KR102276803B1 - Surface protective film - Google Patents

Abstract

Provided is a surface protection film having superhard peelability and low staining properties on the surface of an adherend. The surface protection film of the present invention is a surface protection film having a pressure-sensitive adhesive layer, a polyethylene terephthalate film having a thickness of 25 μm is bonded to the pressure-sensitive adhesive layer, and the polyethylene terephthalate film is peeled off at an angle of 180 degrees after 30 minutes at 23° C. and peeling force at the time of peeling in 6000 mm/min of peeling speed|rate is 0.08 N/25 mm or less.

Description

Surface protection film {SURFACE PROTECTIVE FILM}

The present invention relates to a surface protection film.

In the manufacturing process of an optical member or an electronic member, in order to prevent generation|occurrence|production of a flaw on the surface during processing, assembly, inspection, transport, etc., a surface protection film is generally adhere|attached to an exposed surface. Such a surface protection film peels from an optical member or an electronic member when the need for surface protection is no longer (patent document 1).

In the optical member or electronic member to which such a surface protection film is adhere|attached, when trying to peel a surface protection film as mentioned above, it is important that it can peel smoothly at the interface of this surface protection film and an optical member or an electronic member.

However, when an optical member or an electronic member is provided with a fragile member such as thin glass or a barrier film, if the adhered surface protection film is to be peeled off, even when a conventional surface protection film with light peelability is used, peeling The brittle member may be damaged by the force.

For this reason, compared with the conventional surface protection film provided with light peelability, the surface protection film provided with lighter peelability, ie, super light peelability, is calculated|required.

Here, in order to weaken peeling force, when a conventional peeling agent is contained abundantly in the adhesive layer of a surface protection film, a certain degree of super-hardening peelability may be expressed. However, in this method, after peeling of the surface protection film, the degree of contamination of the surface of the adherend by the release agent is large, and when the surface protection film is to be adhered again, the surface protection film becomes difficult to adhere due to contamination of the surface of the adherend. there is a problem.

In addition, in the manufacturing process of an optical member or an electronic member, the surface protection film adhered to an exposed surface in order to prevent the generation|occurrence|production of a flaw on the surface during processing, assembly, inspection, transportation, etc. is often stored with adhesion. In this case, when a conventional surface protection film is stored with adhere|attaching, there exists a problem that adhesive force will rise in time-lapse|temporality, and it will become heavy peeling.

As described above, in the manufacturing process of the optical member or electronic member, in the surface protection film adhered to the exposed surface to prevent the occurrence of scratches on the surface during processing, assembly, inspection, transportation, etc., some points to be improved, That is, there are points to be improved, such as providing super light peeling property, being able to lower the contamination of the adherend surface, and being able to suppress heavy peeling over time.

Japanese Patent Laid-Open No. 2016-17109

An object of the present invention is to provide a surface protection film to which super light releasability is imparted, to provide a surface protection film capable of lowering staining properties of the surface of an adherend, and to provide a surface protection film capable of suppressing heavy peeling over time is to provide

The surface protection film of the present invention comprises:

It is a surface protection film having an adhesive layer,

A polyethylene terephthalate film having a thickness of 25 µm was bonded to the pressure-sensitive adhesive layer, and after 30 minutes at 23°C, the polyethylene terephthalate film was peeled off at a peeling angle of 180 degrees and a peeling rate of 6000 mm/min. Peeling force was 0.08 N/25mm or less.

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

The surface protection film of the present invention comprises:

It is a surface protection film having an adhesive layer,

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

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

The surface protection film of the present invention comprises:

It is a surface protection film having an adhesive layer,

The peeling force at the time of bonding a 1000-micrometer-thick glass plate together to this adhesive layer, and peeling in the peeling angle 180 degree and a peeling rate of 6000 mm/min from the said glass plate after 30 minutes at 23 degreeC is 0.135 N/25 mm or less.

In one embodiment, the peeling force at the time of bonding a 1000-micrometer-thick glass plate to the said adhesive layer and peeling at 23 degreeC 30 minutes after peeling in 180 degree peeling angle and 300 mm/min of peeling rate from this glass plate is 0.023 N/25mm or less.

The surface protection film of the present invention comprises:

It is a surface protection film having an adhesive layer,

A glass plate having a thickness of 1000 µm is bonded to the pressure-sensitive adhesive layer, and the peeling force is 0.35 N/25 mm or less when it is peeled from the glass plate at a peeling angle of 180 degrees and a peeling rate of 6000 mm/min from the glass plate after 7 days at 80°C.

In one embodiment, the peeling force at the time of bonding a 1000-micrometer-thick glass plate together to the said adhesive layer and peeling in a peeling angle 180 degree and 300 mm/min of peeling rate 300 mm/min from this glass plate after 7 days at 80 degreeC is 0.05 N/25mm or less.

In one embodiment, the residual adhesive rate of the surface protection film of this invention is 50 % or more.

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

In one embodiment, the said silicone additive is at least 1 sort(s) selected from a siloxane bond containing compound, a hydroxyl group containing silicone type compound, and a crosslinkable functional group containing silicone type compound.

In one embodiment, the said fluorine-type additive is at least 1 sort(s) selected from a fluorine-containing compound, a hydroxyl-containing fluorine-type compound, and a crosslinkable functional group containing fluorine-type compound.

In one embodiment, the said base polymer is at least 1 sort(s) chosen from a urethane-type resin, an acrylic resin, a rubber-type resin, and a silicone resin.

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

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

In one embodiment, the said adhesive composition contains fatty acid ester.

As for the optical member of this invention, the surface protection film of this invention is adhere|attached.

As for the electronic member of this invention, the surface protection film of this invention is adhere|attached.

ADVANTAGE OF THE INVENTION According to this invention, it can provide the surface protection film which is provided with superhard peelability and has low contamination property on the surface of an adherend.

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

≪≪Surface protection film≫≫

The surface protection film of this invention has an adhesive layer. If the surface protection film of this invention has an adhesive layer, it may be equipped with arbitrary appropriate other members in the range which does not impair the effect of this invention. Typically, the surface protection film of this invention has a base material layer and an adhesive layer.

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

In FIG. 1, the surface on the opposite side of the base material layer 1 of the adhesive layer 2 may be equipped with arbitrary appropriate release liners for protection until use, etc. (not shown). As the release liner, for example, a release liner in which the surface of a substrate (liner substrate) such as paper or plastic film is treated with silicone, and a release liner in which the surface of a substrate (liner substrate) such as paper or plastic film is laminated with a polyolefin resin. and the like. As a plastic film as a liner base material, For example, a polyethylene film, a polypropylene film, a polybutene film, a polybutadiene film, a polymethylpentene film, a polyvinyl chloride film, a vinyl chloride copolymer film, a polyethylene terephthalate film, a polybutylene tere A phthalate film, a polyurethane film, an ethylene-vinyl acetate copolymer film, etc. are mentioned. As a plastic film as a liner base material, Preferably it is a polyethylene film.

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

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

In one embodiment of the surface protection film of the present invention, a polyethylene terephthalate film having a thickness of 25 μm is bonded to an adhesive layer, and after 30 minutes at 23° C., the polyethylene terephthalate film is peeled at a 180 degree peeling angle, a peeling rate of 6000 mm/ The peeling force at the time of peeling in minutes becomes like this. Preferably it is 0.08N/25mm or less, More preferably, it is 0.075N/25mm or less, More preferably, it is 0.07N/25mm or less, More preferably, it is 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 said peeling force is 0.001 N/25 mm or more realistically. When the said peeling force in the very high peeling speed of 6000 mm/min of peeling speed exists in the said range, the surface protection film of this invention can express the very excellent super light peeling property. In addition, the detail of the measurement of the said peeling force is mentioned later.

In one embodiment of the surface protection film of the present invention, a polyethylene terephthalate film having a thickness of 25 μm is bonded to a pressure-sensitive adhesive layer, and after 30 minutes at 23° C., the polyethylene terephthalate film is peeled off at an angle of 180 degrees and a peeling rate of 300 mm/ The peeling force at the time of peeling in minutes becomes like this. Preferably it is 0.02 N/25 mm or less, More preferably, it is 0.018 N/25 mm or less, More preferably, it is 0.015 N/25 mm or less, Especially preferably, 0.012 N/ 25 mm or less, and most preferably 0.01 N/25 mm or less. The lower limit of the said peeling force is 0.001 N/25 mm or more realistically. When the said peeling force exists in the said range, the surface protection film of this invention can express super light peeling property. In addition, the detail of the measurement of the said peeling force is mentioned later.

In one embodiment of the surface protection film of the present invention, a polyethylene terephthalate film having a thickness of 25 μm is bonded to an adhesive layer, and after 7 days at 80° C., the polyethylene terephthalate film is subjected to a peeling angle of 180 degrees, a peeling rate of 6000 mm/ The peeling force at the time of peeling in minutes becomes like this. Preferably it is 0.35 N/25 mm or less, More preferably, it is 0.33 N/25 mm or less, More preferably, it is 0.3 N/25 mm or less, More preferably, it is 0.27 N. /25 mm or less, particularly preferably 0.25 N/25 mm or less, and most preferably 0.23 N/25 mm or less. The lower limit of the said peeling force is 0.001 N/25 mm or more realistically. When the said peeling force in 7 days after at 80 degreeC exists in the said range, the surface protection film of this invention can fully suppress the heavy peeling in time-lapse|temporality. In addition, the detail of the measurement of the said peeling force is mentioned later.

In one embodiment of the surface protection film of the present invention, a polyethylene terephthalate film having a thickness of 25 μm is bonded to an adhesive layer, and after 7 days at 80° C., the polyethylene terephthalate film is peeled at a peeling angle of 180 degrees and a peeling rate of 300 mm/ Peeling force when peeling in minutes is preferably 0.07 N/25 mm or less, more preferably 0.06 N/25 mm or less, still more preferably 0.05 N/25 mm or less, particularly preferably 0.045 N/25 mm or less. 25 mm or less, and most preferably 0.04 N/25 mm or less. The lower limit of the said peeling force is 0.001 N/25 mm or more realistically. When the said peeling force exists in the said range, the surface protection film of this invention can suppress heavy peeling in time-lapse|temporality. In addition, the detail of the measurement of the said peeling force is mentioned later.

In one embodiment of the surface protection film of the present invention, when a glass plate having a thickness of 1000 μm is bonded to an adhesive layer, and after 30 minutes at 23° C., it is peeled from the glass plate at a peeling angle of 180 degrees and a peeling rate of 6000 mm/min. The peeling force of 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 it is 0.06N/25mm or less, Most preferably, it is 0.055N/25mm or less. The lower limit of the said peeling force is 0.001 N/25 mm or more realistically. When the said peeling force in the very high peeling speed of a peeling speed of 6000 mm/min exists in the said range, the surface protection film of this invention can express the extremely excellent superhard peelability. In addition, the detail of the measurement of the said peeling force is mentioned later.

One embodiment of the surface protection film of the present invention is when a glass plate having a thickness of 1000 μm is bonded to the pressure-sensitive adhesive layer and peeled from the glass plate at a peeling angle of 180 degrees and a peeling rate of 300 mm/min from the glass plate after 30 minutes at 23° C. 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 It is 0.013N/25mm or less. The lower limit of the said peeling force is 0.001 N/25 mm or more realistically. When the said peeling force exists in the said range, the surface protection film of this invention can express super light peeling property. In addition, the detail of the measurement of the said peeling force is mentioned later.

One embodiment of the surface protection film of the present invention is when a glass plate having a thickness of 1000 μm is bonded to an adhesive layer and peeled from the glass plate after 7 days at 80° C. at a peeling angle of 180 degrees and a peeling rate of 6000 mm/min. The peeling force of is preferably 0.35 N/25 mm or less, more preferably 0.3 N/25 mm or less, still more preferably 0.25 N/25 mm or less, still more preferably 0.2 N/25 mm or less, particularly Preferably it is 0.15N/25mm or less, Most preferably, it is 0.1N/25mm or less. The lower limit of the said peeling force is 0.001 N/25 mm or more realistically. When the said peeling force in 7 days after at 80 degreeC exists in the said range, the surface protection film of this invention can fully suppress the heavy peeling in time-lapse|temporality. In addition, the detail of the measurement of the said peeling force is mentioned later.

One embodiment of the surface protection film of the present invention is when a glass plate having a thickness of 1000 μm is bonded to the pressure-sensitive adhesive layer and peeled from the glass plate after 7 days at 80° C. at a peeling angle of 180 degrees and a peeling rate of 300 mm/min. The peeling force of 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, most preferably 0.03N/25mm or less. The lower limit of the said peeling force is 0.001 N/25 mm or more realistically. When the said peeling force exists in the said range, the surface protection film of this invention can suppress heavy peeling in time-lapse|temporality. In addition, the detail of the measurement of the said peeling force is mentioned later.

The surface protection film of the present invention has a residual adhesive ratio of preferably 50% or more, more preferably 55% to 100%, still more preferably 60% to 100%, particularly preferably 65% to 100%, most preferably from 70% to 100%. When the said residual adhesiveness exists in the said range, the surface protection film of this invention can express the effect that the stain|pollution|contamination property of the to-be-adhered body surface is low. In addition, the detail of the measurement of the residual adhesive rate is mentioned later.

The surface protection film of this invention can be manufactured by arbitrary appropriate methods. As such a manufacturing method, for example,

(1) a method of applying a solution of a material for forming the pressure-sensitive adhesive layer or a hot melt solution on the base layer;

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

(3) a method of extruding the forming material of the pressure-sensitive adhesive layer on the base layer to form and apply;

(4) a method of extruding the substrate layer and the pressure-sensitive adhesive layer in two or multiple layers;

(5) a method of laminating a pressure-sensitive adhesive layer in a single layer on a base layer or a method of laminating a pressure-sensitive adhesive layer together with a laminate layer in two layers;

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

It can carry out according to arbitrary suitable manufacturing methods, such as

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

≪Base layer≫

One layer may be sufficient as a base material layer, and two or more layers may be sufficient as it. The base layer may be stretched.

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

For the side of the base layer on which the pressure-sensitive adhesive layer is not laid, for the purpose of forming a wound body that can be easily rewound, for example, fatty acid amide, polyethyleneimine, long-chain alkyl-based additives, etc. are added to the base layer to release treatment. or a coating layer containing any appropriate release agent, such as silicone-based, long-chain alkyl-based, or fluorine-based release agent, can be formed.

As a material of a base material layer, arbitrary suitable materials can be employ|adopted according to a use. For example, plastics, paper, a metal film, a nonwoven fabric, etc. are mentioned. Preferably it is plastic. That is, the base material layer is preferably a plastic film. The base material layer may be comprised from 1 type of material, and may be comprised from 2 or more types of materials. For example, you may be comprised from 2 or more types of plastics.

As said plastics, polyester-type resin, polyamide-type resin, polyolefin resin etc. are mentioned, for example. Examples of the polyester-based resin include polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate. As polyolefin resin, the homopolymer of an olefin monomer, the copolymer of an olefin monomer, etc. are mentioned, for example. Specific examples of the polyolefin-based resin include homopolypropylene; propylene-based copolymers having an ethylene component as a copolymerization component, such as block-based, random-based, and graft-based copolymers; Reactor TPO; ethylene polymers such as low density, high density, linear low density, and ultra low density; Ethylene/propylene copolymer, ethylene/vinyl acetate copolymer, ethylene/methyl acrylate copolymer, ethylene/ethyl acrylate copolymer, ethylene/butyl acrylate copolymer, ethylene/methacrylic acid copolymer, ethylene/methyl methacrylate copolymer ethylene-based copolymers such as; and the like.

The base layer may contain any appropriate additives as needed. As an additive which may be contained in a base material layer, antioxidant, a ultraviolet absorber, a light stabilizer, an antistatic agent, a filler, a pigment, etc. are mentioned, for example. The type, number, and amount of additives that may be contained in the base layer may be appropriately set according to the purpose. In particular, when the material of the base layer is plastic, it is preferable to contain some of the above additives for the purpose of preventing deterioration or the like. From a viewpoint of a weather resistance improvement etc., Especially preferably, antioxidant, a ultraviolet absorber, a light stabilizer, and a filler are mentioned as an additive.

As antioxidant, any suitable antioxidant can be employ|adopted. Examples of such antioxidants include phenol-based antioxidants, phosphorus-based processing heat stabilizers, lactone-based processing thermal stabilizers, sulfur-based heat-resistant stabilizers, and phenol/phosphorus-based antioxidants. The content of the antioxidant is preferably 1% by weight or less, more preferably 0.5% by weight or less, with respect to the base resin of the base layer (when the base layer is a blend, the blend is the base resin), More preferably, it is 0.01 weight% - 0.2 weight%.

As a ultraviolet absorber, arbitrary appropriate ultraviolet absorbers can be employ|adopted. As such an ultraviolet absorber, a benzotriazole type ultraviolet absorber, a triazine type ultraviolet absorber, a benzophenone type ultraviolet absorber, etc. are mentioned, for example. The content of the ultraviolet absorber is preferably 2% by weight or less, and more preferably 1% by weight or less with respect to the base resin forming the base layer (when the base layer is a blend, the blend is the base resin). and more preferably 0.01 wt% to 0.5 wt%.

As the light stabilizer, any appropriate light stabilizer can be employed. As such a light stabilizer, a hindered amine type light stabilizer, a benzoate type light stabilizer, etc. are mentioned, for example. The content of the light stabilizer is preferably 2% by weight or less, and more preferably 1% by weight or less with respect to the base resin forming the base layer (when the base layer is a blend, the blend is the base resin). and more preferably 0.01 wt% to 0.5 wt%.

As the filler, any suitable filler can be employed. As such a filler, an inorganic filler etc. are mentioned, for example. Specific examples of the inorganic filler include carbon black, titanium oxide, and zinc oxide. The content of the filler is preferably 20% by weight or less, and more preferably 10% by weight or less, with respect to the base resin forming the base layer (when the base layer is a blend, the blend is the base resin). , more preferably 0.01 wt% to 10 wt%.

Moreover, as an additive, for the purpose of providing antistatic property, inorganic type antistatic agents, such as surfactant, an inorganic salt, polyhydric alcohol, a metal compound, and carbon, a low molecular weight type, and a high molecular weight type antistatic agent are mentioned preferably. In particular, a high molecular weight antistatic agent and carbon are preferable from a viewpoint of stain|pollution|contamination and adhesive maintenance.

≪Adhesive layer≫

An adhesive layer can be manufactured by arbitrary appropriate manufacturing methods. As such a manufacturing method, the method of apply|coating the composition which is a forming material of an adhesive layer on a base material layer, and forming an adhesive layer on a base material layer is mentioned, for example. Examples of such a coating method include roll coating, gravure coating, reverse coating, roll brush, spray coating, air knife coating, extrusion coating by a die coater, and the like.

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

The pressure-sensitive adhesive layer is constituted by the pressure-sensitive adhesive. The pressure-sensitive adhesive is formed of a pressure-sensitive adhesive composition.

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

The content of the silicone-based additive and/or the fluorine-based additive in the pressure-sensitive adhesive composition is the total amount of the silicone-based additive and the fluorine-based additive relative to 100 parts by weight of the base polymer, preferably 0.01 part by weight to 50 parts by weight, more preferably 0.02 part by weight to 25 parts by weight, more preferably 0.025 parts by weight to 10 parts by weight, particularly preferably 0.03 parts by weight to 5 parts by weight, and most preferably 0.05 parts by weight to 3 parts by weight. When the content of the silicone-based additive and/or the fluorine-based additive in the pressure-sensitive adhesive composition is within the above range, the surface protection film of the present invention can exhibit higher cemented carbide peelability, and can further lower the staining properties of the surface of the adherend.

<Base Polymer>

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

[Urethane-based resin]

As the urethane-based resin, any appropriate urethane-based resin can be employed as long as the effects of the present invention are not impaired. The urethane-based resin is preferably a urethane-based resin formed from a composition containing a polyol (A) and a polyfunctional isocyanate compound (B), or a composition containing a urethane prepolymer (C) and a polyfunctional isocyanate compound (B). It is a urethane resin. By employing the above as the urethane-based resin, the wettability of the pressure-sensitive adhesive layer can be improved, so that the surface protection film of the present invention can be adhered without entraining air bubbles.

Urethane-type resin can contain arbitrary appropriate components in the range which does not impair the effect of this invention. Examples of such components include resin components other than urethane resins, tackifiers, inorganic fillers, organic fillers, metal powders, pigments, thin materials, softeners, antioxidants, conductive agents, ultraviolet absorbers, antioxidants, light stabilizers, surface lubricants. , a leveling agent, a corrosion inhibitor, a heat-resistant stabilizer, a polymerization inhibitor, a lubricant, a solvent, a catalyst, and the like.

The urethane-based resin preferably contains a deterioration inhibitor such as an antioxidant, an ultraviolet absorber, or a light stabilizer. When the urethane-based resin contains a deterioration inhibitor, the adhesive residue prevention property can be improved, such as it is difficult to generate adhesive residue on the adherend even after being adhered to the adherend and then stored in a warm state. The number of deterioration inhibitors may be one, and 2 or more types may be sufficient as them. As the deterioration inhibitor, it is particularly preferably an antioxidant.

As antioxidant, a radical chain inhibitor, a peroxide decomposing agent, etc. are mentioned, for example.

As a radical chain inhibitor, a phenol type antioxidant, an amine type antioxidant, etc. are mentioned, for example.

Examples of the peroxide decomposing agent include sulfur-based antioxidants and phosphorus-based antioxidants.

Examples of the phenol-based antioxidant include monophenol-based antioxidants, bisphenol-based antioxidants, and polymer-type phenol-based antioxidants.

Examples of the monophenolic antioxidant include 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-4-ethylphenol, stearin-β- (3,5-di-t-butyl-4-hydroxyphenyl) propionate etc. are mentioned.

Examples of the bisphenol-based antioxidant include 2,2'-methylenebis(4-methyl-6-t-butylphenol), 2,2'-methylenebis(4-ethyl-6-t-butylphenol), 4 ,4'-thiobis(3-methyl-6-t-butylphenol), 4,4'-butylidenebis(3-methyl-6-t-butylphenol), 3,9-bis[1,1 -Dimethyl-2-[β-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl]2,4,8,10-tetraoxaspiro[5,5]undecane, etc. can be heard

Examples of the high molecular weight phenolic antioxidant include 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane, 1,3,5-trimethyl-2,4,6 -tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, tetrakis-[methylene-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)prop Cypionate]methane, bis[3,3'-bis-(4'-hydroxy-3'-t-butylphenyl)butyl acid]glycol ester, 1,3,5-tris(3',5'-di -t-butyl-4'-hydroxybenzyl)-S-triazine-2,4,6-(1H,3H,5H)trione, tocophenol, etc. are mentioned.

As the sulfur-based antioxidant, for example, dilauryl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate, distearyl 3,3'-thiodipropionate, etc. can be heard

As phosphorus antioxidant, triphenyl phosphite, diphenyl isodecyl phosphite, phenyl diisodecyl phosphite, etc. are mentioned, for example.

Examples of the ultraviolet absorber include a benzophenone-based ultraviolet absorber, a benzotriazole-based ultraviolet absorber, a salicylic acid-based ultraviolet absorber, an oxalic acid anilide-based ultraviolet absorber, a cyanoacrylate-based ultraviolet absorber, and a triazine-based ultraviolet absorber.

As a benzophenone type|system|group ultraviolet absorber, 2, 4- dihydroxy benzophenone, 2-hydroxy-4- methoxybenzophenone, 2-hydroxy-4- octoxy benzophenone, 2-hydroxy-4 are, for example. -Dodecyloxybenzophenone, 2,2'-dihydroxy-4-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4-me oxy-5-sulfobenzophenone, bis(2-methoxy-4-hydroxy-5-benzoylphenyl)methane, etc. are mentioned.

Examples of the benzotriazole-based ultraviolet absorber include 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-5'-tert-butylphenyl)benzotriazole, 2 -(2'-hydroxyl-3',5'-di-tert-butylphenyl)benzotriazole, 2-(2'-hydroxyl-3'-tert-butyl-5'-methylphenyl)-5-chloro Benzotriazole, 2-(2'-hydroxyl-3',5'-di-tert-butylphenyl) 5-chlorobenzotriazole, 2-(2'-hydroxyl-3',5'-di- tert-amylphenyl)benzotriazole, 2-(2'-hydroxy-4'-octoxyphenyl)benzotriazole, 2-[2'-hydroxy-3'-(3",4",5" ,6",-tetrahydrophthalimidomethyl)-5'-methylphenyl]benzotriazole, 2,2'methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzo triazol-2-yl)phenol], 2-(2'-hydroxy-5'-methacryloxyphenyl)-2H-benzotriazole, etc. are mentioned.

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

Examples of the cyanoacrylate-based ultraviolet absorber include 2-ethylhexyl-2-cyano-3,3'-diphenyl acrylate, ethyl-2-cyano-3,3'-diphenyl acrylate, and the like. can be heard

As a light stabilizer, a hindered amine type light stabilizer, an ultraviolet stabilizer, etc. are mentioned, for example.

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 nickel bis(octylphenyl)sulfide, [2,2'-thiobis(4-tert-octylphenolato)]-n-butylamine nickel, nickel complex-3,5-di- tert-butyl-4-hydroxybenzyl-phosphate monoethylate, nickel-dibutyldithiocarbamate, benzoate type ??cha, nickel-dibutyldithiocarbamate, etc. are mentioned.

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

The urethane-based resin formed from the composition containing the polyol (A) and the polyfunctional isocyanate compound (B) is specifically, preferably obtained by curing the composition containing the polyol (A) and the polyfunctional isocyanate compound (B). It is a urethane resin.

The number of polyols (A) may be one, and 2 or more types may be sufficient as them.

The number of polyfunctional isocyanate compounds (B) may be one, and 2 or more types may be sufficient as them.

As polyol (A), Preferably, polyester polyol, polyether polyol, polycaprolactone polyol, polycarbonate polyol, and a castor oil type polyol are mentioned, for example. As a polyol (A), More preferably, it is a polyether polyol.

As a polyester polyol, it can obtain by the esterification reaction of a polyol component and an acid component, for example.

Examples of the polyol component include ethylene glycol, diethylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2-butyl-2-ethyl-1 ,3-propanediol, 2,4-diethyl-1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 2- Methyl-1,8-octanediol, 1,8-decanediol, octadecanediol, glycerin, trimethylolpropane, pentaerythritol, hexanetriol, polypropylene glycol, etc. are mentioned. Examples of the acid component include succinic acid, methylsuccinic acid, adipic acid, pimelic acid, azelaic acid, sebacic acid, 1,12-dodecanoic acid, 1,14-tetradecanoic acid, dimer acid, 2-methyl-1, 4-cyclohexanedicarboxylic acid, 2-ethyl-1,4-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, isophthalic acid, terephthalic acid, 1,4-naphthalenedicarboxylic acid, 4,4' -biphenyldicarboxylic acid, these acid anhydrides, etc. are mentioned.

Examples of the polyether polyol include water, low molecular weight polyols (propylene glycol, ethylene glycol, glycerin, trimethylolpropane, pentaerythritol, etc.), bisphenols (bisphenol A, etc.), dihydroxybenzene (catechol, resorcin, Hydroquinone etc.) etc. as an initiator, and the polyether polyol obtained by addition polymerization of alkylene oxides, such as ethylene oxide, a propylene oxide, a butylene oxide, is mentioned. Specifically, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, etc. are mentioned, for example.

Examples of the polycaprolactone polyol include caprolactone-based polyesterdiol obtained by ring-opening polymerization of cyclic ester monomers such as ε-caprolactone and σ-valerolactone.

As polycarbonate polyol, For example, polycarbonate polyol obtained by making the said polyol component and phosgene polycondensate; The polyol component and dicarbonate such as dimethyl carbonate, diethyl carbonate, dipropyl carbonate, diisopropyl carbonate, dibutyl carbonate, ethyl butyl carbonate, ethylene carbonate, propylene carbonate, diphenyl carbonate, and dibenzyl carbonate polycarbonate polyols obtained by transesterifying esters; Copolymerization polycarbonate polyol obtained by using together 2 or more types of said polyol component; a polycarbonate polyol obtained by esterifying the various polycarbonate polyols with a carboxyl group-containing compound; polycarbonate polyols obtained by etherifying the above various polycarbonate polyols with a hydroxyl group-containing compound; a polycarbonate polyol obtained by transesterifying the various polycarbonate polyols with an ester compound; a polycarbonate polyol obtained by transesterifying the various polycarbonate polyols with a hydroxyl group-containing compound; polyester-based polycarbonate polyols obtained by polycondensation reaction of the various polycarbonate polyols and dicarboxylic acid compounds; copolymerized polyether-based polycarbonate polyols obtained by copolymerizing the various polycarbonate polyols and alkylene oxides; and the like.

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

The number average molecular weight Mn of a polyol (A) becomes like this. Preferably it is 300-100000, More preferably, it is 400-75000, More preferably, it is 450-50000, Especially preferably, it is 500-30000. By adjusting the number average molecular weight Mn of the polyol (A) within the above range, the wettability of the pressure-sensitive adhesive layer can be improved, so that the surface protection film of the present invention can adhere without entraining air bubbles.

The polyol (A) preferably contains a polyol (A1) having three OH groups and having a number average molecular weight Mn of 300 to 100000. The number of polyols (A1) may be one, and 2 or more types may be sufficient as them.

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 ratio of the polyol (A1) in the polyol (A) within the above range, the wettability of the pressure-sensitive adhesive layer can be improved, so that the surface protection film of the present invention can adhere without entraining air bubbles.

The number average molecular weight Mn of the polyol (A1) is preferably from 1000 to 100000, more preferably from 1200 to 80000, still more preferably from 1500 to 70000, still more preferably from 1750 to 50000, particularly preferably is from 1500 to 40000, most preferably from 2000 to 30000. By adjusting the number average molecular weight Mn of the polyol (A1) within the above range, the wettability of the pressure-sensitive adhesive layer can be improved, so that the surface protection film of the present invention can adhere without entraining air bubbles.

The polyol (A) may contain the polyol (A2) whose number average molecular weight Mn which has 3 or more OH groups is 20000 or less. The number of polyols (A2) may be one, and 2 or more types may be sufficient as them. 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. When the number average molecular weight Mn of the polyol (A2) deviates from within the above range, there is a fear that the synergism of the adhesive force with time may increase in particular, and there is a fear that the excellent reworkability may not be expressed. The polyol (A2) is preferably a polyol having three OH groups (triol), a polyol having four OH groups (tetraol), a polyol having five OH groups (pentaol), and a polyol having six OH groups (hexa ol) can be heard.

As the polyol (A2), the total amount of at least one of a polyol having 4 OH groups (tetraol), a polyol having 5 OH groups (pentaol), and a polyol having 6 OH groups (hexaol) is polyol (A) As a content rate in it, Preferably it is 70 weight% or less, More preferably, it is 60 weight% or less, More preferably, it is 40 weight% or less, Especially preferably, it is 30 weight% or less. In the polyol (A), as the polyol (A2), at least one of a polyol having 4 OH groups (tetraol), a polyol having 5 OH groups (pentaol), and a polyol having 6 OH groups (hexaol) as above By adjusting to the range, a urethane-based resin excellent in transparency can be provided and the wettability of the pressure-sensitive adhesive layer can be improved, so that the surface protection film of the present invention can adhere without entraining air bubbles.

The content of the polyol (A2) in the polyol (A) is preferably 95 wt% or less, and more preferably 0 wt% to 75 wt%. By adjusting the content ratio of the polyol (A2) in the polyol (A) within the above range, the wettability of the pressure-sensitive adhesive layer can be improved, so that the surface protection film of the present invention can adhere without entraining air bubbles.

In the polyol (A2), the content ratio of the polyol having 4 or more OH groups and having a number average molecular weight Mn of 20000 or less in the polyol (A) as a whole is preferably less than 70% by weight, more preferably It is 60 weight% or less, More preferably, it is 50 weight% or less, Especially preferably, it is 40 weight% or less, Most preferably, it is 30 weight% or less. By adjusting the content ratio of the polyol having 4 or more OH groups and having a number average molecular weight Mn of 20000 or less in the polyol (A2) to the above range, a urethane-based resin excellent in transparency can be provided, and the wettability of the pressure-sensitive adhesive layer can be improved Therefore, the surface protection film of the present invention can be adhered without entraining air bubbles.

The number of polyfunctional isocyanate compounds (B) may be one, and 2 or more types may be sufficient as them.

As a polyfunctional isocyanate compound (B), arbitrary appropriate polyfunctional isocyanate compounds which can be used for urethanation reaction are employable. As such a polyfunctional isocyanate compound (B), a polyfunctional aliphatic type isocyanate compound, a polyfunctional alicyclic type isocyanate, a polyfunctional aromatic type isocyanate compound, etc. are mentioned, for example.

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

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. and hydrogenated xylylene diisocyanate, hydrogenated tolylene diisocyanate, and hydrogenated tetramethylxylylene diisocyanate.

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

As a polyfunctional isocyanate compound (B), the trimethylol propane adduct body of the above various polyfunctional isocyanate compounds, the biuret body which reacted with water, the trimer etc. which have an isocyanurate ring are mentioned. Moreover, you may use these together.

The equivalent ratio of the NCO group and the OH group in the polyol (A) and the polyfunctional isocyanate compound (B) is, as NCO group/OH group, preferably 5.0 or less, more preferably 0.1 to 3.0, still more preferably is 0.2 to 2.5, particularly preferably 0.3 to 2.25, and most preferably 0.5 to 2.0. By adjusting the equivalent ratio of NCO group/OH group within the above range, the wettability of the pressure-sensitive adhesive layer can be improved, so that the surface protection film of the present invention can adhere without entraining air bubbles.

The content of the polyfunctional isocyanate compound (B) is preferably 1.0 wt% to 30 wt%, more preferably 1.5 wt% to 27 wt% of the polyfunctional isocyanate compound (B) with respect to the polyol (A). %, more preferably 2.0 wt% to 25 wt%, particularly preferably 2.3 wt% to 23 wt%, and most preferably 2.5 wt% to 20 wt%. By adjusting the content rate of the polyfunctional isocyanate compound (B) within the above range, the wettability of the pressure-sensitive adhesive layer can be improved, so that the surface protection film of the present invention can adhere without entraining air bubbles.

Polyurethane-type resin is specifically, Preferably it hardens|cures the composition containing a polyol (A) and a polyfunctional isocyanate compound (B), and is formed.

As a method for forming a urethane-based resin by curing a composition containing a polyol (A) and a polyfunctional isocyanate compound (B), a urethanation reaction method using bulk polymerization or solution polymerization, etc., within a range that does not impair the effects of the present invention Any suitable method may be employed.

For curing the composition containing the polyol (A) and the polyfunctional isocyanate compound (B), a catalyst is preferably used. As such a catalyst, an organometallic compound, a tertiary amine compound, etc. are mentioned, for example.

Examples of the organometallic compound include an iron-based compound, a tin-based compound, a titanium-based compound, a zirconium-based compound, a lead-based compound, a cobalt-based compound, and a zinc-based compound. Among these, an iron-type compound and a tin-type compound are preferable from the point of a reaction rate and the pot life of an adhesive layer.

As an iron-type compound, iron acetylacetonate, 2-ethyl hexanoate iron, etc. are mentioned, for example.

Examples of the tin-based compound include dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin maleate, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin sulfide, Tributyltin methoxide, tributyltin acetate, triethyltin ethoxide, tributyltin ethoxide, dioctyltin oxide, dioctyltin dilaurate, tributyltin chloride, tributyltin trichloroacetate, 2 -Ethyl tin hexanoate, etc. are mentioned.

Examples of the titanium-based compound include dibutyl titanium dichloride, tetrabutyl titanate, and butoxytitanium trichloride.

As a zirconium type compound, zirconium naphthenate, zirconium acetylacetonate, etc. are mentioned, for example.

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

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

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

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

The number of catalysts may be one, and 2 or more types may be sufficient as them. Moreover, you may use together a catalyst, a crosslinking retarder, etc. The amount of the catalyst is preferably 0.005% by weight to 1.00% by weight, more preferably 0.01% by weight to 0.75% by weight, still more preferably 0.01% by weight to 0.50% by weight, particularly with respect to the polyol (A). Preferably it is 0.01 weight% - 0.20 weight%. By adjusting the amount of the catalyst within the above range, the wettability of the pressure-sensitive adhesive layer can be improved, so that the surface protection film of the present invention can be adhered without entraining air bubbles.

In the composition containing a polyol (A) and a polyfunctional isocyanate compound (B), it is a range which does not impair the effect of this invention, and arbitrary appropriate other components can be included. Examples of such other components include resin components other than polyurethane resins, tackifiers, inorganic fillers, organic fillers, metal powders, pigments, thin materials, softeners, antioxidants, conductive agents, ultraviolet absorbers, antioxidants, and light stabilizers. , a surface lubricant, a leveling agent, a corrosion inhibitor, a heat-resistant stabilizer, a polymerization inhibitor, a lubricant, a solvent, a catalyst, and the like.

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

As the urethane-based resin formed from the composition containing the urethane prepolymer (C) and the polyfunctional isocyanate compound (B), any appropriate urethane-based resin can be employed as long as it is a urethane-based resin obtained using a so-called “urethane prepolymer” as a raw material.

A urethane-based resin formed from a composition containing a urethane prepolymer (C) and a polyfunctional isocyanate compound (B) is formed from a composition containing, for example, a polyurethane polyol as a urethane prepolymer (C) and a polyfunctional isocyanate compound (B) and urethane-based resins to be used. The number of urethane prepolymers (C) may be one, and 2 or more types may be sufficient as them. The number of polyfunctional isocyanate compounds (B) may be one, and 2 or more types may be sufficient as them.

The polyurethane polyol as the urethane prepolymer (C) is preferably a polyester polyol (a1) or a polyether polyol (a2) alone or a mixture of (a1) and (a2) in the presence of a catalyst or without a catalyst Below, it is made to react with an organic polyisocyanate compound (a3).

As the polyester polyol (a1), any suitable polyester polyol can be used. As such a polyester polyol (a1), the polyester polyol obtained by making an acid component and a glycol component react, for example is mentioned. As an acid component, terephthalic acid, adipic acid, azelaic acid, sebacic acid, phthalic anhydride, isophthalic acid, trimellitic acid, etc. are mentioned, for example. As the glycol component, for example, ethylene glycol, propylene glycol, diethylene glycol, butylene glycol, 1,6-hexane glycol, 3-methyl-1,5-pentanediol, 3,3'-dimethylolheptane, polyoxy Ethylene glycol, polyoxypropylene glycol, 1,4-butanediol, neopentyl glycol, butyl ethyl pentanediol, glycerol, trimethylol propane, pentaerythritol etc. are mentioned as a polyol component. Examples of the polyester polyol (a1) include a polyester polyol obtained by ring-opening polymerization of lactones such as polycaprolactone, poly(β-methyl-γ-valerolactone), and polyvalerolactone.

As the molecular weight of the polyester polyol (a1), from a low molecular weight to a high molecular weight can be used. As molecular weight of polyester polyol (a1), a number average molecular weight becomes like this. Preferably it is 100-100000. When the number average molecular weight is less than 100, the reactivity becomes high, and there is a possibility that it becomes easy to gel. When the number average molecular weight exceeds 100000, the reactivity becomes low, and there is a possibility that the cohesive force of the polyurethane polyol itself becomes small. The amount of the polyester polyol (a1) used is preferably 0 mol% to 90 mol% in the polyols constituting the polyurethane polyol.

As the polyether polyol (a2), any appropriate polyether polyol can be used. As such a polyether polyol (a2), for example, water, propylene glycol, ethylene glycol, glycerin, trimethylolpropane, etc. low molecular weight polyols are used as initiators, and ethylene oxide, propylene oxide, butylene oxide, tetrahydro Polyether polyol obtained by superposing|polymerizing oxirane compounds, such as furan, is mentioned. Specific examples of the polyether polyol (a2) include polyether polyols having two or more functional groups, such as polypropylene glycol, polyethylene glycol, and polytetramethylene glycol.

As the molecular weight of the polyether polyol (a2), from a low molecular weight to a high molecular weight can be used. As molecular weight of polyether polyol (a2), a number average molecular weight becomes like this. Preferably it is 100-100000. When the number average molecular weight is less than 100, the reactivity becomes high, and there is a possibility that it becomes easy to gel. When the number average molecular weight exceeds 100000, the reactivity becomes low, and there is a possibility that the cohesive force of the polyurethane polyol itself becomes small. The amount of the polyether polyol (a2) used is preferably 0 mol% to 90 mol% in the polyols constituting the polyurethane polyol.

The polyether polyol (a2) may contain a part thereof as needed, glycols such as ethylene glycol, 1,4-butanediol, neopentyl glycol, butylethylpentanediol, glycerin, trimethylolpropane, pentaerythritol, ethylenediamine, Polyvalent amines such as N-aminoethylethanolamine, isophoronediamine, and xylylenediamine can be used in combination.

As the polyether polyol (a2), only a bifunctional polyether polyol may be used, and a polyether polyol having a number average molecular weight of 100 to 100000 and having at least 3 or more hydroxyl groups in one molecule may be partially or entirely used. As the polyether polyol (a2), when a polyether polyol having a number average molecular weight of 100 to 100000 and having at least three or more hydroxyl groups in one molecule is partially or entirely used, the balance between adhesive strength and re-peelability can be improved. In such a polyether polyol, if the number average molecular weight is less than 100, the reactivity becomes high and there exists a possibility that it may become easy to gelatinize. Moreover, in such a polyether polyol, when a number average molecular weight exceeds 100000, reactivity may become low and there exists a possibility that the cohesive force of polyurethane polyol itself may become small further. The number average molecular weight of such a polyether polyol becomes like this. More preferably, it is 100-10000.

As the organic polyisocyanate compound (a3), any appropriate organic polyisocyanate compound can be used. As such an organic polyisocyanate compound (a3), aromatic polyisocyanate, aliphatic polyisocyanate, aromatic aliphatic polyisocyanate, alicyclic polyisocyanate etc. are mentioned, for example.

Examples of the aromatic polyisocyanate include 1,3-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,4-phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, and 2,4-tolyl. Rendiisocyanate, 2,6-tolylene diisocyanate, 4,4'-toluidine diisocyanate, 2,4,6-triisocyanatotoluene, 1,3,5-triisocyanatobenzene, dianisidine diisocyanate, 4 ,4'-diphenyl ether diisocyanate, 4,4',4"-triphenylmethane triisocyanate, etc. are mentioned.

Examples of the aliphatic polyisocyanate include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, and 1,3-butylene diisocyanate. Isocyanate, dodecamethylene diisocyanate, 2,4,4-trimethyl hexamethylene diisocyanate, etc. are mentioned.

As aromatic aliphatic polyisocyanate, for example, ω,ω'-diisocyanato-1,3-dimethylbenzene, ω,ω'-diisocyanato-1,4-dimethylbenzene, ω,ω'-diisocy anato-1,4-diethylbenzene, 1,4-tetramethylxylylenediisocyanate, 1,3-tetramethylxylylenediisocyanate, etc. are mentioned.

Examples of the alicyclic polyisocyanate include 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate, 1,3-cyclopentane diisocyanate, 1,3-cyclohexanediisocyanate, and 1,4- Cyclohexanediisocyanate, methyl-2,4-cyclohexanediisocyanate, methyl-2,6-cyclohexanediisocyanate, 4,4'-methylenebis(cyclohexylisocyanate), 1,4-bis(isocyanato) Methyl) cyclohexane, 1, 4-bis (isocyanatomethyl) cyclohexane, etc. are mentioned.

As an organic polyisocyanate compound (a3), a trimethylol-propane adduct body, the biuret body which reacted with water, the trimer etc. which have an isocyanurate ring can also be used together.

Any suitable catalyst can be used as a catalyst which can be used when obtaining a polyurethane polyol. As such a catalyst, a tertiary amine type compound, an organometallic compound, etc. are mentioned, for example.

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

As an organometallic compound, a tin type compound, a non-tin type compound, etc. are mentioned, for example.

Examples of the tin-based compound include dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin dimaleate, dibutyltin dilaurate (DBTDL), dibutyltin diacetate, and dibutyl Tin sulfide, tributyl tin sulfide, tributyl tin oxide, tributyl tin acetate, triethyl tin ethoxide, tributyl tin ethoxide, dioctyl tin oxide, tributyl tin chloride, tributyl tin trichloroacetate , 2-ethyl tin hexanoate, and the like.

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

When a catalyst is used to obtain a polyurethane polyol, in a system in which two types of polyols, a polyester polyol and a polyether polyol, exist, due to the difference in reactivity, in a system of a single catalyst, gelation or the reaction solution is cloudy It is easy to cause the problem of losing or doing. Then, by using two types of catalysts when obtaining a polyurethane polyol, it becomes easy to control the reaction rate, the selectivity of a catalyst, etc., and these problems can be solved. Examples of the combination of these two catalysts include tertiary amine/organometallic, tin/non-tin, and tin/tin, preferably tin/tin, and more preferably di It is a combination of butyltin dilaurate and tin 2-ethylhexanoate. The compounding ratio is, in terms of weight ratio, 2-ethylhexanoate tin/dibutyltin dilaurate, preferably less than 1, more preferably 0.2 to 0.6. When the compounding ratio is 1 or more, there is a possibility that gelation becomes easy due to the balance of catalyst activity.

When using a catalyst when obtaining a polyurethane polyol, the amount of the catalyst used is preferably 0.01 to 1.0 weight based on the total amount of the polyester polyol (a1), polyether polyol (a2), and organic polyisocyanate compound (a3). %to be.

When a catalyst is used to obtain the polyurethane polyol, the reaction temperature is preferably less than 100°C, more preferably 85°C to 95°C. When it becomes 100 degreeC or more, there exists a possibility that control of a reaction rate and a crosslinked structure may become difficult, and there exists a possibility that it may become difficult to obtain the polyurethane polyol which has a predetermined molecular weight.

When obtaining a polyurethane polyol, it is not necessary to use a catalyst. In that case, reaction temperature becomes like this. Preferably it is 100 degreeC or more, More preferably, it is 110 degreeC or more. Moreover, when obtaining a polyurethane polyol under no catalyst, it is preferable to make it react for 3 hours or more.

As a method of obtaining a polyurethane polyol, for example, 1) a method in which polyester polyol, polyether polyol, catalyst, and organic polyisocyanate are put into a flask, 2) polyester polyol, polyether polyol, and catalyst are put in a flask, The method of adding organic polyisocyanate dropwise is mentioned. As a method of obtaining a polyurethane polyol, the method of 2) is preferable from a viewpoint of controlling reaction.

When obtaining a polyurethane polyol, arbitrary appropriate solvents can be used. As such a solvent, methyl ethyl ketone, ethyl acetate, toluene, xylene, acetone etc. are mentioned, for example. Among these solvents, toluene is preferable.

As a polyfunctional isocyanate compound (B), the thing mentioned above can be used.

In the composition containing a urethane prepolymer (C) and a polyfunctional isocyanate compound (B), it is a range which does not impair the effect of this invention, and arbitrary appropriate other components can be included. Examples of such other components include resin components other than polyurethane resins, tackifiers, inorganic fillers, organic fillers, metal powders, pigments, thin materials, softeners, antioxidants, conductive agents, ultraviolet absorbers, antioxidants, and light stabilizers. , a surface lubricant, a leveling agent, a corrosion inhibitor, a heat-resistant stabilizer, a polymerization inhibitor, a lubricant, a solvent, a catalyst, and the like.

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

The number average molecular weight Mn of the urethane prepolymer (C) is preferably 3000 to 1,000,000.

The equivalent ratio of the NCO group and the OH group in the urethane prepolymer (C) and the polyfunctional isocyanate compound (B) is preferably 5.0 or less, more preferably 0.01 to 3.0, still more preferably NCO group/OH group. preferably 0.02 to 2.5, particularly preferably 0.03 to 2.25, and most preferably 0.05 to 2.0. By adjusting the equivalent ratio of NCO group/OH group within the above range, the wettability of the pressure-sensitive adhesive layer can be improved, so that the surface protection film of the present invention can adhere without entraining air bubbles.

The content of the polyfunctional isocyanate compound (B) is preferably 0.01 to 30% by weight, and more preferably 0.03 to 20% by weight of the polyfunctional isocyanate compound (B) to the urethane prepolymer (C). % by weight, 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. By adjusting the content rate of the polyfunctional isocyanate compound (B) within the above range, the wettability of the pressure-sensitive adhesive layer can be improved, so that the surface protection film of the present invention can adhere without entraining air bubbles.

[Acrylic resin]

As acrylic resin, arbitrary appropriate acrylic adhesives, such as a well-known acrylic adhesive described in Unexamined-Japanese-Patent No. 2013-241606 method etc., can be employ|adopted, for example, in the range which does not impair the effect of this invention.

Acrylic resin can contain arbitrary appropriate components in the range which does not impair the effect of this invention. Examples of such components include resin components other than acrylic resins, tackifiers, inorganic fillers, organic fillers, metal powders, pigments, thin substances, softeners, antioxidants, conductive agents, ultraviolet absorbers, antioxidants, light stabilizers, surface lubricants. , a leveling agent, a corrosion inhibitor, a heat-resistant stabilizer, a polymerization inhibitor, a lubricant, a solvent, a catalyst, and the like.

[Rubber-based resin]

As rubber-type resin, arbitrary appropriate rubber-type adhesives, such as a well-known rubber-type adhesive described in Unexamined-Japanese-Patent No. 2015-074771 etc., can be employ|adopted, for example, in the range which does not impair the effect of this invention. Only 1 type may be sufficient as these, and 2 or more types may be sufficient as them.

The rubber-based resin may contain any appropriate component within a range that does not impair the effects of the present invention. Examples of such components include resin components other than rubber-based resins, tackifiers, inorganic fillers, organic fillers, metal powders, pigments, thin materials, softeners, anti-aging agents, conductive agents, ultraviolet absorbers, antioxidants, light stabilizers, surface lubricants. , a leveling agent, a corrosion inhibitor, a heat-resistant stabilizer, a polymerization inhibitor, a lubricant, a solvent, a catalyst, and the like.

[Silicone-based resin]

As a silicone adhesive, arbitrary appropriate silicone adhesives, such as a well-known silicone adhesive described in Unexamined-Japanese-Patent No. 2014-047280 etc., can be employ|adopted, for example, in the range which does not impair the effect of this invention. Only 1 type may be sufficient as these, and 2 or more types may be sufficient as them.

Silicone-based resin can contain arbitrary appropriate components within the range which does not impair the effect of this invention. Examples of such components include resin components other than silicone resins, tackifiers, inorganic fillers, organic fillers, metal powders, pigments, thin materials, softeners, anti-aging agents, conductive agents, ultraviolet absorbers, antioxidants, light stabilizers, surface lubricants. , a leveling agent, a corrosion inhibitor, a heat-resistant stabilizer, a polymerization inhibitor, a lubricant, a solvent, a catalyst, and the like.

<Silicone-based additive>

As the silicone-based additive, any appropriate silicone-based additive may be employed as long as the effects of the present invention are not impaired. As such a silicone additive, Preferably, at least 1 sort(s) selected from a siloxane bond containing compound, a hydroxyl group containing silicone type compound, and a crosslinkable functional group containing silicone type compound is mentioned.

The number of silicone type additives may be one, and 2 or more types may be sufficient as them.

As the siloxane bond-containing compound, for example, polyether-modified polyorganosiloxane in which a polyether group is introduced into the main chain or side chain of the polyorganosiloxane skeleton (polydimethylsiloxane, etc.), or polyester in the main chain or side chain of the polyorganosiloxane skeleton A polyester-modified polyorganosiloxane having a group introduced therein, an organic compound introduced into the main chain or side chain of the polyorganosiloxane backbone polyorganosiloxane introduced with an organic compound, a silicone-modified polyorganosiloxane introduced into a (meth)acrylic resin ( and meth)acrylic resins, silicone-modified organic compounds obtained by introducing polyorganosiloxane into organic compounds, and silicone-containing organic compounds obtained by copolymerizing organic compounds and silicone compounds. As such a siloxane bond-containing polymer, as a commercially available product, for example, a brand name "LE-302" (manufactured by Kyoesha Chemical Co., Ltd.), a leveling agent of the BYK series manufactured by Bic Chemi 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", "BYK-UV3510", "BYK-UV3570", "BYK-3550", "BYK-SILCLEAN3700", "BYK-SILCLEAN3720", etc.), Algin Chemie AC series leveling agent ("AC") FS180”, “AC FS360”, “AC S20”, etc.), Kyoesha Chemical Co., Ltd. Polyflow series leveling agent (“Polyflow KL-400X”, “Polyflow KL-400HF”, “Polyflow KL-400HF”, “Polyflow”) Flow KL-401”, “Polyflow KL-402”, “Polyflow KL-403”, “Polyflow KL-404”, etc.), Shin-Etsu Chemical Co., Ltd. KP series leveling agent (“KP- 323”, “KP-326”, “KP-341”, “KP-104”, “KP-110”, “KP-112”, etc.), X22 series manufactured by Shin-Etsu Chemical Co., Ltd., KF series, etc. Leveling agent made by Dow Corning (“LP-7001”, “LP-7002”, “8032ADDITIVE”, “57ADDITIVE”, “L-7604”, “FZ-2110”, “FZ-2105”, “67ADDITIVE”) ', "8618ADDITIVE", "3ADDITIVE", "56ADDITIVE", etc.).

As the hydroxyl group-containing silicone compound, for example, polyether-modified polyorganosiloxane in which a polyether group is introduced into the main chain or side chain of the polyorganosiloxane skeleton (polydimethylsiloxane, etc.), or polyester in the main chain or side chain of the polyorganosiloxane skeleton A polyester-modified polyorganosiloxane having a group introduced therein, an organic compound introduced into the main chain or side chain of the polyorganosiloxane backbone polyorganosiloxane introduced with an organic compound, a silicone-modified polyorganosiloxane introduced into a (meth)acrylic resin ( and meth)acrylic resins, silicone-modified organic compounds obtained by introducing polyorganosiloxane into organic compounds, and silicone-containing organic compounds obtained by copolymerizing organic compounds and silicone compounds. In these, polyorganosiloxane frame|skeleton may have a hydroxyl group, and a polyether group, a polyester group, (meth)acryloyl group, and an organic compound may have it. As such a hydroxyl-containing silicone, as a commercial item, it is brand name "X-22-4015", "X-22-4039", "KF6000", "KF6001", "KF6002", "KF6003", "X-22-, for example. 170BX”, “X-22-170DX”, “X-22-176DX”, “X-22-176F” (manufactured by Shin-Etsu Chemical Co., Ltd.), “BYK-370 from Big Chemie Japan Co., Ltd.” ', "BYK-SILCLEAN3700", "BYK-SILCLEAN3720", etc. are mentioned.

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

<Fluorine-based additive>

As the fluorine-based additive, any appropriate fluorine-based additive may be employed as long as the effects of the present invention are not impaired. As such a fluorine-type additive, Preferably at least 1 sort(s) chosen from a fluorine-containing compound, a hydroxyl-containing fluorine-type compound, and a crosslinkable functional group containing fluorine-type compound is mentioned.

The number of fluorine-type additives may be one, and 2 or more types may be sufficient as them.

Examples of the fluorine-containing compound include a compound having a fluoroaliphatic hydrocarbon skeleton, a fluorine-containing organic compound obtained by copolymerizing an organic compound and a fluorine compound, and a fluorine-containing compound containing an organic compound. Examples of the fluoroaliphatic hydrocarbon skeleton include fluoromethane, fluoroethane, fluoropropane, fluoroisopropane, fluorobutane, fluoroisobutane, fluorot-butane, fluoropentane, fluorohexane and the like. and fluoro C1-C10 alkanes. As such a fluorine-containing compound, as a commercial item, for example, AGC Semi Chemical Co., Ltd. Suplon series leveling agent ("S-242", "S-243", "S-420", "S-611") ', "S-651", "S-386", etc.), BYK series leveling agents manufactured by Big Chemie Japan ("BYK-340" etc.), AC series leveling agents manufactured by Algin Chemie ("BYK-340" etc.) AC 110a", "AC 100a", etc.), leveling agent of the Megapac series made by DIC Corporation ("Megapac F-114", "Megapac F-410", "Megapac F-444", "Megapack F-444" Park EXP TP-2066”, “Mega-Park F-430”, “Mega-Park F-472SF”, “Mega-Park F-477”, “Mega-Park F-552”, “Mega-Park F-553”, “Mega Park F-472SF” F-554”, “Mega-Park F-555”, “Mega-Park R-94”, “Mega-Park RS-72-K”, “Mega-Park RS-75”, “Mega-Park F-556”, “Mega-Park R-94” EXP TF-1367", "Megapac EXP TF-1437", "Megapac F-558", "Megapac EXP TF-1537", etc.), Sumitomo 3M Co., Ltd. FC series leveling agent ("FC- 4430", "FC-4432", etc.), Neos Co., Ltd.'s Ptergent series leveling agent ("Ftergent 100", "Ftergent 100C", "Fusergent 110", "Fusergent 150", "Ftergent") "Gent 150CH", "Fusergent AK", "Fusergent 501", "Fusergent 250", "Fusergent 251", "Fusergent 222F", "Fusergent 208G", "Fusergent 300", "Fusergent 310" ’, “Ftergent 400SW”, etc.), Kitamura Chemical Sangyo Co., Ltd. PF series leveling agent (“PF-136A”, “PF-156A”, “PF-151N”, “PF-636”, “ PF-6320", "PF-656", "PF-6520", "PF-651", "PF-652", "PF-3320", etc.).

As a hydroxyl-containing fluorine-type compound, conventionally well-known resin can be used, for example, For example, International Publication No. 94/06870 pamphlet, Unexamined-Japanese-Patent No. 8-12921, Unexamined-Japanese-Patent No. 10-72569, The hydroxyl-containing fluororesin described in Unexamined-Japanese-Patent No. 4-275379, the international publication 97/11130 pamphlet, the international publication 96/26254 pamphlet, etc. are mentioned. As another hydroxyl-containing fluororesin, Unexamined-Japanese-Patent No. 8-231919, Unexamined-Japanese-Patent No. 10-265731, Unexamined-Japanese-Patent No. 10-204374, Unexamined-Japanese-Patent No. 8-12922, for example. The fluoroolefin copolymer etc. which were described in etc. are mentioned. In addition, a copolymer of a compound having an alkyl group fluorinated in a hydroxyl group-containing compound, a fluorine-containing organic compound obtained by copolymerizing a hydroxyl group-containing compound with a fluorine-containing compound, and a fluorine-containing compound containing a hydroxyl group-containing organic compound may be mentioned. As such a hydroxyl-containing fluorine-based compound, commercially available products include, for example, a trade name "Lumiflon" (manufactured by Asahi Glass Co., Ltd.), a trade name "Cefral Coat" (manufactured by Central Glass Co., Ltd.), and a trade name "Zaflon" ( Toagosei Co., Ltd. product), a brand name "Jetple" (made by Daikin Kogyo Co., Ltd.), a brand name "Megapac F-571", "Fluonate" (DIC Corporation product), etc. are mentioned.

Examples of the crosslinkable functional group-containing fluorine-based compound include a carboxylic acid compound having a fluorinated alkyl group such as perfluorooctanoic acid, a copolymer of a compound having a fluorinated alkyl group in a crosslinkable functional group-containing compound, and a crosslinkable functional group-containing compound The fluorine-containing organic compound which copolymerized the fluorine-containing compound, the fluorine-containing compound containing a crosslinkable functional group containing compound, etc. are mentioned. As such a crosslinkable functional group-containing fluorine-based compound, commercially available products include, for example, trade names "Megapac F-570", "Megapac RS-55", "Megapac RS-56", "Megapac RS-72-K", 「Mega Park RS-75」, 「Mega Park RS-76-E」, 「Mega Park RS-76-NS」, 「Mega Park RS-78」, 「Mega Park RS-90」 (manufactured by DIC Co., Ltd.) and the like.

<Other ingredients>

The pressure-sensitive adhesive composition may contain any appropriate other components within a range that does not impair the effects of the present invention. Such other components include, for example, other resin components, tackifiers, inorganic fillers, organic fillers, metal powders, pigments, thin materials, softeners, anti-aging agents, conductive agents, ultraviolet absorbers, antioxidants, light stabilizers, surface lubricants, leveling agents agents, corrosion inhibitors, heat-resistant stabilizers, polymerization inhibitors, lubricants, solvents, catalysts, and the like.

The pressure-sensitive adhesive composition may contain fatty acid ester. The number of fatty acid esters may be one, and 2 or more types may be sufficient as them.

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

As fatty acid ester, any suitable fatty acid ester can be employ|adopted in the range which does not impair the effect of this invention. Examples of such fatty acid ester include polyoxyethylene bisphenol A lauric acid ester, butyl stearate, 2-ethylhexyl palmitic acid, 2-ethylhexyl stearate, monoglyceride behenate, cetyl 2-ethylhexanoate, Isopropyl myristate, isopropyl palmitate, cholesteryl isostearate, lauryl methacrylate, methyl palm fatty acid, methyl laurate, methyl oleate, methyl stearate, myristyl myristate, octyl myristate Dodecyl, pentaerythritol monooleate, pentaerythritol monostearate, pentaerythritol tetrapalmitate, stearyl stearate, isotridecyl stearate, 2-ethylhexanoate triglyceride, butyl laurate, octyl oleate and the like.

When the pressure-sensitive adhesive composition contains a fatty acid ester, the content of the fatty acid ester is, with respect to 100 parts by weight of the base polymer, preferably 1 part by weight to 50 parts by weight, more preferably 1.5 parts by weight to 45 parts by weight, More preferably, it is 2 parts by weight to 40 parts by weight, particularly preferably 2.5 parts by weight to 35 parts by weight, and most preferably 3 parts by weight to 30 parts by weight.

The adhesive composition may contain the ionic liquid containing a fluoro organic anion. Since the pressure-sensitive adhesive composition contains an ionic liquid containing an organic fluoro anion, it is possible to provide a pressure-sensitive adhesive composition having very excellent antistatic properties. One type may be sufficient as such an ionic liquid, and 2 or more types may be sufficient as it.

In this invention, an ionic liquid means the molten salt (ionic compound) which shows a liquid phase at 25 degreeC.

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

As the onium cation capable of constituting the ionic liquid, any suitable onium cation can be employed within a range that does not impair the effects of the present invention. The onium cation is preferably at least one selected from a nitrogen-containing onium cation, a sulfur-containing onium cation, and a phosphorus-containing onium cation. By selecting these onium cations, it is possible to provide a pressure-sensitive adhesive composition having very excellent antistatic properties.

As an onium cation which can comprise an ionic liquid, Preferably, it is at least 1 sort(s) selected from the cation which has a structure represented by General formula (1)-(5).

In the general formula (1), R _a represents a hydrocarbon group having 4 to 20 carbon atoms, which may contain a hetero atom, R _b and R _c are the same or different and represent hydrogen or a hydrocarbon group having 1 to 16 carbon atoms, It may contain a hetero atom. However, when the nitrogen atom contains a double bond, R _c is absent.

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

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

In the general formula (4), Z represents a nitrogen atom, a sulfur atom or a phosphorus atom, R ₁ , R _m , R _n and R _o are the same or different and represent a hydrocarbon group having 1 to 20 carbon atoms, and a hetero atom may be included. provided that when Z is a sulfur atom, R _o is absent.

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

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

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

Among these, from the viewpoint that the effect of the present invention can be further expressed, preferably 1-ethylpyridinium cation, 1-butylpyridinium cation, 1-hexylpyridinium cation, 1-ethyl-3-methylpyri Pyridinium such as dinium cation, 1-butyl-3-methylpyridinium cation, 1-hexyl-3-methylpyridinium cation, 1-butyl-4-methylpyridinium cation, and 1-octyl-4-methylpyridinium cation cation; 1-ethyl-1-methylpyrrolidinium cation, 1-methyl-1-propylpyrrolidinium cation, 1-methyl-1-butylpyrrolidinium cation, 1-methyl-1-pentylpyrrolidinium cation, 1- Methyl-1-hexylpyrrolidinium cation, 1-methyl-1-heptylpyrrolidinium cation, 1-ethyl-1-propylpyrrolidinium cation, 1-ethyl-1-butylpyrrolidinium cation, 1-ethyl- pyrrolidinium cations such as 1-pentylpyrrolidinium cation, 1-ethyl-1-hexylpyrrolidinium cation, and 1-ethyl-1-heptylpyrrolidinium cation; 1-methyl-1-ethylpiperidinium cation, 1-methyl-1-propylpiperidinium cation, 1-methyl-1-butylpiperidinium cation, 1-methyl-1-pentylpiperidinium cation, 1- Methyl-1-hexylpiperidinium cation, 1-methyl-1-heptylpiperidinium cation, 1-ethyl-1-propylpiperidinium cation, 1-ethyl-1-butylpiperidinium cation, 1-ethyl- piperidinium cations such as 1-pentylpiperidinium cation, 1-ethyl-1-hexylpiperidinium cation, 1-ethyl-1-heptylpiperidinium cation, and 1-propyl-1-butylpiperidinium cation; and the like, more preferably 1-hexylpyridinium cation, 1-ethyl-3-methylpyridinium cation, 1-butyl-3-methylpyridinium cation, 1-octyl-4-methylpyridinium cation , 1-methyl-1-propylpyrrolidinium cation, 1-methyl-1-propylpiperidinium cation.

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

Specific examples of the cation represented by the general formula (2) include, for example, 1,3-dimethylimidazolium cation, 1,3-diethylimidazolium cation, 1-ethyl-3-methylimidazolium cation, 1 -Butyl-3-methylimidazolium cation, 1-hexyl-3-methylimidazolium cation, 1-octyl-3-methylimidazolium cation, 1-decyl-3-methylimidazolium cation, 1-dode Syl-3-methylimidazolium cation, 1-tetradecyl-3-methylimidazolium cation, 1,2-dimethyl-3-propylimidazolium cation, 1-ethyl-2,3-dimethylimidazolium cation imidazolium cations such as , 1-butyl-2,3-dimethylimidazolium cation and 1-hexyl-2,3-dimethylimidazolium cation; 1,3-dimethyl-1,4,5,6-tetrahydropyrimidinium cation, 1,2,3-trimethyl-1,4,5,6-tetrahydropyrimidinium cation, 1,2,3, Tetrahydropyri such as 4-tetramethyl-1,4,5,6-tetrahydropyrimidinium cation and 1,2,3,5-tetramethyl-1,4,5,6-tetrahydropyrimidinium cation medium cation; 1,3-dimethyl-1,4-dihydropyrimidinium cation, 1,3-dimethyl-1,6-dihydropyrimidinium cation, 1,2,3-trimethyl-1,4-dihydropyrimidi nium cation, 1,2,3-trimethyl-1,6-dihydropyrimidinium cation, 1,2,3,4-tetramethyl-1,4-dihydropyrimidinium cation, 1,2,3, dihydropyrimidinium cations such as 4-tetramethyl-1,6-dihydropyrimidinium cation; and the like.

Among these, 1,3-dimethylimidazolium cation, 1,3-diethylimidazolium cation, and 1-ethyl-3-methylimida are preferred from the viewpoint that the effect of the present invention can be further expressed. Zolium cation, 1-butyl-3-methylimidazolium cation, 1-hexyl-3-methylimidazolium cation, 1-octyl-3-methylimidazolium cation, 1-decyl-3-methylimidazolium cation imidazolium cations such as , 1-dodecyl-3-methylimidazolium cation and 1-tetradecyl-3-methylimidazolium cation, more preferably 1-ethyl-3-methylimidazolium cation; 1-hexyl-3-methylimidazolium cation.

As a cation represented by General formula (3), a pyrazolium cation, a pyrazolinium cation, etc. are mentioned, for example.

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

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

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, Cation, tributylethylammonium cation, trimethylpropylammonium cation, trimethyldecylammonium cation, N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium cation, glycidyltrimethylammonium cation, trimethylsulfur Phonium cation, triethylsulfonium cation, tributylsulfonium cation, trihexylsulfonium cation, diethylmethylsulfonium cation, dibutylethylsulfonium cation, dimethyldecylsulfonium cation, tetramethylphosphonium cation, tetraethylphosph Phonium cation, tetrabutylphosphonium cation, tetrahexylphosphonium cation, tetraoctylphosphonium cation, triethylmethylphosphonium cation, tributylethylphosphonium cation, trimethyldecylphosphonium cation, diallyldimethylammonium cation, etc. are mentioned. have.

Among these, triethylmethylammonium cation, tributylethylammonium cation, trimethyldecylammonium cation, diethylmethylsulfonium cation, dibutylethylsulfonium cation, from the viewpoint of being able to further express the effect of the present invention, is preferable. Asymmetric tetraalkylammonium cations, such as dimethyldecylsulfonium cation, triethylmethylphosphonium cation, tributylethylphosphonium cation, and trimethyldecylphosphonium cation, trialkylsulfonium cation, tetraalkylphosphonium cation, N, N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium cation, glycidyltrimethylammonium cation, diallyldimethylammonium cation, N,N-dimethyl-N-ethyl-N-propylammonium cation, N,N-dimethyl-N-ethyl-N-butylammonium cation, N,N-dimethyl-N-ethyl-N-pentylammonium cation, N,N-dimethyl-N-ethyl-N-hexylammonium cation, N, N-dimethyl-N-ethyl-N-heptylammonium cation, N,N-dimethyl-N-ethyl-N-nonylammonium cation, N,N-dimethyl-N,N-dipropylammonium cation, N,N-di Ethyl-N-propyl-N-butylammonium cation, N,N-dimethyl-N-propyl-N-pentylammonium cation, N,N-dimethyl-N-propyl-N-hexylammonium cation, N,N-dimethyl- N-propyl-N-heptylammonium cation, N,N-dimethyl-N-butyl-N-hexylammonium cation, N,N-diethyl-N-butyl-N-heptylammonium cation, N,N-dimethyl-N -pentyl-N-hexylammonium cation, N,N-dimethyl-N,N-dihexylammonium cation, trimethylheptylammonium cation, N,N-diethyl-N-methyl-N-propylammonium cation, N,N- Diethyl-N-methyl-N-pentylammonium cation, N,N-diethyl-N-methyl-N-heptylammonium cation, N,N-diethyl-N-propyl-N-pentylammonium cation, triethylpropyl Ammonium cation, triethylpentylammonium cation, triethylheptylammonium cation, N,N-dipropyl-N-methyl-N-ethylammonium cation, N,N-dipropyl-N-methyl-N-pentylammonium cation, N ,N-dipropyl-N-butyl-N-hexylammonium cation, N,N-dipropyl-N,N-dihexylammonium cation, N,N-dibutyl-N-methyl-N-pentylammonium cation, N ,N-dibutyl-N-methyl -N-hexylammonium cation, trioctylmethylammonium cation, N-methyl-N-ethyl-N-propyl-N-pentylammonium cation, etc. are mentioned, More preferably, it is a trimethylpropylammonium cation.

As the fluoroorganic anion capable of constituting the ionic liquid, any suitable fluoroorganic anion can be employed as long as the effects of the present invention are not impaired. Such a fluoroorganic anion may be completely fluorinated (perfluorinated) or may be partially fluorinated.

Examples of the fluoroorganic anion include fluorinated arylsulfonate, perfluoroalkanesulfonate, bis(fluorosulfonyl)imide, bis(perfluoroalkanesulfonyl)imide, cyanoperfluoro Alkanesulfonylamide, bis(cyano)perfluoroalkanesulfonylmethide, cyano-bis-(perfluoroalkanesulfonyl)methide, tris(perfluoroalkanesulfonyl)methide, trifluoroacetate , perfluoroalkylate, tris(perfluoroalkanesulfonyl)methide, (perfluoroalkanesulfonyl)trifluoroacetamide, and the like.

Among these fluoroorganic anions, more preferably, they are perfluoroalkylsulfonate, bis(fluorosulfonyl)imide, and bis(perfluoroalkanesulfonyl)imide, and more specifically, for example, fluoromethanesulfonate, pentafluoroethanesulfonate, heptafluoropropanesulfonate, nonafluorobutanesulfonate, bis(fluorosulfonyl)imide, and bis(trifluoromethanesulfonyl)imide.

As a specific example of an ionic liquid, it can be used, selecting suitably from the combination of the said cation component and the said anion component. Specific examples of such an ionic liquid include 1-hexylpyridiniumbis(fluorosulfonyl)imide, 1-ethyl-3-methylpyridinium trifluoromethanesulfonate, 1-ethyl-3-methyl Pyridinium pentafluoroethanesulfonate, 1-ethyl-3-methylpyridinium heptafluoropropanesulfonate, 1-ethyl-3-methylpyridinium nonafluorobutanesulfonate, 1-butyl-3-methylpyridinium Trifluoromethanesulfonate, 1-butyl-3-methylpyridiniumbis(trifluoromethanesulfonyl)imide, 1-butyl-3-methylpyridiniumbis(pentafluoroethanesulfonyl)imide, 1 -Octyl-4-methylpyridiniumbis(fluorosulfonyl)imide, 1,1-dimethylpyrrolidiniumbis(trifluoromethanesulfonyl)imide, 1-methyl-1-ethylpyrrolidiniumbis( Trifluoromethanesulfonyl)imide, 1-methyl-1-propylpyrrolidiniumbis(trifluoromethanesulfonyl)imide, 1-methyl-1-propylpyrrolidiniumbis(fluorosulfonyl)imide De, 1-methyl-1-butylpyrrolidinium bis(trifluoromethanesulfonyl)imide, 1-methyl-1-pentylpyrrolidiniumbis(trifluoromethanesulfonyl)imide, 1-methyl- 1-Hexylpyrrolidiniumbis(trifluoromethanesulfonyl)imide, 1-methyl-1-heptylpyrrolidiniumbis(trifluoromethanesulfonyl)imide, 1-ethyl-1-propylpyrrolidinium Bis(trifluoromethanesulfonyl)imide, 1-ethyl-1-butylpyrrolidiniumbis(trifluoromethanesulfonyl)imide, 1-ethyl-1-pentylpyrrolidiniumbis(trifluoromethane sulfonyl)imide, 1-ethyl-1-hexylpyrrolidiniumbis(trifluoromethanesulfonyl)imide, 1-ethyl-1-heptylpyrrolidiniumbis(trifluoromethanesulfonyl)imide; 1,1-dipropylpyrrolidiniumbis(trifluoromethanesulfonyl)imide, 1-propyl-1-butylpyrrolidiniumbis(trifluoromethanesulfonyl)imide, 1,1-dibutylpyr Rollidiniumbis(trifluoromethanesulfonyl)imide, 1-propylpiperidiniumbis(trifluoromethanesulfonyl)imide, 1-pentylpiperidiniumbis(trifluoromethanesulfonyl)imide; 1,1-dimethylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-ethylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-propyl pipe Lidiniumbis(trifluoromethanesulfonyl)imide, 1-methyl-1-propylpiperidinium Bis(fluorosulfonyl)imide, 1-methyl-1-butylpiperidiniumbis(trifluoromethanesulfonyl)imide, 1-methyl-1-pentylpiperidiniumbis(trifluoromethanesulfonyl) )imide, 1-methyl-1-hexylpiperidiniumbis(trifluoromethanesulfonyl)imide, 1-methyl-1-heptylpiperidiniumbis(trifluoromethanesulfonyl)imide, 1- Ethyl-1-propylpiperidiniumbis(trifluoromethanesulfonyl)imide, 1-ethyl-1-butylpiperidiniumbis(trifluoromethanesulfonyl)imide, 1-ethyl-1-pentylpipe Lidinium bis(trifluoromethanesulfonyl)imide, 1-ethyl-1-hexylpiperidiniumbis(trifluoromethanesulfonyl)imide, 1-ethyl-1-heptylpiperidiniumbis(trifluoro Romethanesulfonyl)imide, 1,1-dipropylpiperidiniumbis(trifluoromethanesulfonyl)imide, 1-propyl-1-butylpiperidiniumbis(trifluoromethanesulfonyl)imide , 1,1-dibutylpiperidiniumbis(trifluoromethanesulfonyl)imide, 1,1-dimethylpyrrolidiniumbis(pentafluoroethanesulfonyl)imide, 1-methyl-1-ethylpi Rollidiniumbis(pentafluoroethanesulfonyl)imide, 1-methyl-1-propylpyrrolidiniumbis(pentafluoroethanesulfonyl)imide, 1-methyl-1-butylpyrrolidiniumbis(pentafluoro Loethanesulfonyl)imide, 1-methyl-1-pentylpyrrolidiniumbis(pentafluoroethanesulfonyl)imide, 1-methyl-1-hexylpyrrolidiniumbis(pentafluoroethanesulfonyl)imide De, 1-methyl-1-heptylpyrrolidiniumbis(pentafluoroethanesulfonyl)imide, 1-ethyl-1-propylpyrrolidiniumbis(pentafluoroethanesulfonyl)imide, 1-ethyl- 1-Butylpyrrolidiniumbis(pentafluoroethanesulfonyl)imide, 1-ethyl-1-pentylpyrrolidiniumbis(pentafluoroethanesulfonyl)imide, 1-ethyl-1-hexylpyrrolidinium Bis(pentafluoroethanesulfonyl)imide, 1-ethyl-1-heptylpyrrolidiniumbis(pentafluoroethanesulfonyl)imide, 1,1-dipropylpyrrolidiniumbis(pentafluoroethanesulfonyl) Ponyl)imide, 1-propyl-1-butylpyrrolidiniumbis(pentafluoroethanesulfonyl)imide, 1,1-dibutylpyrrolidiniumbis(pentafluoroethanesulfonyl)imide, 1- Propylpiperidiniumbis(pentafluoroethanesulfonyl)imide, 1-pentylpiperidiniumbis(pentafluoroethanesulfonyl)imide, 1,1-dimethylpiperid Diniumbis(pentafluoroethanesulfonyl)imide, 1-methyl-1-ethylpiperidiniumbis(pentafluoroethanesulfonyl)imide, 1-methyl-1-propylpiperidiniumbis(pentafluoro Ethanesulfonyl)imide, 1-methyl-1-butylpiperidiniumbis(pentafluoroethanesulfonyl)imide, 1-methyl-1-pentylpiperidiniumbis(pentafluoroethanesulfonyl)imide , 1-methyl-1-hexylpiperidiniumbis(pentafluoroethanesulfonyl)imide, 1-methyl-1-heptylpiperidiniumbis(pentafluoroethanesulfonyl)imide, 1-ethyl-1 -Propylpiperidiniumbis(pentafluoroethanesulfonyl)imide, 1-ethyl-1-butylpiperidiniumbis(pentafluoroethanesulfonyl)imide, 1-ethyl-1-pentylpiperidiniumbis (Pentafluoroethanesulfonyl)imide, 1-ethyl-1-hexylpiperidiniumbis(pentafluoroethanesulfonyl)imide, 1-ethyl-1-heptylpiperidiniumbis(pentafluoroethanesulfonyl)imide Ponyl)imide, 1,1-dipropylpiperidiniumbis(pentafluoroethanesulfonyl)imide, 1-propyl-1-butylpiperidiniumbis(pentafluoroethanesulfonyl)imide, 1, 1-dibutylpiperidiniumbis(pentafluoroethanesulfonyl)imide, 1-ethyl-3-methylimidazolium trifluoroacetate, 1-ethyl-3-methylimidazolium heptafluorobutyrate, 1 -ethyl-3-methylimidazolium trifluoromethanesulfonate, 1-ethyl-3-methylimidazolium heptafluoropropanesulfonate, 1-ethyl-3-methylimidazolium nonafluorobutanesulfonate; 1-ethyl-3-methylimidazoliumbis(trifluoromethanesulfonyl)imide, 1-ethyl-3-methylimidazoliumbis(fluorosulfonyl)imide, 1-ethyl-3-methyl Midazoliumbis(pentafluoroethanesulfonyl)imide, 1-ethyl-3-methylimidazoliumtris(trifluoromethanesulfonyl)methide, 1-butyl-3-methylimidazoliumtrifluoroacetate , 1-butyl-3-methylimidazolium heptafluorobutyrate, 1-butyl-3-methylimidazolium trifluoromethanesulfonate, 1-butyl-3-methylimidazolium perfluorobutanesulfonate, 1-Butyl-3-methylimidazoliumbis(trifluoromethanesulfonyl)imide, 1-hexyl-3-methylimidazoliumtrifluoromethanesulfonate, 1-hexyl-3-methylimidazoliumbis (Fluorosulfonyl)imide, 1,2-dimethyl-3-propylimidazoliumbis(tri Fluoromethanesulfonyl)imide, 1-ethyl-2,3,5-trimethylpyrazoliumbis(trifluoromethanesulfonyl)imide, 1-propyl-2,3,5-trimethylpyrazoliumbis(tri Fluoromethanesulfonyl)imide, 1-butyl-2,3,5-trimethylpyrazoliumbis(trifluoromethanesulfonyl)imide, 1-ethyl-2,3,5-trimethylpyrazoliumbis(penta Fluoroethanesulfonyl)imide, 1-propyl-2,3,5-trimethylpyrazoliumbis(pentafluoroethanesulfonyl)imide, 1-butyl-2,3,5-trimethylpyrazoliumbis(penta Fluoroethanesulfonyl)imide, 1-ethyl-2,3,5-trimethylpyrazolium (trifluoromethanesulfonyl)trifluoroacetamide, 1-propyl-2,3,5-trimethylpyrazolium ( Trifluoromethanesulfonyl)trifluoroacetamide, 1-butyl-2,3,5-trimethylpyrazolium (trifluoromethanesulfonyl)trifluoroacetamide, trimethylpropylammonium bis(trifluoromethanesulfonyl) Ponyl)imide, N,N-dimethyl-N-ethyl-N-propylammoniumbis(trifluoromethanesulfonyl)imide, N,N-dimethyl-N-ethyl-N-butylammoniumbis(trifluoro Methanesulfonyl)imide, N,N-dimethyl-N-ethyl-N-pentylammoniumbis(trifluoromethanesulfonyl)imide, N,N-dimethyl-N-ethyl-N-hexylammoniumbis(tri Fluoromethanesulfonyl)imide, N,N-dimethyl-N-ethyl-N-heptylammoniumbis(trifluoromethanesulfonyl)imide, N,N-dimethyl-N-ethyl-N-nonylammoniumbis (trifluoromethanesulfonyl)imide, N,N-dimethyl-N,N-dipropylammoniumbis(trifluoromethanesulfonyl)imide, N,N-dimethyl-N-propyl-N-butylammonium Bis(trifluoromethanesulfonyl)imide, N,N-dimethyl-N-propyl-N-pentylammoniumbis(trifluoromethanesulfonyl)imide, N,N-dimethyl-N-propyl-N- Hexylammoniumbis(trifluoromethanesulfonyl)imide, N,N-dimethyl-N-propyl-N-heptylammoniumbis(trifluoromethanesulfonyl)imide, N,N-dimethyl-N-butyl- N-Hexylammoniumbis(trifluoromethanesulfonyl)imide, N,N-dimethyl-N-butyl-N-heptylammoniumbis(trifluoromethanesulfonyl)imide, N,N-dimethyl-N- Pentyl-N-hexylammoniumbis(trifluoromethanesulfonyl)imide, N,N-dimethyl-N,N-dihexylam Moniumbis(trifluoromethanesulfonyl)imide, trimethylheptylammoniumbis(trifluoromethanesulfonyl)imide, N,N-diethyl-N-methyl-N-propylammoniumbis(trifluoromethanesulfonyl)imide Ponyl)imide, N,N-diethyl-N-methyl-N-pentylammoniumbis(trifluoromethanesulfonyl)imide, N,N-diethyl-N-methyl-N,N-heptylammoniumbis (trifluoromethanesulfonyl)imide, N,N-diethyl-N-propyl-N-pentylammoniumbis(trifluoromethanesulfonyl)imide, triethylpropylammoniumbis(trifluoromethanesulfonyl) ) imide, triethylpentylammoniumbis(trifluoromethanesulfonyl)imide, triethylheptylammoniumbis(trifluoromethanesulfonyl)imide, N,N-dipropyl-N-methyl-N-ethyl Ammoniumbis(trifluoromethanesulfonyl)imide, N,N-dipropyl-N-methyl-N-pentylammoniumbis(trifluoromethanesulfonyl)imide, N,N-dipropyl-N-butyl -N-Hexylammoniumbis(trifluoromethanesulfonyl)imide, N,N-dipropyl-N,N-dihexylammoniumbis(trifluoromethanesulfonyl)imide, N,N-dibutyl- N-methyl-N-pentylammoniumbis(trifluoromethanesulfonyl)imide, N,N-dibutyl-N-methyl-N-hexylammoniumbis(trifluoromethanesulfonyl)imide, trioctylmethyl Ammoniumbis(trifluoromethanesulfonyl)imide, N-methyl-N-ethyl-N-propyl-N-pentylammoniumbis(trifluoromethanesulfonyl)imide, 1-butylpyridinium (trifluoro Methanesulfonyl)trifluoroacetamide, 1-butyl-3-methylpyridinium (trifluoromethanesulfonyl)trifluoroacetamide, 1-ethyl-3-methylimidazolium (trifluoromethanesulfonyl) ) Trifluoroacetamide, tetrahexylammonium bis(trifluoromethanesulfonyl)imide, diallyldimethylammonium trifluoromethanesulfonate, diallyldimethylammonium bis(trifluoromethanesulfonyl)imide, di Allyldimethylammonium bis(pentafluoroethanesulfonyl)imide, N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium trifluoromethanesulfonate, N,N-diethyl- N-methyl-N-(2-methoxyethyl)ammoniumbis(trifluoromethanesulfonyl)imide, N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammoniumbis(penta Fluoroethanesulfonyl)imide, glycidyltrimethylammoniumtrifluoromethanesulfo Nate, glycidyltrimethylammonium bis(trifluoromethanesulfonyl)imide, glycidyltrimethylammoniumbis(pentafluoroethanesulfonyl)imide, diallyldimethylammonium bis(trifluoromethanesulfonyl)imide de, diallyldimethylbis(pentafluoroethanesulfonyl)imide, lithium bis(trifluoromethanesulfonyl)imide, lithium bis(fluorosulfonyl)imide, and the like.

Among these ionic liquids, more preferably 1-hexylpyridiniumbis(fluorosulfonyl)imide, 1-ethyl-3-methylpyridinium trifluoromethanesulfonate, 1-ethyl-3-methylpyri Dinium pentafluoroethanesulfonate, 1-ethyl-3-methylpyridinium heptafluoropropanesulfonate, 1-ethyl-3-methylpyridinium nonafluorobutanesulfonate, 1-butyl-3-methylpyridinium tri Fluoromethanesulfonate, 1-butyl-3-methylpyridiniumbis(trifluoromethanesulfonyl)imide, 1-octyl-4-methylpyridiniumbis(fluorosulfonyl)imide, 1-methyl- 1-propylpyrrolidiniumbis(trifluoromethanesulfonyl)imide, 1-methyl-1-propylpyrrolidiniumbis(fluorosulfonyl)imide, 1-methyl-1-propylpiperidiniumbis( Trifluoromethanesulfonyl)imide, 1-methyl-1-propylpiperidiniumbis(fluorosulfonyl)imide, 1-ethyl-3-methylimidazoliumtrifluoromethanesulfonate, 1-ethyl -3-methylimidazolium heptafluoropropanesulfonate, 1-ethyl-3-methylimidazoliumbis(trifluoromethanesulfonyl)imide, 1-ethyl-3-methylimidazoliumbis(fluoro Sulfonyl)imide, 1-hexyl-3-methylimidazoliumbis(fluorosulfonyl)imide, trimethylpropylammoniumbis(trifluoromethanesulfonyl)imide, lithium bis(trifluoromethanesulfonyl) ) imide, and lithium bis(fluorosulfonyl)imide.

A commercially available ionic liquid may be used, but it is also possible to synthesize|combine it as follows. The method for synthesizing the ionic liquid is not particularly limited as long as the target ionic liquid is obtained, but generally described in the document "Ionic liquid - the front line and future of development -" (published by CMC Publishing Co., Ltd.) As described above, halide method, hydroxide method, acid ester method, complex formation method, neutralization method and the like are used.

For the halide method, the hydroxide method, the acid ester method, the complex formation method and the neutralization method, the synthesis method is shown using nitrogen-containing onium salt as an example, but other sulfur-containing onium salts, phosphorus-containing onium salts, etc. It can be obtained by the same method also about an external ionic liquid.

The halide method is a method performed by a reaction as shown in Reaction Formulas (1) to (3). First, a halide is obtained by reacting a tertiary amine with an alkyl halide (reaction formula (1), chlorine, bromine and iodine are used as halogen).

The obtained halide is an acid (HA) or salt (MA and M are cations that form a salt with the target anion, such as ammonium, lithium, sodium, potassium, etc.) having an anionic structure (A ^{- ) of an ionic liquid, and} A target ionic liquid (R ₄ NA) is obtained by reacting.

The hydroxide method is a method performed by a reaction as shown in the reaction formulas (4) to (8). First, a halide (R ₄ NX) is a hydroxide by an ion exchange membrane method electrolysis (Scheme (4)), an OH type ion exchange resin method (Scheme (5)), or _{a reaction of silver oxide (Ag 2} O) (Scheme (6)) (R ₄ NOH) is obtained (chlorine, bromine and iodine are used as halogen).

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

The acid ester method is a method performed by a reaction as shown in Reaction Formulas (9) to (11). First, a tertiary amine (R ₃ N) is reacted with an acid ester to obtain an acid ester (reaction formula (9). As the acid ester, esters of inorganic acids such as sulfuric acid, sulfurous acid, phosphoric acid, phosphorous acid, and carbonic acid, methanesulfonic acid, methylphosphonic acid , esters of organic acids such as formic acid, etc.).

_{The target ionic liquid (R 4} NA) is obtained by using the reactions of the reaction formulas (10) to (11) in the same manner as in the above halogenation method for the obtained acid ester. Moreover, an ionic liquid can also be obtained directly by using methyltrifluoromethanesulfonate, methyltrifluoroacetate, etc. as an acid ester.

The neutralization method is a method performed by a reaction as shown in Scheme (12). Can be obtained by reacting a tertiary amine with an organic acid such _{as CF 3} COOH, CF ₃ SO ₃ H, (CF ₃ SO ₂ ) ₂ NH, (CF ₃ SO ₂ ) ₃ CH, (C ₂ F ₅ SO ₂ ) _{2 NH} have.

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

The blending amount of the ionic liquid cannot be defined uniformly because it changes depending on the compatibility of the polymer and the ionic liquid to be used, but in general, it is preferably 0.001 to 50 parts by weight based on 100 parts by weight of the base polymer. , more preferably 0.01 parts by weight to 40 parts by weight, still more preferably 0.01 parts by weight to 30 parts by weight, particularly preferably 0.01 parts by weight to 20 parts by weight, most preferably 0.01 parts by weight to 10 parts by weight is wealth By adjusting the compounding quantity of an ionic liquid within the said range, the adhesive composition excellent in antistatic property can be provided. When the amount of the ionic liquid is less than 0.01 part by weight, there is a fear that sufficient antistatic properties cannot be obtained. When the above compounding amount of the ionic liquid exceeds 50 parts by weight, contamination on the adherend tends to increase.

The adhesive composition may contain the modified silicone oil in the range which does not impair the effect of this invention. When the pressure-sensitive adhesive composition contains the modified silicone oil, the effect of the antistatic property can be expressed. In particular, by using together with an ionic liquid, the effect of an antistatic property can be expressed still more effectively.

When the pressure-sensitive adhesive composition contains the modified silicone oil, the content thereof is preferably 0.001 parts by weight to 50 parts by weight, more preferably 0.005 parts by weight to 40 parts by weight, with respect to 100 parts by weight of the base polymer, further Preferably it is 0.007 weight part - 30 weight part, Especially preferably, it is 0.008 weight part - 20 weight part, Most preferably, it is 0.01 weight part - 10 weight part. By adjusting the content rate of the modified silicone oil within the above range, the effect of the antistatic property can be more effectively expressed.

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

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

Examples of the polyether-modified silicone oil include side-chain polyether-modified silicone oil and both terminal polyether-modified silicone oil. Among these, the polyether-modified silicone oil of both terminal type is preferable at the point that the effect of an antistatic property can be fully and more effectively expressed.

≪≪Use≫≫

The surface protection film of this invention is equipped with superhard peelability, and has low contamination property on the to-be-adhered body surface. For this reason, it can use suitably for the surface protection of an optical member or an electronic member. As for the optical member of this invention, the surface protection film of this invention is adhere|attached. As for the electronic member of this invention, the surface protection film of this invention is adhere|attached.

<Example>

Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited at all to these Examples. In addition, the test and evaluation method in an Example etc. are as follows. In addition, when it describes as "part", unless there is a special notice, "weight part" is meant, and when it describes as "%", it means "weight%" unless there is a special notice.

<Peel force versus PET (peel force after 23°C × 30 minutes and peel force after 80°C × 7 days) at a peeling rate of 6000 mm/min>

A polyethylene terephthalate film having a thickness of 25 μm was bonded to the pressure-sensitive adhesive layer, and the peel force when the polyethylene terephthalate film was peeled at 23° C., a peel angle of 180 degrees, and a peel rate of 6000 mm/min was measured as follows.

2 kg of SUS304 plate through double-sided adhesive tape (manufactured by Nitto Denko Corporation, trade name "No. 531") on the entire surface of the surface opposite to the pressure-sensitive adhesive layer of the surface protection film (width 50 mm x length 140 mm) from which the separator was peeled. It was adhered using a hand roller.

Next, on the surface of the pressure-sensitive adhesive layer, a polyethylene terephthalate film (manufactured by Toray Corporation, trade name "Lumirer S-10", thickness: 25 µm, width: 25 mm) was adhered (temperature: 23°C, humidity: 65%, 2 kg roller) 1 round trip).

The sample for evaluation obtained as mentioned above was measured by the tensile test. As a tensile testing machine, the brand name "Autograph AG-Xplus HS 6000 mm/min high-speed model (AG-50NX plus)" manufactured by Shimadzu Corporation was used. After setting the sample for evaluation in the tensile tester, the tensile test was started after leaving it to stand for 30 minutes under an environmental temperature of 23°C or for 7 days under a temperature environment of 80°C. The conditions of the tensile test were: peeling angle: 180 degrees, peeling speed (tensile speed): 6000 mm/min. The load when the PET film was peeled from the said surface protection film was measured, and the average load at that time was made into the peeling force of the surface protection film.

<Peel force to PET (peel force after 23°C × 30 minutes and peel force after 80°C × 7 days) at a peeling rate of 300 mm/min>

A polyethylene terephthalate film having a thickness of 25 µm was bonded to the pressure-sensitive adhesive layer, and the peel force when the polyethylene terephthalate film was peeled at 23° C., a peeling angle of 180 degrees, and a peeling rate of 300 mm/min was measured as follows.

2 kg of SUS304 plate through double-sided adhesive tape (manufactured by Nitto Denko Corporation, trade name "No. 531") on the entire surface of the surface opposite to the pressure-sensitive adhesive layer of the surface protection film (width 50 mm x length 140 mm) from which the separator was peeled. It was adhered using a hand roller.

Next, on the surface of the pressure-sensitive adhesive layer, a polyethylene terephthalate film (manufactured by Toray Corporation, trade name "Lumirer S-10", thickness: 25 µm, width: 25 mm) was adhered (temperature: 23°C, humidity: 65%, 2 kg roller) 1 round trip).

The sample for evaluation obtained as mentioned above was used for a tensile test. As a tensile tester, the brand name "Autograph AG-Xplus HS 6000 mm/min high-speed model (AG-50NX plus)" manufactured by Shimadzu Corporation was used. After setting the sample for evaluation in the tensile tester, the tensile test was started after leaving it to stand for 30 minutes under an environmental temperature of 23°C or for 7 days under a temperature environment of 80°C. The conditions of the tensile test were: peeling angle: 180 degrees, peeling speed (tensile speed): 300 mm/min. The load when the PET film was peeled from the said surface protection film was measured, and the average load at that time was made into the peeling force of the surface protection film.

<Residual adhesion rate>

A surface protection film was bonded to the entire surface of a glass plate (manufactured by Matsunami Glass, 1.35 mm × 10 cm × 10 cm) with a hand roller, and stored at a temperature of 23° C. and a humidity of 55% RH for 24 hours. The surface protection film was peeled off at a speed of 0.3 m/min, and a 19 mm wide No. 31B tape (manufactured by Nitto Denko Co., Ltd., substrate thickness: 25 µm) cut to a length of 150 mm was applied at a temperature of 23°C and a humidity of 55% RH. It was affixed by 1 reciprocation of a 2.0 kg roller in atmosphere. After curing for 30 minutes in an atmosphere of temperature 23° C. and humidity 55% RH, a tensile tester (“Autograph AG-Xplus HS 6000 mm/min high-speed model (AG-50NX plus)” manufactured by Shimadzu Corporation) was used. Thus, it was peeled at a peeling angle of 180 degrees and a tensile rate of 300 mm/min, and the adhesive force was measured.

Separately, also about the glass plate which did not perform the above process, the adhesive force of the No. 31B tape of 19 mm width was similarly measured, and the residual adhesive rate was computed with the following formula.

Residual adhesive rate (%) = (No.31B adhesive force with respect to the glass plate after surface protection film peeling / No.31B adhesive force with respect to a glass plate) *100

This residual adhesive rate becomes an index|index of how much the adhesive component of a surface protection film is transcribe|transferred and contaminated on the surface with respect to to-be-adhered body. The higher the value of the residual adhesion rate, the better the surface protection film does not contaminate the adherend, and the lower the value of the residual adhesion rate, the more contaminating the surface of the adherend with the pressure-sensitive adhesive component or the like.

<To glass peel force at a peeling rate of 6000 mm/min (peel force after 23° C.×30 minutes and peel force after 80° C.×7 days)>

The surface protection film (width 25mm x length 140mm) from which the separator was peeled was adhere|attached to glass (soda-lime glass, the Matsunami Glass Kogyo Co., Ltd. make) with 1 reciprocating 2kg hand roller.

The sample for evaluation obtained as mentioned above was measured with the tensile tester. As a tensile tester, the brand name "Autograph AG-Xplus HS 6000 mm/min high-speed model (AG-50NX plus)" manufactured by Shimadzu Corporation was used. After setting the sample for evaluation in the tensile tester, the tensile test was started after leaving it to stand for 30 minutes under an environmental temperature of 23°C or for 7 days under a temperature environment of 80°C. The conditions of the tensile test were: peeling angle: 180 degrees, peeling speed (tensile speed): 6000 mm/min. The load at the time of peeling a surface protection film from the said glass was measured, and the average load at that time was made into the peeling force of the surface protection film.

<To glass peel force at a peeling rate of 300 mm/min (peel force after 23° C.×30 minutes and peel force after 80° C.×7 days)>

The surface protection film (width 25mm x length 140mm) from which the separator was peeled was adhere|attached to glass (soda-lime glass, the Matsunami Glass Kogyo Co., Ltd. make) with 1 reciprocating 2kg hand roller.

The sample for evaluation obtained as mentioned above was measured with the tensile tester. As a tensile tester, the brand name "Autograph AG-Xplus HS 6000 mm/min high-speed model (AG-50NX plus)" manufactured by Shimadzu Corporation was used. After setting the sample for evaluation in the tensile tester, the tensile test was started after leaving it to stand for 30 minutes under an environmental temperature of 23°C or for 7 days under a temperature environment of 80°C. The conditions of the tensile test were: peeling angle: 180 degrees, peeling speed (tensile speed): 300 mm/min. The load at the time of peeling a surface protection film from the said glass was measured, and the average load at that time was made into the peeling force of the surface protection film.

[Example 1]

As the polyol (A), Preminol S3011, a polyol having three OH groups (manufactured by Asahi Glass Co., Ltd., Mn=10000): 85 parts by weight, Sannix GP-3000, a polyol having three OH groups (Sanyo Chemical Co., Ltd.) manufactured by Shiki, Mn=3000): 13 parts by weight, Sannix GP-1000, a polyol having three OH groups (manufactured by Sanyo Chemical Co., Ltd., Mn=1000): 2 parts by weight, as a polyfunctional isocyanate compound (B) Coronate HX, a polyfunctional alicyclic isocyanate compound (manufactured by Nippon Polyurethane Kogyo Co., Ltd.): 18 parts by weight, catalyst (manufactured by Nippon Chemical Industries, Ltd., trade name: Nasem Ferric): 0.1 parts by weight, fatty acid ester Isopropyl myristate (manufactured by Kao Corporation, trade name: Exepal IPM, Mn = 270): 20 parts by weight, 1-ethyl-3-methylimidazolium bis(fluoromethanesulfonyl)imide (di Ichi Kogyo Seyaku Co., Ltd. make, trade name: AS110): 1.5 parts by weight, polyether-modified silicone oil of both ends (Shin-Etsu Chemical Co., Ltd., trade name: KF-6004): 0.02 parts by weight, siloxane bond Containing polymer (Kyoesha Chemical Co., Ltd. make, trade name: LE-302): 0.25 weight part, ethyl acetate was added as a diluting solvent, mixing stirring was performed, and the adhesive composition (1) was manufactured.

The obtained pressure-sensitive adhesive composition (1) is applied to a base material "Lumiror S10" (thickness 38 µm, manufactured by Toray Corporation) containing a polyester resin so that the thickness after drying becomes 10 µm with a fountain roll, and a drying temperature of 130 ° C., It was cured and dried under the conditions of a drying time of 30 seconds. In this way, the adhesive layer was produced on the base material. Next, the silicone-treated surface of the base material (separator) containing the 25-micrometer-thick polyester resin which silicone-treated on the surface of the adhesive layer was bonded together, and the surface protection film (1) with a separator was obtained.

The results are shown in Table 1.

[Example 2]

1-Ethyl-3-methylimidazolium bis(fluoromethanesulfonyl)imide (manufactured by Daiichi Kogyo Seyaku Co., Ltd., trade name: AS110) is not used, and a siloxane bond-containing polymer (Kyoesha Co., Ltd.) is not used. A fluorine-containing polymer (manufactured by DIC, trade name: F-571): 0.50 parts by weight was used instead of using 0.25 parts by weight of LE-302): The same procedure as in Example 1 was carried out, and the pressure-sensitive adhesive composition was used. (2) was manufactured and the surface protection film (2) with a separator was obtained.

The results are shown in Table 1.

[Example 3]

Except having changed the usage-amount of a fluorine-containing polymer (DIC product, brand name: F-571) into 1.00 weight part, it carried out similarly to Example 2, the adhesive composition (3) was manufactured, and the separator-equipped surface protection film (3) was obtained.

The results are shown in Table 1.

[Example 4]

When producing the pressure-sensitive adhesive composition, the pressure-sensitive adhesive composition (4) was prepared in the same manner as in Example 1 except that 0.30 parts by weight of a fluorine-containing polymer (manufactured by DIC, trade name: F-571): 0.30 parts by weight was used, and surface protection with a separator Film (4) was obtained.

The results are shown in Table 1.

[Example 5]

Siloxane bond-containing polymer (manufactured by Kyoesha Chemical Co., Ltd., trade name: LE-302): Instead of using 0.25 parts by weight, fluorine-containing polymer (manufactured by DIC, trade name: F-571): 0.30 parts by weight was used, It carried out similarly to Example 1, the adhesive composition (5) was manufactured, and the surface protection film (5) with a separator was obtained.

The results are shown in Table 1.

[Example 6]

As the polyol (A), Sannix GP-3000, a polyol having three OH groups (manufactured by Sanyo Chemical Co., Ltd., Mn=3000): 100 parts by weight, as the polyfunctional isocyanate compound (B), which is a polyfunctional alicyclic isocyanate compound Coronate HX (manufactured by Nippon Polyurethane Kogyo Co., Ltd.): 18 parts by weight, catalyst (manufactured by Nippon Chemical Industries, Ltd., trade name: Nasem Ferric): 0.1 parts by weight, hydroxyl group-containing silicone (Shin-Etsu Chemical Co., Ltd.) The Shiki Corporation make, brand name: X-22-4015): 0.25 weight part, ethyl acetate was added as a diluting solvent, mixing stirring was performed, and the adhesive composition (6) was manufactured.

It carried out similarly to Example 1 using the adhesive composition (6), and obtained the surface protection film (6) with a separator.

The results are shown in Table 1.

[Comparative Example 1]

As the polyol (A), Preminol S3011, a polyol having three OH groups (manufactured by Asahi Glass Co., Ltd., Mn=10000): 85 parts by weight, Sannix GP-3000, a polyol having three OH groups (Sanyo Chemical Co., Ltd.) manufactured by Shiki, Mn=3000): 13 parts by weight, Sannix GP-1000, a polyol having three OH groups (manufactured by Sanyo Chemical Co., Ltd., Mn=1000): 2 parts by weight, as a polyfunctional isocyanate compound (B) Coronate HX, a polyfunctional alicyclic isocyanate compound (manufactured by Nippon Polyurethane Kogyo Co., Ltd.): 18 parts by weight, catalyst (manufactured by Nippon Chemical Industries, Ltd., trade name: Nasem Ferric): 0.1 parts by weight, diluting solvent As ethyl acetate was added, mixing and stirring were performed, and the adhesive composition (C1) was manufactured.

It carried out similarly to Example 1 using the adhesive composition (C1), and obtained the surface protection film (C1) with a separator.

The results are shown in Table 1.

[Comparative Example 2]

When producing the pressure-sensitive adhesive composition, polyether-modified silicone oil with both ends (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KF-6004): 0.02 parts by weight except that 0.02 parts by weight was used, in the same manner as in Comparative Example 1, The composition (C2) was manufactured, and the surface protection film with a separator (C2) was obtained.

The results are shown in Table 1.

[Comparative Example 3]

As the polyol (A), Sannix GP-3000, a polyol having three OH groups (manufactured by Sanyo Chemical Co., Ltd., Mn=3000): 100 parts by weight, as the polyfunctional isocyanate compound (B), which is a polyfunctional alicyclic isocyanate compound Coronate HX (manufactured by Nippon Polyurethane Kogyo Co., Ltd.): 18 parts by weight, catalyst (manufactured by Nippon Chemical Industries, Ltd., trade name: Nasem Ferric): 0.1 parts by weight, ethyl acetate as a diluting solvent is added and mixed It stirred and produced the adhesive composition (C3).

Using the adhesive composition (C3), it carried out similarly to Example 1, and obtained the surface protection film (C3) with a separator.

The results are shown in Table 1.

[Comparative Example 4]

1-ethyl-3-methylimidazolium bis(fluoromethanesulfonyl)imide (manufactured by Daiichi Kogyo Seyaku Co., Ltd., trade name: AS110) and a siloxane bond-containing polymer (manufactured by Kyoesha Chemical Co., Ltd.) , brand name: LE-302) was not used, but it carried out similarly to Example 1, the adhesive composition (C4) was manufactured, and the surface protection film with a separator (C4) was obtained.

The results are shown in Table 1.

[Comparative Example 5]

Without using a siloxane bond-containing polymer, the amount of isopropyl myristate (manufactured by Kao Corporation, trade name: Exepal IPM, Mn = 270) was changed to 30 parts by weight, and both terminal polyether-modified silicone oil (Shin-Etsu) Except having changed the usage-amount of the Kagaku Kogyo Co., Ltd. make, brand name: KF-6004) into 0.01 weight part, it carried out similarly to Example 1, the adhesive composition (C5) was manufactured, and the surface protection film with a separator (C5) was obtained .

The results are shown in Table 1.

[Comparative Example 6]

When producing the pressure-sensitive adhesive composition, isopropyl myristate (manufactured by Kao Corporation, trade name: Exepal IPM, Mn = 270): 25 parts by weight except that 25 parts by weight were used in the same manner as in Comparative Example 1, the pressure-sensitive adhesive composition (C6 ) was prepared, and a surface protection film with a separator (C6) was obtained.

The results are shown in Table 1.

[Comparative Example 7]

Both-terminal polyether-modified silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KF-6004): 0.01 parts by weight of a silicone release agent (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KS-) 776A): Except having used 0.15 weight part, it carried out similarly to the comparative example 5, the adhesive composition (C7) was manufactured, and the separator-equipped surface protection film (C7) was obtained.

The results are shown in Table 1.

[Example 7]

"Cyabain SH-109" (solid content 54%, fatty acid ester containing, Toyo Ink Co., Ltd. make) as urethane prepolymer (C): 100 weight part, Coronate HX which is a polyfunctional alicyclic isocyanate compound as a polyfunctional isocyanate compound (B) (manufactured by Nippon Polyurethane Kogyo Co., Ltd.): 7.05 parts by weight, fluorine-containing polymer (manufactured by DIC, trade name: F-571): 1.00 parts by weight, toluene as a diluting solvent: 208 parts by weight, stirred with a disper, A pressure-sensitive adhesive composition (7) was prepared.

The obtained pressure-sensitive adhesive composition (7) is applied to a base material "Lumiror S10" (thickness 38 µm, manufactured by Toray Corporation) containing a polyester resin so that the thickness after drying becomes 10 µm with a fountain roll, and a drying temperature of 130 ° C., It was cured and dried under the conditions of a drying time of 30 seconds. In this way, the adhesive layer was produced on the base material. Next, the silicone-treated surface of the base material (separator) containing the 25-micrometer-thick polyester resin which silicone-treated on the surface of the adhesive layer was bonded together, and the surface protection film (7) with a separator was obtained.

The results are shown in Table 2.

[Example 8]

Except having changed the usage-amount of a fluorine-containing polymer (made by DIC, brand name: F-571) into 2.00 weight part, it carried out similarly to Example 7, the adhesive composition (8) was manufactured, and the separator-equipped surface protection film (8) was obtained.

The results are shown in Table 2.

[Example 9]

Except having changed the usage-amount of the fluorine-containing polymer (made by DIC, brand name: F-571) into 3.00 weight part, it carried out similarly to Example 7, the adhesive composition (9) was manufactured, and the separator-equipped surface protection film (9) was obtained.

The results are shown in Table 2.

[Example 10]

"Cyabain SH-109" (solid content 54%, fatty acid ester containing, Toyo Ink Co., Ltd. make) as urethane prepolymer (C): 100 weight part, Coronate HX which is a polyfunctional alicyclic isocyanate compound as a polyfunctional isocyanate compound (B) (manufactured by Nippon Polyurethane Kogyo Co., Ltd.): 3.6 parts by weight, fluorine-containing polymer (manufactured by DIC, trade name: F-571): 1.00 parts by weight, toluene as a diluting solvent: 208 parts by weight, stirred with a disper, A pressure-sensitive adhesive composition (10) was prepared.

The obtained pressure-sensitive adhesive composition (10) is applied to a base material "Lumiror S10" (thickness 38 µm, manufactured by Toray Corporation) containing a polyester resin so that the thickness after drying becomes 50 µm with a fountain roll, and a drying temperature of 130 ° C., It was cured and dried under the conditions of a drying time of 30 seconds. In this way, the adhesive layer was produced on the base material. Next, the silicone-treated surface of the base material (separator) containing the 25-micrometer-thick polyester resin which silicone-treated on the surface of the adhesive layer was bonded to the surface of the adhesive layer, and the surface protection film 10 with a separator was obtained.

The results are shown in Tables 3 and 4.

[Example 11]

Except having changed the usage-amount of a fluorine-containing polymer (made by DIC, brand name: F-571) into 3.00 weight part, it carried out similarly to Example 10, the adhesive composition (11) was manufactured, and the separator-equipped surface protection film (11) was obtained.

The results are shown in Tables 3 and 4.

[Example 12]

Except having changed the usage-amount of a fluorine-containing polymer (made by DIC, brand name: F-571) into 5.00 weight part, it carried out similarly to Example 10, the adhesive composition (12) was manufactured, and the separator-equipped surface protection film (12) was obtained.

The results are shown in Tables 3 and 4.

[Comparative Example 8]

Except not having used the fluorine-containing polymer (made by DIC, brand name: F-571), it carried out similarly to Example 10, the adhesive composition (C8) was manufactured, and the separator-equipped surface protection film (C8) was obtained.

The results are shown in Tables 3 and 4.

[Comparative Example 9]

The same procedure as in Example 10 was performed except that the amount of Coronate HX (manufactured by Nippon Polyurethane Kogyo Co., Ltd.) was changed to 7.05 parts by weight and not using a fluorine-containing polymer (manufactured by DIC, trade name: F-571), and the pressure-sensitive adhesive composition (C9) was manufactured and the surface protection film with a separator (C9) was obtained.

The results are shown in Tables 3 and 4.

[Example 13]

"Cyabain SH-109" (solid content 54%, fatty acid ester containing, Toyo Ink Co., Ltd. make) as urethane prepolymer (C): 100 weight part, Coronate HX which is a polyfunctional alicyclic isocyanate compound as a polyfunctional isocyanate compound (B) (manufactured by Nippon Polyurethane Kogyo Co., Ltd.): 7.05 parts by weight, fluorine-containing polymer (manufactured by DIC, trade name: F-571): 1.00 parts by weight, toluene as a diluting solvent: 208 parts by weight, stirred with a disper, A pressure-sensitive adhesive composition (13) was prepared.

The obtained pressure-sensitive adhesive composition (13) is applied to a base material "Lumiror S10" (thickness 38 µm, manufactured by Toray Corporation) containing a polyester resin so that the thickness after drying becomes 50 µm with a fountain roll, and a drying temperature of 130 ° C., It was cured and dried under the conditions of a drying time of 30 seconds. In this way, the adhesive layer was produced on the base material. Next, the silicone-treated surface of the base material (separator) containing the 25-micrometer-thick polyester resin which silicone-treated on the surface of the adhesive layer was bonded to the surface of the adhesive layer, and the surface protection film 13 with a separator was obtained.

The results are shown in Tables 3 and 4.

[Example 14]

Except having changed the usage-amount of the fluorine-containing polymer (made by DIC, brand name: F-571) into 3.00 weight part, it carried out similarly to Example 13, the adhesive composition (14) was manufactured, and the separator-equipped surface protection film (14) was obtained.

The results are shown in Tables 3 and 4.

[Example 15]

Except having changed the usage-amount of a fluorine-containing polymer (made by DIC, brand name: F-571) into 5.00 weight part, it carried out similarly to Example 13, the adhesive composition (15) was manufactured, and the separator-equipped surface protection film (15) was obtained.

The results are shown in Tables 3 and 4.

[Comparative Example 10]

A fluorine-containing polymer (manufactured by DIC, trade name: F-571) was not used, and a silicone release agent (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KS-776A): 1 part by weight was used except that 1 part by weight was used in the same manner as in Example 13. , the pressure-sensitive adhesive composition (C10) was prepared, and a separator-equipped surface protection film (C10) was obtained.

The results are shown in Tables 3 and 4.

[Comparative Example 11]

A fluorine-containing polymer (manufactured by DIC, trade name: F-571) was not used, and a silicone release agent (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KS-776A): 3 parts by weight except that 3 parts by weight was used. , the pressure-sensitive adhesive composition (C11) was prepared, and a separator-equipped surface protection film (C11) was obtained.

The results are shown in Tables 3 and 4.

[Comparative Example 12]

The amount of Coronate HX (manufactured by Nippon Polyurethane Kogyo Co., Ltd.) was changed to 17.7 parts by weight, and without using a fluorine-containing polymer (manufactured by DIC, trade name: F-571), the thickness of the pressure-sensitive adhesive layer was made to be 10 µm Other than that, it carried out similarly to Example 13, the adhesive composition (C12) was manufactured, and the surface protection film with a separator (C12) was obtained.

The results are shown in Tables 3 and 4.

[Comparative Example 13]

The amount of Coronate HX (manufactured by Nippon Polyurethane Kogyo Co., Ltd.) was changed to 17.7 parts by weight, and without using a fluorine-containing polymer (manufactured by DIC, trade name: F-571), the thickness of the pressure-sensitive adhesive layer was made to be 25 µm Other than that, it carried out similarly to Example 13, the adhesive composition (C13) was manufactured, and the surface protection film with a separator (C13) was obtained.

The results are shown in Tables 3 and 4.

[Example 16]

As the polyol (A), Preminol S3011, a polyol having three OH groups (manufactured by Asahi Glass Co., Ltd., Mn=10000): 85 parts by weight, Sannix GP-3000, a polyol having three OH groups (Sanyo Chemical Co., Ltd.) manufactured by Shiki, Mn=3000): 13 parts by weight, Sannix GP-1000, a polyol having three OH groups (manufactured by Sanyo Chemical Co., Ltd., Mn=1000): 2 parts by weight, as a polyfunctional isocyanate compound (B) Coronate HX, a polyfunctional alicyclic isocyanate compound (manufactured by Nippon Polyurethane Kogyo Co., Ltd.): 17.7 parts by weight, fluorine-containing polymer (manufactured by DIC, trade name: F-571): 0.3 parts by weight, ethyl acetate as a diluting solvent: 200 The parts by weight were blended and stirred with a disper to prepare a pressure-sensitive adhesive composition (16).

The obtained pressure-sensitive adhesive composition (16) is applied to a base material "Lumiror S10" (thickness 38 µm, manufactured by Toray Corporation) containing a polyester resin so that the thickness after drying is 10 µm with a fountain roll, and a drying temperature of 130 ° C., It was cured and dried under the conditions of a drying time of 30 seconds. In this way, the adhesive layer was produced on the base material. Next, the silicone-treated surface of the base material (separator) containing the 25-micrometer-thick polyester resin which silicone-treated on the surface of the adhesive layer was bonded to the surface of the adhesive layer, and the surface protection film 16 with a separator was obtained.

The results are shown in Tables 3 and 4.

[Example 17]

Except having made the thickness of an adhesive layer set to 25 micrometers, it carried out similarly to Example 16, the adhesive composition (17) was manufactured, and the surface protection film (17) with a separator was obtained.

The results are shown in Tables 3 and 4.

[Example 18]

As the polyol (A), Preminol S3011, a polyol having three OH groups (manufactured by Asahi Glass Co., Ltd., Mn=10000): 85 parts by weight, Sannix GP-3000, a polyol having three OH groups (Sanyo Chemical Co., Ltd.) manufactured by Shiki, Mn=3000): 13 parts by weight, Sannix GP-1000, a polyol having three OH groups (manufactured by Sanyo Chemical Co., Ltd., Mn=1000): 2 parts by weight, as a polyfunctional isocyanate compound (B) Coronate HX, a polyfunctional alicyclic isocyanate compound (manufactured by Nippon Polyurethane Kogyo Co., Ltd.): 17.7 parts by weight, hydroxyl group-containing silicone (Shin-Etsu Chemical Co., Ltd., trade name: X-22-4015): 0.3 parts by weight , ethyl acetate: 200 parts by weight as a diluent solvent was blended and stirred with a disper to prepare a pressure-sensitive adhesive composition (18).

The obtained pressure-sensitive adhesive composition (18) is applied to a base material "Lumiror S10" (thickness 38 µm, manufactured by Toray Corporation) containing a polyester resin so that the thickness after drying becomes 10 µm with a fountain roll, and a drying temperature of 130 ° C., It was cured and dried under the conditions of a drying time of 30 seconds. In this way, the adhesive layer was produced on the base material. Next, the silicone-treated surface of the base material (separator) containing the 25-micrometer-thick polyester resin which silicone-treated on the surface of the adhesive layer was bonded together, and the surface protection film 18 with a separator was obtained.

The results are shown in Tables 3 and 4.

[Example 19]

Except having made the thickness of an adhesive layer set to 25 micrometers, it carried out similarly to Example 18, the adhesive composition (19) was manufactured, and the surface protection film (19) with a separator was obtained.

The results are shown in Tables 3 and 4.

[Example 20]

The separator of the surface protection film with a separator (1) obtained in Example 1 was peeled off, and the adhesive layer side was adhered to a polarizing plate (manufactured by Nitto Denko Corporation, trade name "TEG1465DUHC") as an optical member, and the surface protection film was adhered optical got the absence.

[Example 21]

The separator of the surface protection film with a separator (2) obtained in Example 2 was peeled off, and the adhesive layer side was adhered to a polarizing plate as an optical member (manufactured by Nitto Denko Co., Ltd., trade name "TEG1465DUHC"), and the surface protection film was adhered optical got the absence.

[Example 22]

The separator of the surface protection film with a separator (3) obtained in Example 3 was peeled off, and the adhesive layer side was adhered to a polarizing plate (manufactured by Nitto Denko Corporation, trade name "TEG1465DUHC") as an optical member, and the surface protection film was adhered optical got the absence.

[Example 23]

The separator of the surface protection film with a separator (4) obtained in Example 4 was peeled off, and the adhesive layer side was adhered to a polarizing plate (manufactured by Nitto Denko Co., Ltd., trade name "TEG1465DUHC") as an optical member, and the surface protection film was adhered optical got the absence.

[Example 24]

The separator of the surface protection film with a separator (5) obtained in Example 5 was peeled off, and the adhesive layer side was adhered to a polarizing plate as an optical member (manufactured by Nitto Denko Corporation, trade name "TEG1465DUHC"), and the surface protection film was adhered optical got the absence.

[Example 25]

The separator of the surface protection film with a separator (6) obtained in Example 6 was peeled off, and the adhesive layer side was adhered to a polarizing plate as an optical member (manufactured by Nitto Denko Corporation, trade name "TEG1465DUHC"), and the surface protection film was adhered optical got the absence.

[Example 26]

The separator of the surface protection film (1) with a separator obtained in Example 1 was peeled off, and the adhesive layer side was adhered to the conductive film (made by Nitto Denko Co., Ltd., trade name "Elecrysta V270L-TFMP") which is an electronic member, and surface protection was carried out An electronic member to which the film was adhered was obtained.

[Example 27]

The separator of the surface protection film with a separator (2) obtained in Example 2 was peeled off, and the adhesive layer side was adhered to the conductive film as an electronic member (manufactured by Nitto Denko Corporation, trade name "Elecrista V270L-TFMP") to protect the surface An electronic member to which the film was adhered was obtained.

[Example 28]

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

[Example 29]

The separator of the surface protection film (4) with a separator obtained in Example 4 was peeled off, and the adhesive layer side was adhered to an electronic member conductive film (manufactured by Nitto Denko Corporation, trade name "Elecrista V270L-TFMP") to protect the surface. An electronic member to which the film was adhered was obtained.

[Example 30]

The separator of the surface protection film with a separator (5) obtained in Example 5 was peeled off, and the adhesive layer side was adhered to an electronic member conductive film (manufactured by Nitto Denko Corporation, trade name "Elecrista V270L-TFMP") to protect the surface. An electronic member to which the film was adhered was obtained.

[Example 31]

The separator of the surface protection film with a separator (6) obtained in Example 6 was peeled off, and the adhesive layer side was adhered to an electronic member conductive film (manufactured by Nitto Denko Corporation, trade name "Elecrista V270L-TFMP") to protect the surface. An electronic member to which the film was adhered was obtained.

[Example 32]

The separator of the surface protection film with a separator (7) obtained in Example 7 was peeled off, and the adhesive layer side was adhered to a polarizing plate (manufactured by Nitto Denko Corporation, trade name "TEG1465DUHC") as an optical member, and the surface protection film was adhered optical got the absence.

[Example 33]

The separator of the surface protection film 10 with a separator obtained in Example 10 was peeled off, and the adhesive layer side was adhered to a polarizing plate (manufactured by Nitto Denko Corporation, trade name "TEG1465DUHC") as an optical member, and the surface protection film was adhered optical got the absence.

[Example 34]

The separator of the surface protection film 13 with a separator obtained in Example 13 was peeled off, and the adhesive layer side was adhered to the polarizing plate (made by Nitto Denko Co., Ltd., trade name "TEG1465DUHC") as an optical member, and the surface protection film was adhered optical got the absence.

[Example 35]

The separator of the surface protection film 16 with a separator obtained in Example 16 was peeled off, and the adhesive layer side was adhered to the polarizing plate (made by Nitto Denko Co., Ltd., trade name "TEG1465DUHC") as an optical member, and the surface protection film was adhered optical got the absence.

[Example 36]

The separator of the surface protection film 18 with a separator obtained in Example 18 was peeled off, the adhesive layer side was adhered to the polarizing plate (made by Nitto Denko Co., Ltd., trade name "TEG1465DUHC") as an optical member, and the surface protection film was adhered optical got the absence.

[Example 37]

The separator of the surface protection film with a separator (7) obtained in Example 7 was peeled off, and the adhesive layer side was adhered to an electronic member conductive film (manufactured by Nitto Denko Co., Ltd., trade name "Elecrista V270L-TFMP") to protect the surface. An electronic member to which the film was adhered was obtained.

[Example 38]

The separator of the surface protection film 10 with a separator obtained in Example 10 was peeled off, and the adhesive layer side was adhered to the conductive film (Nitto Denko Co., Ltd. make, trade name "Elecristar V270L-TFMP") which is an electronic member, and surface protection was carried out An electronic member to which the film was adhered was obtained.

[Example 39]

The separator of the surface protection film 13 with a separator obtained in Example 13 was peeled off, and the adhesive layer side was adhered to the electroconductive film (Nitto Denko Co., Ltd. make, trade name "Elecristar V270L-TFMP") which is an electronic member, and surface protection An electronic member to which the film was adhered was obtained.

[Example 40]

The separator of the surface protection film 16 with a separator obtained in Example 16 was peeled off, and the adhesive layer side was adhered to the electroconductive film (Nitto Denko Co., Ltd. make, brand name "Elecristar V270L-TFMP") as an electronic member, and surface protection was carried out An electronic member to which the film was adhered was obtained.

[Example 41]

The separator of the surface protection film 18 with a separator obtained in Example 18 was peeled off, and the adhesive layer side was adhered to the conductive film (Nitto Denko Co., Ltd. make, trade name "Elecrysta V270L-TFMP") which is an electronic member, and surface protection was carried out An electronic member to which the film was adhered was obtained.

The surface protection film of this invention can be used for arbitrary appropriate uses. Preferably, the surface protection film of this invention is used suitably in the field|area of an optical member and an electronic member.

1: base layer
2: adhesive layer
10: surface protection film

Claims (12)

It is a surface protection film having an adhesive layer,
A polyethylene terephthalate film having a thickness of 25 µm was bonded to the pressure-sensitive adhesive layer, and after 30 minutes at 23°C, the polyethylene terephthalate film was peeled off at a peeling angle of 180 degrees and a peeling rate of 6000 mm/min. 0.001N/25mm or more and 0.08N/25mm or less,
A polyethylene terephthalate film having a thickness of 25 µm was bonded to the pressure-sensitive adhesive layer, and after 30 minutes at 23° C., the polyethylene terephthalate film was peeled off at a peeling angle of 180 degrees and a peeling rate of 300 mm/min. 0.001N/25mm or more and 0.02N/25mm or less,
The pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer is formed of a pressure-sensitive adhesive composition,
The pressure-sensitive adhesive composition contains a base polymer, a silicone-based additive and/or a fluorine-based additive,
The base polymer is a urethane prepolymer,
The silicone-based additive is at least one selected from a hydroxyl group-containing silicone-based compound and a crosslinkable functional group-containing silicone-based compound,
The fluorine-based additive is at least one selected from a compound having a fluoroaliphatic hydrocarbon skeleton, a fluorine-containing organic compound obtained by copolymerizing an organic compound and a fluorine compound, a hydroxyl group-containing fluorine compound, and a crosslinkable functional group-containing fluorine-based compound,
The content of the silicone-based additive and/or the fluorine-based additive in the pressure-sensitive adhesive composition is 0.01 parts by weight to 50 parts by weight as a total amount of the silicone-based additive and the fluorine-based additive relative to 100 parts by weight of the base polymer.
However, the pressure-sensitive adhesive composition is 100 parts by weight of "Cyabain SH-109H" (54% solids, manufactured by Toyochem Co., Ltd.) as a urethane adhesive, and "Cyabine BXX-6269" (Toyochem Co., Ltd.) as a crosslinking agent. Agent) 6.9 parts by weight, leveling agent (Grandic PC4100 (silicone), manufactured by DIC): 0.05 parts by weight or 0.01 parts by weight, diluted with toluene so that the solid content of the pressure-sensitive adhesive composition becomes 45%, and stirred with a disper. Except for compositions. It is a surface protection film having an adhesive layer,
A polyethylene terephthalate film having a thickness of 25 µm was bonded to the pressure-sensitive adhesive layer, and after 7 days at 80°C, the polyethylene terephthalate film was peeled off at a peeling angle of 180 degrees and a peeling rate of 6000 mm/min. 0.001N/25mm or more and 0.35N/25mm or less,
A polyethylene terephthalate film having a thickness of 25 µm was bonded to the pressure-sensitive adhesive layer, and after 7 days at 80°C, the polyethylene terephthalate film was peeled off at a peeling angle of 180 degrees and a peeling rate of 300 mm/min. 0.001N/25mm or more and 0.07N/25mm or less,
The pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer is formed of a pressure-sensitive adhesive composition,
The pressure-sensitive adhesive composition contains a base polymer, a silicone-based additive and/or a fluorine-based additive,
The base polymer is a urethane prepolymer,
The silicone-based additive is at least one selected from a hydroxyl group-containing silicone-based compound and a crosslinkable functional group-containing silicone-based compound,
The fluorine-based additive is at least one selected from a compound having a fluoroaliphatic hydrocarbon skeleton, a fluorine-containing organic compound obtained by copolymerizing an organic compound and a fluorine compound, a hydroxyl group-containing fluorine compound, and a crosslinkable functional group-containing fluorine-based compound,
The content of the silicone-based additive and/or the fluorine-based additive in the pressure-sensitive adhesive composition is 0.01 parts by weight to 50 parts by weight as a total amount of the silicone-based additive and the fluorine-based additive with respect to 100 parts by weight of the base polymer.
However, the pressure-sensitive adhesive composition is 100 parts by weight of "Cyabain SH-109H" (54% solids, manufactured by Toyochem Co., Ltd.) as a urethane adhesive, and "Cyabine BXX-6269" (Toyochem Co., Ltd.) as a crosslinking agent. Agent) 6.9 parts by weight, leveling agent (Grandic PC4100 (silicone), manufactured by DIC): 0.05 parts by weight or 0.01 parts by weight, diluted with toluene so that the solid content of the pressure-sensitive adhesive composition becomes 45%, and stirred with a disper. Except for compositions. It is a surface protection film having an adhesive layer,
The peeling force at the time of bonding a 1000-micrometer-thick glass plate together to the said adhesive layer and peeling in the peeling angle 180 degree and peeling rate 6000 mm/min from the said glass plate 30 minutes at 23 degreeC is 0.001N/25mm or more 0.135 N/25mm or less,
The peeling force at the time of bonding a 1000-micrometer-thick glass plate together to the said adhesive layer and peeling in the peeling angle 180 degrees and 300 mm/min of peeling speed 300 mm/min from the said glass plate 30 minutes at 23 degreeC is 0.001N/25mm or more, 0.023 N/25mm or less,
The pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer is formed of a pressure-sensitive adhesive composition,
The pressure-sensitive adhesive composition contains a base polymer, a silicone-based additive and/or a fluorine-based additive,
The base polymer is a urethane prepolymer,
The silicone-based additive is at least one selected from a hydroxyl group-containing silicone-based compound and a crosslinkable functional group-containing silicone-based compound,
The fluorine-based additive is at least one selected from a compound having a fluoroaliphatic hydrocarbon skeleton, a fluorine-containing organic compound obtained by copolymerizing an organic compound and a fluorine compound, a hydroxyl group-containing fluorine compound, and a crosslinkable functional group-containing fluorine-based compound,
The content of the silicone-based additive and/or the fluorine-based additive in the pressure-sensitive adhesive composition is 0.01 parts by weight to 50 parts by weight as a total amount of the silicone-based additive and the fluorine-based additive with respect to 100 parts by weight of the base polymer.
However, the pressure-sensitive adhesive composition is 100 parts by weight of "Cyabain SH-109H" (54% solids, manufactured by Toyochem Co., Ltd.) as a urethane adhesive, and "Cyabain BXX-6269" (Toyochem Co., Ltd.) as a crosslinking agent. Agent) 6.9 parts by weight, leveling agent (Grandic PC4100 (silicone), manufactured by DIC): 0.05 parts by weight or 0.01 parts by weight, diluted with toluene so that the solid content of the pressure-sensitive adhesive composition becomes 45%, and stirred with a disper. Except for compositions. It is a surface protection film having an adhesive layer,
A glass plate having a thickness of 1000 µm is bonded to the pressure-sensitive adhesive layer, and the peeling force is 0.001 N/25 mm or more and 0.35 when it is peeled from the glass plate at a peeling angle of 180 degrees and a peeling rate of 6000 mm/min after 7 days at 80°C. N/25 mm or less,
The peeling force at the time of bonding a 1000-micrometer-thick glass plate together to the said adhesive layer and peeling in the peeling angle 180 degree and peeling rate 300 mm/min from this glass plate after 7 days at 80 degreeC is 0.001N/25mm or more 0.05 N/25mm or less,
The pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer is formed of a pressure-sensitive adhesive composition,
The pressure-sensitive adhesive composition contains a base polymer, a silicone-based additive and/or a fluorine-based additive,
The base polymer is a urethane prepolymer,
The silicone-based additive is at least one selected from a hydroxyl group-containing silicone-based compound and a crosslinkable functional group-containing silicone-based compound,
The fluorine-based additive is at least one selected from a compound having a fluoroaliphatic hydrocarbon skeleton, a fluorine-containing organic compound obtained by copolymerizing an organic compound and a fluorine compound, a hydroxyl group-containing fluorine compound, and a crosslinkable functional group-containing fluorine-based compound,
The content of the silicone-based additive and/or the fluorine-based additive in the pressure-sensitive adhesive composition is 0.01 parts by weight to 50 parts by weight as a total amount of the silicone-based additive and the fluorine-based additive with respect to 100 parts by weight of the base polymer.
However, the pressure-sensitive adhesive composition is 100 parts by weight of "Cyabain SH-109H" (54% solids, manufactured by Toyochem Co., Ltd.) as a urethane adhesive, and "Cyabain BXX-6269" (Toyochem Co., Ltd.) as a crosslinking agent. Agent) 6.9 parts by weight, leveling agent (Grandic PC4100 (silicone), manufactured by DIC): 0.05 parts by weight or 0.01 parts by weight, diluted with toluene so that the solid content of the pressure-sensitive adhesive composition becomes 45%, and stirred with a disper. Except for compositions. 5. The method according to any one of claims 1 to 4,
A surface protection film having a residual adhesive ratio of 50% or more. 5. The method according to any one of claims 1 to 4,
The pressure-sensitive adhesive composition comprising a fatty acid ester, a surface protection film. The optical member to which the surface protection film in any one of Claims 1-4 was adhere|attached. The electronic member to which the surface protection film in any one of Claims 1-4 was adhere|attached. delete delete delete delete

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