film (C9) with a separator.

The results are shown in tables 3 and 4.

[ example 13]

An adhesive composition (13) was prepared by mixing 100 parts by weight of "CYABINE SH-109" (54% solid content, fatty acid ester-containing product, manufactured by Toyo Ink Co.), 7.05 parts by weight of a polyfunctional alicyclic isocyanate compound Coronate HX (manufactured by Nippon Polyurethane Industry Co.), 1.00 part by weight of a fluorine-containing polymer (manufactured by DIC Co., Ltd., trade name: F-571), and 208 parts by weight of toluene as a diluting solvent into a urethane prepolymer (C), and stirring them with a disperser.

The obtained adhesive composition (13) was applied to a substrate "lumiror S10" (thickness 38 μm, manufactured by Toray corporation) made of a polyester resin by using a dip roll so as to be cured and dried at a drying temperature of 130 ℃ for a drying time of 30 seconds, with the dried thickness being 50 μm. Thus, an adhesive layer was produced on the substrate. Then, the silicone-treated surface of a 25 μm thick polyester resin base material (separator) having one surface subjected to silicone treatment was bonded to the surface of the adhesive layer, thereby obtaining a surface protective film (13) with a separator.

The results are shown in tables 3 and 4.

[ example 14]

An adhesive composition (14) was prepared in the same manner as in example 13 except that the amount of the fluoropolymer (trade name: F-571, manufactured by DIC) used was changed to 3.00 parts by weight, to obtain a surface protective film (14) with a separator.

The results are shown in tables 3 and 4.

[ example 15]

An adhesive composition (15) was prepared in the same manner as in example 13 except that the amount of the fluoropolymer (trade name: F-571, manufactured by DIC) used was changed to 5.00 parts by weight, to obtain a surface protective film (15) with a separator.

The results are shown in tables 3 and 4.

Comparative example 10

An adhesive composition (C10) was prepared in the same manner as in example 13 except that 1 part by weight of a silicone release agent (KS-776A, trade name, manufactured by shin-Etsu chemical Co., Ltd.) was used in place of the fluoropolymer (F-571, manufactured by DIC) to obtain a surface protective film (C10) with a separator.

The results are shown in tables 3 and 4.

Comparative example 11

An adhesive composition (C11) was prepared in the same manner as in example 13 except that 3 parts by weight of a silicone release agent (KS-776A, trade name, manufactured by shin-Etsu chemical Co., Ltd.) was used in place of the fluoropolymer (F-571, manufactured by DIC) to obtain a surface protective film (C11) with a separator.

The results are shown in tables 3 and 4.

Comparative example 12

An adhesive composition (C12) was prepared in the same manner as in example 13 except that the amount of Coronate HX (manufactured by Nippon Polyurethane Industry Co.) was changed to 17.7 parts by weight, a fluoropolymer (manufactured by DIC Co., Ltd., trade name: F-571) was not used, and the thickness of the adhesive layer was changed to 10 μm, thereby obtaining a surface protective film (C12) with a separator.

The results are shown in tables 3 and 4.

Comparative example 13

An adhesive composition (C13) was prepared in the same manner as in example 13 except that the amount of Coronate HX (manufactured by Nippon Polyurethane Industry Co.) was changed to 17.7 parts by weight, a fluoropolymer (manufactured by DIC Co., Ltd., trade name: F-571) was not used, and the thickness of the adhesive layer was changed to 25 μm, thereby obtaining a surface protective film (C13) with a separator.

The results are shown in tables 3 and 4.

[ example 16]

Polyol PREMINOL S3011 (manufactured by asahi glass co., ltd., Mn: 10000) having 3 OH groups as polyol (a), polyol sannari GP-3000 (manufactured by sannarian chemical co., ltd., Mn: 3000) having 3 OH groups as polyol (a), polyol sannari GP-1000 (manufactured by sannarian chemical co., ltd., Mn: 1000) having 3 OH groups as polyol (B), polyfunctional alicyclic isocyanate compound Coronate HX (manufactured by Nippon Polyurethane Industry) 17.7 parts by weight as polyfunctional isocyanate compound (B), fluoropolymer (manufactured by DIC corporation, trade name: F-571)0.3 part by weight, and ethyl acetate 200 parts by weight as a diluent solvent were mixed and stirred by a disperser to produce adhesive composition (16).

The obtained adhesive composition (16) was applied to a substrate "lumiror S10" (thickness 38 μm, manufactured by Toray corporation) made of a polyester resin by using a dip roll so that the thickness after drying was 10 μm, and cured and dried at a drying temperature of 130 ℃ for a drying time of 30 seconds. Thereby, an adhesive layer was produced on the substrate. Then, the silicone-treated surface of the base material (separator) having a thickness of 25 μm, one surface of which was silicone-treated, was bonded to the surface of the pressure-sensitive adhesive layer, thereby obtaining a surface protective film (16) with a separator.

The results are shown in tables 3 and 4.

[ example 17]

An adhesive composition (17) was produced in the same manner as in example 16 except that the thickness of the adhesive layer was changed to 25 μm, and a surface protective film (17) with a separator was obtained.

The results are shown in tables 3 and 4.

[ example 18]

Polyol PREMINOL S3011 (manufactured by asahi glass co., ltd., Mn: 10000) having 3 OH groups as polyol (a), polyol sannari GP-3000 (manufactured by sanyo chemical co., ltd., Mn: 3000) having 3 OH groups as polyol (a), polyol sannari GP-1000 (manufactured by sannari chemical co., ltd., Mn: 1000) having 3 OH groups as polyol (B), polyfunctional alicyclic isocyanate compound Coronate HX (manufactured by Nippon Polyurethane Industry) 17.7 parts by weight, hydroxyl-containing silicone (manufactured by shin chemical Industry ltd., trade name: X-22-4015)0.3 part by weight, and ethyl acetate as a diluting solvent were mixed and stirred by a dispersing machine to prepare adhesive composition (18).

The obtained adhesive composition (18) was applied to a substrate "lumiror S10" (thickness 38 μm, manufactured by Toray corporation) made of a polyester resin by using a dip roll so that the thickness after drying was 10 μm, and cured and dried at a drying temperature of 130 ℃ for a drying time of 30 seconds. Thereby, an adhesive layer was produced on the substrate. Then, the silicone-treated surface of a 25 μm thick polyester resin substrate (separator) having one surface subjected to silicone treatment was bonded to the surface of the pressure-sensitive adhesive layer, thereby obtaining a surface protective film (18) with a separator.

The results are shown in tables 3 and 4.

[ example 19]

An adhesive composition (19) was produced in the same manner as in example 18 except that the thickness of the adhesive layer was changed to 25 μm, and a surface protective film (19) with a separator was obtained.

The results are shown in tables 3 and 4.

[ Table 3]

[ example 20]

The separator with the surface protective film (1) of the separator obtained in example 1 was peeled off, and the pressure-sensitive adhesive layer side was attached to a polarizing plate (product name "TEG 1465 DUHC" manufactured by hitong electric corporation) as an optical member, to obtain an optical member to which a surface protective film was attached.

[ example 21]

The separator with the surface protective film (2) of the separator obtained in example 2 was peeled off, and the pressure-sensitive adhesive layer side was attached to a polarizing plate (product name "TEG 1465 DUHC" manufactured by hitong electric corporation) as an optical member, to obtain an optical member to which a surface protective film was attached.

[ example 22]

The separator with the surface protective film (3) of the separator obtained in example 3 was peeled off, and the pressure-sensitive adhesive layer side was attached to a polarizing plate (product name "TEG 1465 DUHC" manufactured by hitong electric corporation) as an optical member, to obtain an optical member to which a surface protective film was attached.

[ example 23]

The separator with the surface protective film (4) of the separator obtained in example 4 was peeled off, and the pressure-sensitive adhesive layer side was attached to a polarizing plate (product name "TEG 1465 DUHC" manufactured by ritodn electric corporation) as an optical member to obtain an optical member to which a surface protective film was attached.

[ example 24]

The separator with the surface protective film (5) of the separator obtained in example 5 was peeled off, and the pressure-sensitive adhesive layer side was attached to a polarizing plate (product name "TEG 1465 DUHC" manufactured by hitong electric corporation) as an optical member, to obtain an optical member to which a surface protective film was attached.

[ example 25]

The separator with the surface protective film (6) of the separator obtained in example 6 was peeled off, and the pressure-sensitive adhesive layer side was attached to a polarizing plate (product name "TEG 1465 DUHC" manufactured by ritodn electric corporation) as an optical member to obtain an optical member to which a surface protective film was attached.

[ example 26]

The separator with the surface protective film (1) of the separator obtained in example 1 was peeled off, and the pressure-sensitive adhesive layer side was bonded to a conductive film (product name "ELECRYSTA V270L-TFMP" manufactured by ritonan electric corporation) as an electronic component, to obtain an electronic component to which a surface protective film was bonded.

[ example 27]

The separator with the surface protective film (2) of the separator obtained in example 2 was peeled off, and the pressure-sensitive adhesive layer side was bonded to a conductive film (product name "ELECRYSTA V270L-TFMP" manufactured by ritonan electric corporation) as an electronic component, to obtain an electronic component to which a surface protective film was bonded.

[ example 28]

The separator with the surface protective film (3) of the separator obtained in example 3 was peeled off, and the pressure-sensitive adhesive layer side was bonded to a conductive film (product name "ELECRYSTA V270L-TFMP" manufactured by ritonan electric corporation) as an electronic component, to obtain an electronic component to which a surface protective film was bonded.

[ example 29]

The separator with the surface protective film (4) of the separator obtained in example 4 was peeled off, and the pressure-sensitive adhesive layer side was bonded to a conductive film (product name "ELECRYSTA V270L-TFMP" manufactured by ritonan electric corporation) as an electronic component, to obtain an electronic component to which a surface protective film was bonded.

[ example 30]

The separator with the surface protective film (5) of the separator obtained in example 5 was peeled off, and the pressure-sensitive adhesive layer side was bonded to a conductive film (product name "ELECRYSTA V270L-TFMP" manufactured by ritonan electric corporation) as an electronic component, to obtain an electronic component to which a surface protective film was bonded.

[ example 31]

The separator with the surface protective film (6) of the separator obtained in example 6 was peeled off, and the pressure-sensitive adhesive layer side was bonded to a conductive film (product name "ELECRYSTA V270L-TFMP" manufactured by ritonan electric corporation) as an electronic component, to obtain an electronic component to which a surface protective film was bonded.

[ example 32]

The separator with the surface protective film (7) of the separator obtained in example 7 was peeled off, and the pressure-sensitive adhesive layer side was attached to a polarizing plate (product name "TEG 1465 DUHC" manufactured by hitong electric corporation) as an optical member, to obtain an optical member to which a surface protective film was attached.

[ example 33]

The separator with the surface protective film (10) of the separator obtained in example 10 was peeled off, and the pressure-sensitive adhesive layer side was attached to a polarizing plate (product name "TEG 1465 DUHC" manufactured by hitong electric corporation) as an optical member, to obtain an optical member to which a surface protective film was attached.

[ example 34]

The separator with the surface protective film (13) of the separator obtained in example 13 was peeled off, and the pressure-sensitive adhesive layer side was attached to a polarizing plate (product name "TEG 1465 DUHC" manufactured by hitong electric corporation) as an optical member, to obtain an optical member to which a surface protective film was attached.

[ example 35]

The separator with the surface protective film (16) of the separator obtained in example 16 was peeled off, and the pressure-sensitive adhesive layer side was attached to a polarizing plate (product name "TEG 1465 DUHC" manufactured by hitong electric corporation) as an optical member, to obtain an optical member to which a surface protective film was attached.

[ example 36]

The separator with the surface protective film (18) of the separator obtained in example 18 was peeled off, and the pressure-sensitive adhesive layer side was attached to a polarizing plate (product name "TEG 1465 DUHC" manufactured by hitong electric corporation) as an optical member, to obtain an optical member to which a surface protective film was attached.

[ example 37]

The separator with the surface protective film (7) of the separator obtained in example 7 was peeled off, and the pressure-sensitive adhesive layer side was bonded to a conductive film (product name "ELECRYSTA V270L-TFMP" manufactured by ritonan electric corporation) as an electronic component, to obtain an electronic component to which a surface protective film was bonded.

[ example 38]

The separator with the surface protective film (10) of the separator obtained in example 10 was peeled off, and the pressure-sensitive adhesive layer side was attached to a conductive film (product name "ELECRYSTA V270L-TFMP" manufactured by ritonan electric corporation) as an electronic component, to obtain an electronic component to which a surface protective film was attached.

[ example 39]

The separator with the surface protective film (13) of the separator obtained in example 13 was peeled off, and the pressure-sensitive adhesive layer side was attached to a conductive film (product name "ELECRYSTA V270L-TFMP" manufactured by ritonan electric corporation) as an electronic component, to obtain an electronic component to which a surface protective film was attached.

[ example 40]

The separator with the surface protective film (16) of the separator obtained in example 16 was peeled off, and the adhesive layer side was bonded to a conductive film (product name "ELECRYSTA V270L-TFMP" manufactured by ritto electrical corporation) as an electronic component, to obtain an electronic component to which a surface protective film was bonded.

[ example 41]

The separator with the surface protective film (18) of the separator obtained in example 18 was peeled off, and the pressure-sensitive adhesive layer side was attached to a conductive film (product name "ELECRYSTA V270L-TFMP" manufactured by ritonan electric corporation) as an electronic component, to obtain an electronic component to which a surface protective film was attached.

Industrial applicability

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

Claims

1. A surface protective film having an adhesive layer, wherein,

a polyethylene terephthalate film having a thickness of 25 μm is bonded to the pressure-sensitive adhesive layer, and after 30 minutes at 23 ℃ the peel force is 0.08N/25mm or less when the polyethylene terephthalate film is peeled at a peel angle of 180 degrees and a peel speed of 6000 mm/min,

the adhesive constituting the adhesive layer is formed of an adhesive composition,

the adhesive composition comprises a base polymer and contains a silicone-based additive and/or a fluorine-based additive,

the organic silicon additive is at least one selected from hydroxyl-containing organic silicon compounds and crosslinking functional group-containing organic silicon compounds,

the fluorine-containing additive is at least one selected from the group consisting of a compound having a fluorinated aliphatic hydrocarbon skeleton, a fluorine-containing organic compound obtained by copolymerizing an organic compound with a fluorine compound, a hydroxyl group-containing fluorine-containing compound, and a fluorine-containing compound having a crosslinkable functional group,

the content of the silicone additive and/or the fluorine additive in the adhesive composition is 0.05 to 50 parts by weight based on 100 parts by weight of the base polymer in total of the silicone additive and the fluorine additive.

2. A surface protective film having an adhesive layer, wherein,

a polyethylene terephthalate film having a thickness of 25 μm is bonded to the pressure-sensitive adhesive layer, and after 7 days at 80 ℃, when the polyethylene terephthalate film is peeled at a peeling angle of 180 degrees and a peeling speed of 6000 mm/min, the peeling force is 0.35N/25mm or less,

3. A surface protective film having an adhesive layer, wherein,

a glass plate having a thickness of 1000 μm is bonded to the adhesive layer, and when the glass plate is peeled from the adhesive layer at a peeling angle of 180 degrees and a peeling speed of 6000 mm/min after 30 minutes at 23 ℃, the peeling force is 0.135N/25mm or less,

4. A surface protective film having an adhesive layer, wherein,

a glass plate having a thickness of 1000 μm is bonded to the adhesive layer, and when the glass plate is peeled from the adhesive layer at a peeling angle of 180 degrees and a peeling speed of 6000 mm/min after 7 days at 80 ℃, the peeling force is 0.35N/25mm or less,

5. The surface protective film according to any one of claims 1 to 4, which has a residual adhesion ratio of 50% or more.

6. The surface protective film according to any one of claims 1 to 4, wherein the adhesive composition contains a fatty acid ester.

7. An optical member to which the surface protective film according to any one of claims 1 to 6 is attached.

8. An electronic component to which the surface protective film according to any one of claims 1 to 6 is attached.