KR20210096565A - Surface protection film - Google Patents

Abstract

Provided is a surface protection film including an adhesive layer to be attached on an exposed surface of an optical member or an electronic member to prevent a flaw on a surface of the optical member or the electronic member at processing, assembly, inspection, transportation, etc. typically, in a manufacturing process of the optical member or the electronic member, the surface protection film capable of sufficiently suppressing peeling electrification voltage and avoiding a damage on the optical member or the electronic member at peeling. The surface protection film includes the adhesive layer. An adhesive agent forming the adhesive layer is composed of an adhesive composition. The adhesive composition includes a base polymer, an ionic compound, and a fluorine-based compound. A surface free energy on a surface of the adhesive layer to diiodomethane is 6 mJ/m^2 to 30 mJ/m^2.

Description

Surface Protection Film {SURFACE PROTECTION 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 a flaw from occurring on the surface of the said optical member or the said electronic member when processing, assembling, inspection, transport, etc., generally, the said optical member or the said electronic member A surface protection film is affixed on the exposed surface of a member. 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).

Usually, a surface protection film, an optical member, and an electronic member have high electrical insulation, and generate|occur|produce static electricity by friction or peeling. For this reason, also when peeling a surface protection film from an optical member or an electronic member, it is easy to generate|occur|produce static electricity. In such a case, for example, if a voltage is applied to the liquid crystal while static electricity remains, the alignment of the liquid crystal molecules may be lost or the panel may be damaged. In addition, the presence of static electricity can be a factor that attracts dust or reduces workability.

In order to prevent static electricity, antistatic treatment is performed on the surface protection film. For example, it is reported that an antistatic function is imparted by forming an antistatic layer or applying an antistatic coating as a surface layer (top coating layer, back layer) of a surface protection film (Patent Documents 2 and 3).

In addition, in order to impart antistatic properties to the pressure-sensitive adhesive layer itself constituting the surface protection film, an ionic compound such as an alkali metal salt or an ionic liquid that functions as an antistatic agent is contained in the pressure-sensitive adhesive layer and transferred to an adherend is performed. It is losing (patent document 4).

Japanese Patent Laid-Open No. 2016-17109 Japanese Patent Laid-Open No. 2004-223923 Japanese Patent Laid-Open No. 2008-255332 Japanese Patent Laid-Open No. 9-165460

The subject of the present invention is, typically, in the manufacturing process of an optical member or an electronic member, in order to prevent the occurrence of surface defects of the optical member or the electronic member during processing, assembling, inspection, transportation, etc., the optical member To provide a surface protection film that is adhered to the exposed surface of the electronic member and includes a pressure-sensitive adhesive layer, which sufficiently suppresses peeling electrification voltage, and does not damage the optical member or the electronic member at the time of peeling The purpose.

A surface protection film according to an embodiment of the present invention,

It is a surface protection film comprising an adhesive layer,

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, an ionic compound, and a fluorine-based compound,

The surface free energy of the surface of the pressure-sensitive adhesive layer with respect to diiodomethane is 6 mJ/m 2 to 30 mJ/m 2 .

In one embodiment, the content ratio of the said ionic compound with respect to 100 weight part of said base polymers is 0.2 weight part or more.

In one embodiment, the content ratio of the said fluorine-type compound with respect to 100 weight part of said base polymers is 0.05 weight part or more.

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

In one embodiment, after bonding the said adhesive layer contained in the said surface protection film to a glass plate and leaving it to stand at the temperature of 23 degreeC for 30 minutes, the said surface protection film is peeled from the said glass plate at a temperature of 23 degreeC at a peeling angle of 180 degrees The peeling force at the time of peeling at a speed|rate of 300 mm/min is 0.005 N/25 mm - 0.1 N/25 mm.

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

In the electronic member according to the embodiment of the present invention, the surface protection film is adhered thereto.

According to the present invention, typically, in the manufacturing process of the optical member or electronic member, in order to prevent the occurrence of surface defects of the optical member or the electronic member during processing, assembly, inspection, transportation, etc. It is a surface protection film comprising a pressure-sensitive adhesive layer adhered to the exposed surface of the electronic member, the peeling electrification voltage is sufficiently suppressed, and a surface protection film that does not damage the optical member or the electronic member at the time of peeling can be provided. .

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic sectional drawing of the surface protection film by one Embodiment of this invention.

≪≪A. Surface Protection Film»»

The surface protection film by embodiment of this invention contains an adhesive layer.

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

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic sectional drawing of the surface protection film by one Embodiment of this invention. In FIG. 1 , the surface protection film 10 includes a base material layer 1 and an adhesive layer 2 . In FIG. 1, the base material layer 1 and the adhesive layer 2 are laminated|stacked directly.

In FIG. 1, even if any suitable release liner (also referred to as a release sheet or a separator) is provided on the surface of the pressure-sensitive adhesive layer 2 on the opposite side of the base layer 1 for protection until use or the like. (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.

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. .

The pressure-sensitive adhesive layer included in the surface protection film has a surface free energy to diiodomethane of 6 mJ/m 2 to 30 mJ/m 2 , more preferably 8 mJ/m 2 to 30 mJ/m 2 , still more preferably 10 mJ/m2 m2 to 30 mJ/m 2 , particularly preferably 12 mJ/m 2 to 30 mJ/m 2 . When the surface free energy of the pressure-sensitive adhesive layer contained in the surface protection film with respect to diiodomethane is within the above range, the peeling electrification voltage is sufficiently suppressed and the adherend (typically, an optical member or an electronic member) is damaged at the time of peeling. It is possible to provide a surface protection film that does not do this. When the surface free energy with respect to the diiodomethane of the adhesive layer contained in a surface protection film is too low outside the said range, there exists a possibility that peeling electrification voltage may not fully be suppressed. When the surface free energy of the pressure-sensitive adhesive layer included in the surface protection film with respect to diiodomethane is too high outside the above range, there is a risk of contaminating the adherend.

In addition, as will be described later, the surface free energy of the pressure-sensitive adhesive layer contained in the surface protection film can be easily measured, and the pressure-sensitive adhesive layer is designed so that the surface free energy falls within the predetermined range. , it is possible to provide a surface protection film that sufficiently suppresses a peeling electrification voltage and does not damage an adherend (typically, an optical member or an electronic member) at the time of peeling. Here, as a point of designing said adhesive layer, in this invention, using an ionic compound and a fluorine-type compound together is typical, and selection of a fluorine compound. And, the selection of the fluorine compound includes, for example, selecting one whose surface free energy falls within the predetermined range from among a specific category of fluorine compounds. It is an action of a level that can be performed without even having to do so.

The pressure-sensitive adhesive layer included in the surface protection film is bonded to a glass plate and left at a temperature of 23 ° C. for 30 minutes, then the surface protection film is peeled from the glass plate at a temperature of 23 ° C. at a peeling angle of 180 degrees and a peeling rate of 300 mm / min. The peeling force at the time is preferably 0.005N/25mm to 0.1N/25mm, more preferably 0.007N/25mm to 0.08N/25mm, still more preferably 0.01N/25mm to 0.05N/25mm , particularly preferably 0.01N/25mm to 0.03N/25mm, and most preferably 0.01N/25mm to 0.02N/25mm. When the peeling force is within the above range, it is difficult to peel easily from the adherend, and typically, during the manufacturing process of the optical member or the electronic member, peeling after sticking to the exposed surface of the optical member or the electronic member It is hard to generate|occur|produce, and when peeling becomes necessary, the surface protection film which can peel easily can be provided.

A surface protection film 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;

etc., it can carry out according to arbitrary suitable manufacturing methods.

As a method of application|coating, the roll coater method, the comma coater method, the die coater method, the reverse coater method, the silkscreen method, the gravure coater method etc. can be used, for example.

The surface protection film according to the embodiment of the present invention typically prevents the occurrence of surface defects of the optical member or the electronic member during processing, assembling, inspection, transportation, etc. in the manufacturing process of the optical member or the electronic member. For this purpose, it is a surface protection film comprising an adhesive layer, which is adhered to the exposed surface of the optical member or the electronic member, and sufficiently suppresses the peeling electrification voltage, and does not damage the optical member or the electronic member at the time of peeling. am.

The surface protection film according to the embodiment of the present invention has a glass peel electrification voltage of preferably 3.0 kV or less, more preferably 2.5 kV or less, still more preferably 2.0 kV or less, particularly preferably 1.7 kV or less, and most preferably 1.5 kV or less. The measuring method of the glass-to-glass peeling electrification voltage is mentioned later.

The surface protection film according to the embodiment of the present invention has an acrylic plate peeling electrification voltage, preferably 4.0 kV or less, more preferably 3.5 kV or less, still more preferably 3.0 kV or less, even more preferably It is preferably 2.5 kV or less, particularly preferably 2.0 kV or less, and most preferably 1.5 kV or less. A method of measuring the to-acrylic plate peeling electrification voltage will be described later.

The surface protection film according to the embodiment of the present invention has a haze of preferably 5% or less, more preferably 4% or less, still more preferably 3% or less, particularly preferably 2.8% or less, , most preferably 2.5% or less. When the haze of the surface protection film by embodiment of this invention exists in the said range, it will become a thing suitable as a surface protection film adhere|attached to the exposed surface of an optical member or an electronic member. In particular, when the haze of the surface protection film according to the embodiment of the present invention can be reduced to 3% or less, since the inspection property of the surface protection film according to the embodiment of the present invention is further improved, it is more preferable. The haze measurement method will be described later.

The surface protection film according to the embodiment of the present invention has a glass-to-glass residual adhesive force of preferably 70% or more, more preferably 80% or more, still more preferably 85% or more, particularly preferably 88% or more. % or more, and most preferably 90% or more. This vs. glass residual adhesive force is an index of how much the pressure-sensitive adhesive layer component of the surface protection film is transferred to and contaminated with respect to the adherend. The higher the value of this-to-glass residual adhesion ratio, the higher the possibility of contaminating the adherend. am. The measuring method of this vs. glass residual adhesion rate is mentioned later.

«A-1. Adhesive layer≫

The pressure-sensitive adhesive layer is composed of an adhesive. An adhesive is formed from an adhesive composition. That is, it becomes an adhesive layer when the adhesive formed from an adhesive composition comprises layer shape.

An adhesive can be prescribed|regulated as what is formed from an adhesive composition. This is because the pressure-sensitive adhesive composition becomes a pressure-sensitive adhesive when the pressure-sensitive adhesive composition undergoes a crosslinking reaction or the like by heating or ultraviolet irradiation. Impossible/impossible circumstances") exist, and therefore, the pressure-sensitive adhesive is appropriately specified as "water" by the provision of "formed from the pressure-sensitive adhesive composition".

An adhesive layer can be formed by arbitrary appropriate methods. As such a method, for example, an adhesive composition is apply|coated on arbitrary suitable base materials, it heats and dries as needed, it hardens|cures as needed, and the method of forming an adhesive layer on this base material is mentioned. As a method of such application|coating, For example, methods, such as a gravure roll coater, a reverse roll coater, a kiss roll coater, a dip roll coater, a bar coater, a knife coater, an air knife coater, a spray coater, a comma coater, a direct coater, a roll brush coater can be heard

Since the thickness of an adhesive layer can express the effect of this invention more, Preferably they are 0.5 micrometer - 150 micrometers, More preferably, they are 1 micrometer - 100 micrometers, More preferably, they are 2 micrometers - 80 micrometers. and particularly preferably 3 μm to 50 μm, and most preferably 5 μm to 30 μm.

The pressure-sensitive adhesive composition contains a base polymer, an ionic compound, and a fluorine-based compound. Since the pressure-sensitive adhesive composition contains a base polymer, an ionic compound and a fluorine-based compound, typically, in the manufacturing process of an optical member or an electronic member, the optical member or the electronic member during processing, assembling, inspection, transportation, etc. It is a surface protection film comprising a pressure-sensitive adhesive layer that is adhered to the exposed surface of the optical member or the electronic member in order to prevent the occurrence of surface flaws, sufficiently suppresses the peeling electrification voltage, and damages the optical member or the electronic member at the time of peeling It is possible to provide a surface protection film that does not do this.

In this invention, the effect of this invention can be expressed when an adhesive composition contains both an ionic compound and a fluorine-type compound in addition to a base polymer. In particular, by including (in combination with) both the ionic compound and the fluorine-based compound according to a preferred embodiment described later (sometimes referred to as a "specific fluorine-based compound"), the effects of the present invention can be remarkably expressed. This is a synergistic effect with a fluorine-based compound (preferably a specific fluorine-based compound) by coexisting an ionic compound capable of exhibiting an antistatic effect in the pressure-sensitive adhesive composition with a fluorine-based compound (preferably, a specific fluorine-based compound). It is estimated that this is because the ionic compound becomes unevenly distributed on the surface side (the side to be bonded to the adherend) of the pressure-sensitive adhesive layer.

The content ratio of the base polymer in the pressure-sensitive adhesive composition is preferably 60% by weight to 99.9% by weight, more preferably 65% by weight to 99.9% by weight, and still more preferably 70% by weight to 99.9% by weight in terms of solid content. %, particularly preferably 75% to 99.9% by weight, and most preferably 80% to 99.9% by weight. When the content of the base polymer in the pressure-sensitive adhesive composition is within the above range in terms of solid content, the peeling electrification voltage is sufficiently suppressed, and a surface protection film that does not damage an adherend (typically, an optical member or an electronic member) at the time of peeling is provided. can do.

The content of the ionic compound relative to 100 parts by weight of the base polymer is preferably 0.2 parts by weight or more, more preferably 0.3 parts by weight to 5.0 parts by weight, and still more preferably 0.5 parts by weight to 3.0 parts by weight. , particularly preferably 0.7 parts by weight to 2.0 parts by weight, and most preferably 0.8 parts by weight to 1.5 parts by weight. When the content of the ionic compound with respect to 100 parts by weight of the base polymer is within the above range, the peeling electrification voltage is sufficiently suppressed and the surface protection film does not damage the adherend (typically, an optical member or an electronic member) at the time of peeling. can provide When the content ratio of the ionic compound with respect to 100 parts by weight of the base polymer is too low outside the above range, there is a fear that the peeling electrification voltage cannot be sufficiently suppressed. When the content ratio of the ionic compound to 100 parts by weight of the base polymer is too high outside the above range, there is a risk of contaminating the adherend.

The content of the fluorine-based compound relative to 100 parts by weight of the base polymer is preferably 0.05 parts by weight or more, more preferably 0.1 to 5.0 parts by weight, still more preferably 0.15 to 3.0 parts by weight, Especially preferably, it is 0.2 weight part - 2.0 weight part, Most preferably, it is 0.23 weight part - 1.5 weight part. When the content of the fluorine-based compound with respect to 100 parts by weight of the base polymer is within the above range, a surface protection film that sufficiently suppresses the peeling electrification voltage and does not damage the adherend (typically, an optical member or an electronic member) during peeling can provide When the content ratio of the fluorine-based compound with respect to 100 parts by weight of the base polymer is too low outside the above range, there is a fear that the peeling electrification voltage cannot be sufficiently suppressed. When the content ratio of the fluorine-based compound to 100 parts by weight of the base polymer is too high outside the above range, there is a risk of contaminating the adherend.

<A-1-1. 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. When the base polymer is at least one selected from a urethane-based resin, an acrylic resin, a rubber-based resin, and a silicone-based resin, the peeling electrification voltage is more sufficiently suppressed, and the adherend (typically, an optical member or an electronic member) is further reduced during peeling. A surface protection film that does not break can be provided.

[A-1-1-1. polyol]

The polyol preferably reacts with a polyfunctional isocyanate compound to form a urethane-based resin. More specifically, preferably, a urethane-based resin is formed from a composition containing a polyol and a polyfunctional isocyanate compound, and specifically, a composition containing a polyol and a polyfunctional isocyanate compound is cured to form a urethane-based resin. As a method of curing a composition containing a polyol and a polyfunctional isocyanate compound to form a urethane-based resin, any suitable method can be used within a range that does not impair the effects of the present invention, such as a urethanation reaction method using bulk polymerization or solution polymerization. can be hired

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

The polyol is preferably at least one selected from polyester polyol, polyether polyol, polycaprolactone polyol, polycarbonate polyol, and castor oil-based polyol. Since the effect of this invention can be expressed more, As a polyol, 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, polyether polyols obtained by addition polymerization of alkylene oxides such as ethylene oxide, propylene oxide and butylene oxide using hydroquinone and the like) as an initiator. 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, ethylbutyl 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; polycarbonate polyols 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; polycarbonate polyols 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 above 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 a castor oil-based polyol obtained by reacting a castor oil fatty acid with polypropylene glycol.

The number average molecular weight Mn of the polyol is preferably 300 to 100000, more preferably 400 to 75000, still more preferably 450 to 50000, particularly preferably 500 to 30000. When the number average molecular weight Mn of the polyol is within the above range, it is difficult to peel more easily from the adherend, and typically, in the manufacturing process of the optical member or the electronic member, it is adhered to the exposed surface of the optical member or the electronic member. The later peeling is more difficult to generate|occur|produce, and when peeling becomes necessary, the surface protection film which can peel more easily can be provided.

The polyol preferably contains the 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 is preferably 5% by weight or more, more preferably 25% by weight to 100% by weight, still more preferably 50% by weight to 100% by weight, particularly preferably is 70% to 100% by weight, and most preferably 90% to 100% by weight. When the content ratio of the polyol (A1) in the polyol is within the above range, it is difficult to peel more easily from the adherend, and typically, in the manufacturing process of the optical member or the electronic member, the exposed surface of the optical member or the electronic member. When peeling after affixing to the surface is more difficult to occur and peeling is required, the surface protection film which can peel more easily can be provided.

As polyol (A1), Preferably, the number average molecular weight Mn of 3 OH groups contains the polyol (A1a) of 8000-20000. The number of polyols (A1a) may be one, and 2 or more types may be sufficient as them.

The content of the polyol (A1a) in the polyol (A1) is preferably 50% by weight or more, more preferably 60% by weight to 100% by weight, still more preferably 70% by weight to 95% by weight, Especially preferably, it is 75 weight% - 93 weight%, Most preferably, it is 80 weight% - 90 weight%. When the content of the polyol (A1a) in the polyol (A1) is within the above range, it is difficult to peel more easily from the adherend, and typically, in the manufacturing process of the optical member or the electronic member, the optical member or the electronic member. When peeling after affixing on the exposed surface of . is more difficult to occur, and peeling becomes necessary, the surface protection film which can peel more easily can be provided.

The number average molecular weight Mn of the polyol (A1a) is 8000 to 20000, preferably 8000 to 18000, more preferably 8500 to 17000, still more preferably 9000 to 16000, particularly preferably 9500 to 15500, , most preferably from 10000 to 15000. When the number average molecular weight Mn of the polyol (A1a) is within the above range, it is difficult to peel more easily from the adherend, and typically, in the manufacturing process of the optical member or the electronic member, the exposed surface of the optical member or the electronic member When peeling after affixing to the surface is more difficult to occur and peeling is required, the surface protection film which can peel more easily can be provided.

The polyol (A1) may contain the polyol (A1b) having 3 or more OH groups and a number average molecular weight Mn of 5000 or less. The number of polyols (A1b) may be one, and 2 or more types may be sufficient as them.

The polyol (A1b) is preferably a polyol having 3 OH groups (triol), a polyol having 4 OH groups (tetraol), a polyol having 5 OH groups (pentaol), and a polyol having 6 OH groups (hexane All) is at least one selected from.

The content of the polyol (A1b) in the polyol (A1) is preferably 50 wt% or less, more preferably 0 wt% to 40 wt%, still more preferably 5 wt% to 30 wt%, Especially preferably, it is 7 weight% - 25 weight%, Most preferably, it is 10 weight% - 20 weight%. When the content ratio of the polyol (A1b) in the polyol (A1) is within the above range, it is difficult to peel more easily from the adherend, and typically, during the manufacturing process of the optical member or the electronic member, the optical member or the electronic member. When peeling after affixing on the exposed surface of . is more difficult to occur, and peeling becomes necessary, the surface protection film which can peel more easily can be provided.

The number average molecular weight Mn of the polyol (A1b) is preferably 500 to 5000, more preferably 600 to 4500, still more preferably 700 to 4000, particularly preferably 800 to 3500, most preferably is 900 to 3300. When the number average molecular weight Mn of the polyol (A1b) is within the above range, it is difficult to peel more easily from the adherend, typically in the manufacturing process of the optical member or electronic member, on the exposed surface of the optical member or the electronic member. When peeling after sticking is more difficult to generate|occur|produce and peeling becomes necessary, the surface protection film which can peel more easily can be provided. When the number average molecular weight Mn of the polyol (A1b) is out of the above range, there is a fear that particularly the synergism of the adhesive force with time may increase, and there is a fear that excellent reworkability may not be expressed.

The polyol (A1b) is at least one selected from a polyol having 4 OH groups (tetraol), a polyol having 5 OH groups (pentaol), and a polyol having 6 OH groups (hexanol), their total amount The content of silver in the polyol (A1) is preferably 40 wt% or less, more preferably 0 wt% to 30 wt%, still more preferably 3 wt% to 20 wt%, particularly preferably is 5% to 15% by weight, and most preferably 7% to 10% by weight. In the polyol (A1), the polyol (A1b) is at least one selected from a polyol having 4 OH groups (tetraol), a polyol having 5 OH groups (pentaol), and a polyol having 6 OH groups (hexanol) When the total amount of these cases is within the above range, it is difficult to peel more easily from the adherend, and typically, during the manufacturing process of the optical member or the electronic member, after affixing to the exposed surface of the optical member or the electronic member When peeling is more difficult to generate|occur|produce and peeling becomes necessary, the surface protection film which can peel more easily can be provided. In addition, it can be a surface protection film excellent in transparency.

The polyol (A1b) is at least one selected from among polyols having 4 OH groups (tetraol), polyols having 5 OH groups (pentaol), and polyols having 6 OH groups (hexanol). The content of the polyol (A1) as a whole is preferably less than 10% by weight, more preferably 7% by weight or less, still more preferably 5% by weight or less, and particularly preferably 3% by weight or less. and most preferably 1% by weight or less. In the polyol (A1b), the content ratio of at least one selected from a polyol having 4 OH groups (tetraol), a polyol having 5 OH groups (pentaol), and a polyol having 6 OH groups (hexanol) is the above If it is within the range, it is difficult to peel more easily from the adherend, typically, during the manufacturing process of the optical member or the electronic member, peeling after sticking to the exposed surface of the optical member or the electronic member is more difficult to occur, Moreover, when peeling becomes necessary, the surface protection film which can peel more easily can be provided. In addition, the content ratio of at least one selected from polyol (tetraol) having 4 OH groups, polyol having 5 OH groups (pentaol), and polyol having 6 OH groups (hexanol) in the polyol (A1b) When it deviates from this range, there exists a possibility that transparency of a surface protection film may fall.

The polyol (A1) may contain the polyol (A1c) having 4 or more OH groups and having a number average molecular weight Mn of 20000 or less. The number of polyols (A1c) may be one, and two or more types may be sufficient as them.

The content ratio of the polyol (A1c) having 4 or more OH groups and having a number average molecular weight Mn of 20000 or less in the polyol (A1) is preferably less than 70% by weight, more preferably 60% by weight or less, and further Preferably it is 50 weight% or less, Especially preferably, it is 40 weight% or less, Most preferably, it is 30 weight% or less. When the content ratio of the polyol (A1c) having 4 or more OH groups and having a number average molecular weight Mn of 20000 or less in the polyol (A1) is within the above range, it is difficult to peel more easily from the adherend, and typically, an optical member or During the manufacturing process of the electronic member, peeling after sticking to the exposed surface of the optical member or the electronic member is more difficult to occur, and when peeling is required, a surface protection film that can be peeled more easily. can In addition, it can be a surface protection film excellent in transparency.

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

The urethane prepolymer preferably reacts with a polyfunctional isocyanate compound to form a urethane-based resin. More specifically, preferably, a urethane resin is formed from a composition containing a urethane prepolymer and a polyfunctional isocyanate compound, and specifically, a composition containing a urethane prepolymer and a polyfunctional isocyanate compound is cured to form a urethane resin. As a method for forming a urethane-based resin by curing a composition containing a polyol and a polyfunctional isocyanate compound, any suitable production method can be adopted as long as it is a method for producing a urethane-based resin using a so-called “urethane prepolymer” as a raw material.

In the description of the present invention, "urethane prepolymer" is a "urethane prepolymer" commonly called by those skilled in the art in the production of urethane resins, and is different from "polyol" described in A-1-1-1. do.

The number of urethane prepolymers may be one, and 2 or more types may be sufficient as them.

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

The urethane prepolymer is preferably a polyurethane polyol, and more preferably, a polyester polyol (a1) or a polyether polyol (a2), each alone or as a mixture of (a1) and (a2), in the presence of a catalyst It is made by making it react with a polyfunctional isocyanate compound under the under or non-catalyst. The number of polyester polyols (a1) may be one, and 2 or more types may be sufficient as them. The number of polyether polyols (a2) may be one, and 2 or more types may be sufficient as them.

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 molecular weight of polyester polyol (a1), it can use from low molecular weight to high molecular weight. As molecular weight of polyester polyol (a1), number average molecular weight Mn becomes like this. Preferably it is 100-100000. When the number average molecular weight Mn is less than 100, the reactivity becomes high and there exists a possibility that it may become easy to gelatinize. When the number average molecular weight Mn exceeds 100000, the reactivity becomes low, and there exists a possibility that the cohesive force of polyurethane polyol itself may become small further. 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 molecular weight of polyether polyol (a2), it can use from low molecular weight to high molecular weight. As molecular weight of polyether polyol (a2), number average molecular weight Mn becomes like this. Preferably it is 100-100000. When the number average molecular weight Mn is less than 100, the reactivity becomes high and there exists a possibility that it may become easy to gelatinize. When the number average molecular weight Mn exceeds 100000, the reactivity becomes low, and there exists a possibility that the cohesive force of polyurethane polyol itself may become small further. The usage-amount of polyether polyol (a2) becomes like this in the polyol which comprises a polyurethane polyol, Preferably it is 0 mol% - 90 mol%.

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, a polyether polyol having a number average molecular weight Mn of 100 to 100000, and having at least three or more hydroxyl groups in one molecule may be partially or entirely used. do. As the polyether polyol (a2), when a polyether polyol having a number average molecular weight Mn 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. there is. In such a polyether polyol, when the number average molecular weight Mn 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 the number average molecular weight Mn exceeds 100000, the 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 Mn of such polyether polyol is more preferably from 100 to 10000.

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 dibutyl tin dichloride, dibutyl tin oxide, dibutyl tin dibromide, dibutyl tin dimaleate, dibutyl tin dilaurate (DBTDL), dibutyl tin diacetate, 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, etc. are mentioned.

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.

In the case of using a catalyst when obtaining a polyurethane polyol, in a system in which two types of polyols, a polyester polyol and a polyether polyol, exist, the problem of gelation or the reaction solution becomes cloudy in a single catalyst system because of the difference in reactivity is likely to occur 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 butyl tin dilaurate and 2-ethyl tin hexanoate. The blending ratio is, in terms of weight ratio, 2-ethyl tin hexanoate/dibutyl tin 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 catalytic activity.

When using a catalyst when obtaining a polyurethane polyol, the usage-amount of a catalyst with respect to the total amount of polyester polyol (a1), polyether polyol (a2), and a polyfunctional isocyanate compound, Preferably it is 0.01 to 1.0 weight%. am.

When a catalyst is used when obtaining a 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) polyester polyol, polyether polyol, catalyst, and polyfunctional isocyanate compound are charged to the flask, 2) polyester polyol, polyether polyol, and catalyst are charged to the flask and the method of adding a polyfunctional isocyanate compound dropwise is mentioned. As a method of obtaining a polyurethane polyol, in controlling reaction, the method of 2) is preferable.

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.

[A-1-1-3. acrylic resin]

As acrylic resin, any suitable acrylic resin can be employ|adopted in the range which does not impair the effect of this invention. One type may be sufficient as acrylic resin, and 2 or more types may be sufficient as it.

Since the weight average molecular weight of acrylic resin can express the effect of this invention more, Preferably it is 300,000-2.5 million, More preferably, it is 350,000-2 million, More preferably, it is 400,000- It is 1.8 million, Especially preferably, it is 500,000-1,500,000.

As an acrylic resin, from the point which can express the effect of this invention more, Preferably (a component) (meth)acrylic acid alkylester whose alkyl group carbon number of an alkylester part is 4-12, (b component) has an OH group (component b) It is an acrylic resin formed by polymerization from the composition (B) containing at least 1 sort(s) selected from the group which consists of meth)acrylic acid ester and (meth)acrylic acid. (a component) and (b component) may each independently be 1 type, and 2 or more types may be sufficient as them.

Examples of the (meth)acrylic acid alkyl ester (component a) having 4 to 12 carbon atoms in the alkyl group of the alkyl ester moiety include n-butyl (meth)acrylate, isobutyl (meth)acrylate, s-butyl (meth)acrylate, (meth) acrylate t-butyl, (meth) acrylate pentyl, (meth) acrylate hexyl, (meth) acrylate heptyl, (meth) acrylate octyl, (meth) acrylate 2-ethylhexyl, (meth) acrylate isooctyl, (meth) acrylate ) Nonyl acrylate, (meth) acrylate isononyl, (meth) acrylate decyl, (meth) acrylate isodecyl, (meth) acrylate undecyl, (meth) acrylate dodecyl, etc. are mentioned. Among these, from the point which can express the effect of this invention more, Preferably they are (meth)acrylic-acid n-butyl and (meth)acrylic-acid 2-ethylhexyl, More preferably, they are n-butyl acrylate and 2-ethyl acrylate. It is hexyl.

As at least one (component b) selected from the group consisting of (meth)acrylic acid ester and (meth)acrylic acid having an OH group, for example, (meth)acrylic acid hydroxyethyl, (meth)acrylic acid hydroxypropyl, (meth) (meth)acrylic acid ester, (meth)acrylic acid, etc. which have OH groups, such as hydroxybutyl acrylate, are mentioned. Among these, since the effect of this invention can be expressed more, Preferably they are (meth)acrylic-acid hydroxyethyl and (meth)acrylic acid, More preferably, they are hydroxyethyl acrylate and acrylic acid.

The composition (B) may contain copolymerizable monomers other than the component (a) and the component (b). The number of copolymerizable monomers may be one, and 2 or more types may be sufficient as them. Examples of such a copolymerizable monomer include itaconic acid, maleic acid, fumaric acid, crotonic acid, isocrotonic acid, and acid anhydrides thereof (for example, acid anhydride group-containing monomers such as maleic anhydride and itaconic anhydride). carboxyl group-containing monomers (except (meth)acrylic acid); (meth)acrylamide, N,N-dimethyl (meth)acrylamide, N-methylol (meth)acrylamide, N-methoxymethyl (meth)acrylamide, N-butoxymethyl (meth)acrylamide, N -amide group containing monomers, such as hydroxyethyl (meth)acrylamide; amino group-containing monomers such as aminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, and t-butylaminoethyl (meth)acrylate; Epoxy group-containing monomers, such as (meth)acrylic-acid glycidyl and (meth)acrylic-acid methylglycidyl; cyano group-containing monomers such as acrylonitrile and methacrylonitrile; N-vinyl-2-pyrrolidone, (meth)acryloylmorpholine, N-vinylpiperidone, N-vinylpiperazine, N-vinylpyrrole, N-vinylimidazole, vinylpyridine, vinylpyrimidine, Heterocyclic containing vinyl-type monomers, such as vinyloxazole; Sulfonic acid group-containing monomers, such as sodium vinylsulfonate; phosphoric acid group-containing monomers such as 2-hydroxyethyl acryloyl phosphate; imide group-containing monomers such as cyclohexyl maleimide and isopropyl maleimide; isocyanate group-containing monomers such as 2-methacryloyloxyethyl isocyanate; (meth)acrylic acid ester having an alicyclic hydrocarbon group such as cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, and isobornyl (meth)acrylate; (meth)acrylic acid ester having an aromatic hydrocarbon group such as phenyl (meth)acrylate, phenoxyethyl (meth)acrylate, and benzyl (meth)acrylate; vinyl esters such as vinyl acetate and vinyl propionate; aromatic vinyl compounds such as styrene and vinyltoluene; olefins and dienes such as ethylene, butadiene, isoprene, and isobutylene; vinyl ethers such as vinyl alkyl ether; vinyl chloride; and the like.

As a copolymerizable monomer, a polyfunctional monomer can also be employ|adopted. A polyfunctional monomer means the monomer which has two or more ethylenically unsaturated groups in 1 molecule. As an ethylenically unsaturated group, any suitable ethylenically unsaturated group can be employ|adopted in the range which does not impair the effect of this invention. As such an ethylenically unsaturated group, radically polymerizable functional groups, such as a vinyl group, a propenyl group, an isopropenyl group, a vinyl ether group (vinyloxy group), and an allyl ether group (allyloxy group), are mentioned, for example. Examples of the polyfunctional monomer include hexanediol di(meth)acrylate, butanediol di(meth)acrylate, (poly)ethylene glycol di(meth)acrylate, (poly)propylene glycol di(meth)acrylate, neo Pentyl glycol di (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, trimethylol propane tri (meth) acrylate, Tetramethylolmethane tri(meth)acrylate, allyl (meth)acrylate, vinyl (meth)acrylate, divinylbenzene, epoxy acrylate, polyester acrylate, urethane acrylate, etc. are mentioned. The number of such polyfunctional monomers may be one, and 2 or more types may be sufficient as them.

As a copolymerizable monomer, (meth)acrylic-acid alkoxyalkyl ester is also employable. As the (meth)acrylic acid alkoxyalkyl ester, for example, (meth)acrylic acid 2-methoxyethyl, (meth)acrylic acid 2-ethoxyethyl, (meth)acrylic acid methoxytriethylene glycol, (meth)acrylic acid 3-methoxy propyl, (meth)acrylic acid 3-ethoxypropyl, (meth)acrylic acid 4-methoxybutyl, (meth)acrylic acid 4-ethoxybutyl, etc. are mentioned. The number of (meth)acrylic acid alkoxyalkyl esters may be one, and 2 or more types may be sufficient as them.

The content of the (meth)acrylic acid alkyl ester (component a) having 4 to 12 carbon atoms in the alkyl group of the alkyl ester portion is the total amount of the monomer components constituting the acrylic polymer (100% by weight) from the viewpoint that the effect of the present invention can be more expressed. ), preferably 30 wt% or more, more preferably 35 wt% to 99 wt%, still more preferably 40 wt% to 98 wt%, particularly preferably 50 wt% to 95 wt% %am.

The content of at least one (component b) selected from the group consisting of (meth)acrylic acid ester having an OH group and (meth)acrylic acid is a monomer component constituting the acrylic polymer from the viewpoint that the effect of the present invention can be more expressed. With respect to the whole amount (100 weight%), Preferably it is 1 weight% or more, More preferably, it is 1 weight% - 30 weight%, More preferably, it is 2 weight% - 20 weight%, Especially preferably, it is 3 weight%. % to 10% by weight.

The composition (B) may contain any appropriate other component within the range which does not impair the effect of this invention. As such other components, a polymerization initiator, a chain transfer agent, a solvent, etc. are mentioned, for example. Any suitable content can be employ|adopted for content of these other components in the range which does not impair the effect of this invention.

As a polymerization initiator, a thermal polymerization initiator, a photoinitiator (photoinitiator), etc. can be employ|adopted according to the kind of polymerization reaction. The number of polymerization initiators may be one, and 2 or more types may be sufficient as them.

A thermal polymerization initiator, Preferably, when obtaining an acrylic resin by solution polymerization, it can be employ|adopted. Examples of such thermal polymerization initiators include azo polymerization initiators, peroxide polymerization initiators (eg, dibenzoyl peroxide, tert-butyl permaleate, etc.), redox polymerization initiators, and the like. Among these thermal polymerization initiators, the azo-type initiator disclosed in Unexamined-Japanese-Patent No. 2002-69411 is especially preferable. Such an azo polymerization initiator is preferable in that the decomposition product of the polymerization initiator does not easily remain in the acrylic resin as a portion causing generation of a gas (outgas) generated by heating. Examples of the azo polymerization initiator include 2,2'-azobisisobutyronitrile (hereinafter, may be referred to as AIBN), 2,2'-azobis-2-methylbutyronitrile (hereinafter referred to as AMBN in some cases) ), 2,2'-azobis(2-methylpropionic acid)dimethyl, and 4,4'-azobis-4-cyanovaleric acid.

A photoinitiator, Preferably, when obtaining an acrylic polymer by active energy ray polymerization, it can be employ|adopted. Examples of the photopolymerization initiator include a benzoin ether-based photopolymerization initiator, an acetophenone-based photopolymerization initiator, an α-ketol-based photopolymerization initiator, an aromatic sulfonyl chloride-based photopolymerization initiator, a photoactive oxime-based photopolymerization initiator, a benzoin-based photopolymerization initiator, and a benzyl-based photopolymerization initiator. An initiator, a benzophenone type photoinitiator, a ketal type photoinitiator, a thioxanthone type photoinitiator, etc. are mentioned.

As a benzoin ether type photoinitiator, for example, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2,2-dimethoxy-1,2-di phenylethan-1-one, anisolemethyl ether, and the like. Examples of the acetophenone-based photopolymerization initiator include 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenylketone, 4-phenoxydichloroacetophenone, 4 -(t-butyl)dichloroacetophenone etc. are mentioned. Examples of the α-ketol-based photopolymerization initiator include 2-methyl-2-hydroxypropiophenone and 1-[4-(2-hydroxyethyl)phenyl]-2-methylpropan-1-one. there is. As an aromatic sulfonyl chloride type|system|group photoinitiator, 2-naphthalene sulfonyl chloride etc. are mentioned, for example. Examples of the photoactive oxime-based photopolymerization initiator include 1-phenyl-1,1-propanedione-2-(o-ethoxycarbonyl)-oxime. As a benzoin type photoinitiator, benzoin etc. are mentioned, for example. As a benzyl type photoinitiator, benzyl etc. are mentioned, for example. Examples of the benzophenone-based photopolymerization initiator include benzophenone, benzoylbenzoic acid, 3,3'-dimethyl-4-methoxybenzophenone, polyvinylbenzophenone, and α-hydroxycyclohexylphenylketone. As a ketal-type photoinitiator, benzyl dimethyl ketal etc. are mentioned, for example. As a thioxanthone type photoinitiator, For example, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2, 4- dimethyl thioxanthone, isopropyl thioxanthone, 2,4-diiso A propyl thioxanthone, dodecyl thioxanthone, etc. are mentioned.

Moreover, when a base polymer is an acrylic resin, the adhesive composition may contain the crosslinking agent. By using a crosslinking agent, the cohesive force of an adhesive can be improved and the effect of this invention can be expressed more. The number of crosslinking agents may be one, and 2 or more types may be sufficient as them.

Examples of the crosslinking agent include polyfunctional isocyanate crosslinking agents, epoxy crosslinking agents, melamine crosslinking agents, peroxide crosslinking agents, urea crosslinking agents, metal alkoxide crosslinking agents, metal chelate crosslinking agents, metal salt crosslinking agents, carbodiimide crosslinking agents, oxazoline crosslinking agents. , an aziridine-based crosslinking agent, an amine-based crosslinking agent, and the like. Among these, it is at least 1 sort(s) selected from the group which preferably consists of a polyfunctional isocyanate type crosslinking agent and an epoxy type crosslinking agent from the point which can express the effect of this invention more.

Examples of the polyfunctional isocyanate-based crosslinking agent include lower aliphatic polyisocyanates such as 1,2-ethylene diisocyanate, 1,4-butylene diisocyanate and 1,6-hexamethylene diisocyanate; alicyclic polyisocyanates such as cyclopentylene diisocyanate, cyclohexylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, and hydrogenated xylene diisocyanate; and aromatic polyisocyanates such as 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate and xylylene diisocyanate. Examples of the polyfunctional isocyanate-based crosslinking agent include trimethylolpropane/tolylene diisocyanate adduct (manufactured by Nippon Polyurethane Kogyo Co., Ltd., trade name "Coronate L"), trimethylolpropane/hexamethylene diisocyanate adduct (Nippon Polyurethane) Urethane Kogyo Co., Ltd. make, trade name "Coronate HL"), trade name "Coronate HX" (Nippon Polyurethane Kogyo Co., Ltd.), trimethylolpropane/xylylene diisocyanate adduct (Mitsui Chemical Co., Ltd. make, Commercial items, such as a brand name "Takenate 110N"), are also mentioned.

As the epoxy crosslinking agent (polyfunctional epoxy compound), for example, N,N,N',N'-tetraglycidyl-m-xylenediamine, diglycidylaniline, 1,3-bis(N,N-) Diglycidylaminomethyl)cyclohexane, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polyethylene glycol di Glycidyl ether, polypropylene glycol diglycidyl ether, sorbitol polyglycidyl ether, glycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, polyglycerol polyglycidyl ether, sorbitan polyglycidyl ether Dil ether, trimethylolpropane polyglycidyl ether, adipic acid diglycidyl ester, o-phthalic acid diglycidyl ester, triglycidyl-tris(2-hydroxyethyl) isocyanurate, resorcindiglycidyl ester In addition to cidyl ether and bisphenol-S-diglycidyl ether, an epoxy-based resin having two or more epoxy groups in the molecule may be mentioned. As an epoxy-type crosslinking agent, commercial items, such as a brand name "Tetrad C" (made by Mitsubishi Gas Chemical Co., Ltd.), are also mentioned.

Any suitable content can be employ|adopted for content of the crosslinking agent in an adhesive composition in the range which does not impair the effect of this invention. As such content, for example, from the point which can express the effect of this invention more, with respect to solid content (100 weight part) of acrylic resin, Preferably it is 0.05 weight part - 20 weight part, More preferably, it is 0.1 weight part. It is a part - 18 weight part, More preferably, it is 0.5 weight part - 15 weight part, Especially preferably, it is 0.5 weight part - 10 weight part.

[A-1-1-4. rubber-based resin]

As the rubber-based resin, a rubber-based resin used for any appropriate rubber-based adhesive, such as a known rubber-based adhesive described in Japanese Patent Application Laid-Open No. 2015-074771, etc., can be employed as long as the effects of the present invention are not impaired. . One type may be sufficient as these, and 2 or more types may be sufficient as them.

[A-1-1-5. silicone resin]

As the silicone-based resin, silicone-based resins used for any appropriate silicone-based adhesive, such as the well-known silicone-based adhesive described in Japanese Patent Application Laid-Open No. 2014-047280, etc., can be employed within a range that does not impair the effects of the present invention. . One type may be sufficient as these, and 2 or more types may be sufficient as them.

<A-1-2. Urethane-based resin>

As described above, the polyol as the base polymer preferably reacts with a polyfunctional isocyanate compound to form a urethane-based resin. More specifically, preferably, a urethane-based resin is formed from a composition containing a polyol and a polyfunctional isocyanate compound, and specifically, a composition containing a polyol and a polyfunctional isocyanate compound is cured to form a urethane-based resin. As a method of curing a composition containing a polyol and a polyfunctional isocyanate compound to form a urethane-based resin, any suitable method can be used within a range that does not impair the effects of the present invention, such as a urethanation reaction method using bulk polymerization or solution polymerization. can be hired

Further, as described above, the urethane prepolymer as the base polymer preferably reacts with a polyfunctional isocyanate compound to form a urethane-based resin. More specifically, preferably, a urethane resin is formed from a composition containing a urethane prepolymer and a polyfunctional isocyanate compound, and specifically, a composition containing a urethane prepolymer and a polyfunctional isocyanate compound is cured to form a urethane resin. As a method for forming a urethane-based resin by curing a composition containing a polyol and a polyfunctional isocyanate compound, any suitable production method can be adopted as long as it is a method for producing a urethane-based resin using a so-called “urethane prepolymer” as a raw material.

That is, one preferable embodiment of a urethane-type resin is a urethane-type resin formed from the composition containing a polyol and a polyfunctional isocyanate compound. Another preferred embodiment of the urethane-based resin is a urethane-based resin formed from a composition containing a urethane prepolymer and a polyfunctional isocyanate compound.

[A-1-2-1. Urethane-based resin formed from a composition containing a polyol and a polyfunctional isocyanate compound]

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

As the polyfunctional isocyanate compound, any suitable polyfunctional isocyanate compound that can be used in the urethanation reaction can be employed. Examples of the polyfunctional isocyanate compound include a polyfunctional aliphatic isocyanate compound, a polyfunctional alicyclic isocyanate, a polyfunctional aromatic isocyanate compound, and a polyfunctional aromatic aliphatic isocyanate compound.

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

Examples of the polyfunctional alicyclic isocyanate compound include 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate, 1,3-cyclopentane diisocyanate, 1,3-cyclohexanediisocyanate, 1, 4-cyclohexanediisocyanate, isophorone diisocyanate, methyl-2,4-cyclohexanediisocyanate, methyl-2,6-cyclohexanediisocyanate, 4,4'-methylenebis(cyclohexylisocyanate), 1,4 -Bis(isocyanatomethyl)cyclohexane, 1,4-bis(isocyanatomethyl)cyclohexane, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated Tetramethyl xylylene diisocyanate etc. are mentioned.

Examples of the polyfunctional aromatic diisocyanate compound include 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, and 2,2'-diisocyanate. Phenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-toluidine diisocyanate, 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate benzene, 4,4'- Diphenyl ether diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 4,4',4''-triphenylmethane triisocyanate, dianisidine diisocyanate, xylylene diisocyanate, etc. can be heard

Examples of the polyfunctional aromatic aliphatic isocyanate compound include ω,ω'-diisocyanate-1,3-dimethylbenzene, ω,ω'-diisocyanate-1,4-dimethylbenzene, ω,ω'-diisocyanate- 1,4-diethylbenzene, 1,4-tetramethylxylylenediisocyanate, 1,3-tetramethylxylylenediisocyanate, etc. are mentioned.

As a polyfunctional isocyanate compound, 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 and the polyfunctional isocyanate compound is preferably 5.0 or less, more preferably 0.1 to 3.0, still more preferably 0.2 to 2.5, as NCO group/OH group. , even more preferably from 0.3 to 2.5, still more preferably from 0.3 to 2.0, particularly preferably from 0.5 to 2.0, and most preferably from 0.5 to 1.8. When the equivalent ratio of NCO group / OH group is within the above range, it is difficult to peel easily from the adherend, and typically, in the manufacturing process of an optical member or an electronic member, it is adhered to the exposed surface of the optical member or the electronic member. It is hard to generate|occur|produce after peeling, and when peeling becomes necessary, the surface protection film which can peel easily can be provided. Moreover, when the equivalent ratio of NCO group/OH group exists in the said range, it becomes possible to reduce a haze. In particular, when a haze can be reduced to 3 % or less, the testability of the surface protection film by embodiment of this invention will improve more.

The content of the polyfunctional isocyanate compound is, with respect to the polyol, the polyfunctional isocyanate compound, preferably 1.0 wt% to 30 wt%, more preferably 1.5 wt% to 27 wt%, still more preferably 2.0 % by weight to 25% by weight, even more preferably from 2.3% to 23% by weight, still more preferably from 2.3% to 18% by weight, particularly preferably from 2.5% to 18% by weight, and most Preferably it is 2.5 weight% - 16 weight%. When the content ratio of the polyfunctional isocyanate compound is within the above range, it is difficult to peel easily from the adherend, and typically, during the manufacturing process of the optical member or the electronic member, it is adhered to the exposed surface of the optical member or the electronic member. It is hard to generate|occur|produce after peeling, and when peeling becomes necessary, the surface protection film which can peel easily can be provided. Moreover, when the content rate of a polyfunctional isocyanate compound exists in the said range, it becomes possible to reduce a haze. In particular, when a haze can be reduced to 3 % or less, the testability of the surface protection film by embodiment of this invention will improve more.

In order to cure a composition containing a polyol and a polyfunctional isocyanate compound, a catalyst is preferably used. As such a catalyst, an organometallic compound, a tertiary amine compound, etc. are mentioned, for example. The number of catalysts may be one, and 2 or more types may be sufficient as them.

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 dibutyl tin dichloride, dibutyl tin oxide, dibutyl tin dibromide, dibutyl tin maleate, dibutyl tin dilaurate, dibutyl tin diacetate, and dibutyl tin sulfide. , tributyl tin methoxide, tributyl tin acetate, triethyl tin ethoxide, tributyl tin ethoxide, dioctyl tin oxide, dioctyl tin dilaurate, tributyl tin chloride, tributyl tin 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 amount of 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 preferably based on the polyol. is 0.01 wt% to 0.20 wt%. When the amount of the catalyst is within the above range, it is difficult to peel easily from the adherend, and typically, in the manufacturing process of the optical member or the electronic member, peeling occurs after sticking to the exposed surface of the optical member or the electronic member. It is difficult to do it, and when peeling becomes necessary, the surface protection film which can peel easily can be provided.

In the composition containing the polyol and the polyfunctional isocyanate compound, any appropriate other components may be included within a range that does not impair the effects of the present invention. Examples of such other components include antioxidants, ultraviolet absorbers, light stabilizers, resin components, tackifiers, crosslinking retarders, inorganic fillers, organic fillers, metal powders, pigments, thin substances, softeners, anti-aging agents, conductive agents. , a surface lubricant, a leveling agent, a corrosion inhibitor, a heat-resistant stabilizer, a polymerization inhibitor, a lubricant, a solvent, and the like.

Among these other components, it is a preferable embodiment to include a deterioration inhibitor such as an antioxidant, an ultraviolet absorber, or a light stabilizer. When the pressure-sensitive adhesive composition contains the deterioration inhibitor, the adhesive residue prevention property can be excellent, such as it is difficult to generate an adhesive residue on the adherend even after affixing the formed pressure-sensitive adhesive layer to the adherend and then storing it in a warm state. The number of deterioration inhibitors may be one, and 2 or more types may be sufficient as them. As a deterioration inhibitor, Especially preferably, it is 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.

As a phenolic antioxidant, a monophenol-type antioxidant, a bisphenol-type antioxidant, a polymer type phenol-type antioxidant, etc. are mentioned, for example.

Examples of the monophenolic antioxidant include 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-4-ethylphenol, stear-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)butyric acid]glycol ester, 1,3,5-tris(3',5'- Di-t-butyl-4'-hydroxybenzyl)-S-triazine-2,4,6-(1H,3H,5H)trione, tocophenol, 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. -Dodecyloxy benzophenone, 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, and the like.

Examples of the benzotriazole-based ultraviolet absorber include 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-5'-tert-butylphenyl)benzotriazole, 2 -(2'-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-benzotriazol-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 nickelbis(octylphenyl)sulfide, [2,2'-thiobis(4-tert-octylphenolate)]-n-butylamine nickel, nickel complex-3,5-di- tert-butyl-4-hydroxybenzyl-phosphate monoethylate, nickel-dibutyldithiocarbamate, benzoate type nitrate, nickel-dibutyldithiocarbamate, etc. are mentioned.

[A-1--2-2. Urethane-based resin formed from a composition containing a urethane prepolymer and a polyfunctional isocyanate compound]

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

As the polyfunctional isocyanate compound, any suitable polyfunctional isocyanate compound that can be used in the urethanation reaction can be employed. As such a polyfunctional isocyanate compound, the "polyfunctional isocyanate compound" demonstrated by A-1-2, for example is mentioned.

In the composition containing the urethane prepolymer and the polyfunctional isocyanate compound, any appropriate other components may be included in the range not impairing the effects of the present invention. Examples of such other components include antioxidants, ultraviolet absorbers, light stabilizers, resin components, tackifiers, crosslinking retarders, inorganic fillers, organic fillers, metal powders, pigments, thin substances, softeners, anti-aging agents, conductive agents. , a surface lubricant, a leveling agent, a corrosion inhibitor, a heat-resistant stabilizer, a polymerization inhibitor, a lubricant, a solvent, and the like.

Among these other components, it is a preferable embodiment to include a deterioration inhibitor such as an antioxidant, an ultraviolet absorber, or a light stabilizer. When the pressure-sensitive adhesive composition contains the deterioration inhibitor, the adhesive residue prevention property can be excellent, such as it is difficult to generate an adhesive residue on the adherend even after affixing the formed pressure-sensitive adhesive layer to the adherend and then storing it in a warm state. The number of deterioration inhibitors may be one, and 2 or more types may be sufficient as them. As a deterioration inhibitor, Especially preferably, it is antioxidant. About the detail of antioxidant, a ultraviolet absorber, and a light stabilizer, the description in A-1-2-1 can be referred.

The equivalent ratio of the NCO group and the OH group in the urethane prepolymer and the polyfunctional isocyanate compound is preferably 5.0 or less, more preferably 0.01 to 3.0, still more preferably 0.02 to 2.0, as NCO group/OH group. and even more preferably 0.03 to 2.0, still more preferably 0.03 to 1.9, particularly preferably 0.05 to 1.9, and most preferably 0.05 to 1.8. When the equivalent ratio of NCO group / OH group is within the above range, it is difficult to peel easily from the adherend, and typically, in the manufacturing process of an optical member or an electronic member, it is adhered to the exposed surface of the optical member or the electronic member. It is hard to generate|occur|produce after peeling, and when peeling becomes necessary, the surface protection film which can peel easily can be provided. Moreover, when the equivalent ratio of NCO group/OH group exists in the said range, it becomes possible to reduce a haze. In particular, when a haze can be reduced to 3 % or less, the testability of the surface protection film by embodiment of this invention will improve more.

The content of the polyfunctional isocyanate compound is, with respect to the urethane prepolymer, the polyfunctional isocyanate compound, preferably 0.01 wt% to 30 wt%, more preferably 0.05 wt% to 25 wt%, still more preferably 0.1 wt% to 25 wt%, even more preferably 0.5 wt% to 25 wt%, still more preferably 0.5 wt% to 23 wt%, particularly preferably 1 wt% to 23 wt%, Most preferably, it is 1 wt% to 21 wt%. When the content ratio of the polyfunctional isocyanate compound is within the above range, it is difficult to peel easily from the adherend, and typically, during the manufacturing process of the optical member or the electronic member, it is adhered to the exposed surface of the optical member or the electronic member. It is hard to generate|occur|produce after peeling, and when peeling becomes necessary, the surface protection film which can peel easily can be provided. Moreover, when the content rate of a polyfunctional isocyanate compound exists in the said range, it becomes possible to reduce a haze. In particular, when a haze can be reduced to 3 % or less, the testability of the surface protection film by embodiment of this invention will improve more.

<A-1-3. Ionic Compounds>

As the ionic compound, any appropriate ionic compound can be employed as long as the effects of the present invention are not impaired. As such an ionic compound, Preferably it is an ionic liquid, More preferably, it is an ionic liquid containing a fluoro organic anion. The pressure-sensitive adhesive composition is added to the base polymer and contains both an ionic compound and a fluorine-based compound to be described later, so typically, in the manufacturing process of an optical member or an electronic member, processing, assembling, inspection, transport, etc. It is a surface protection film including a pressure-sensitive adhesive layer that is adhered to the exposed surface of the optical member or the electronic member in order to prevent the occurrence of surface defects of the optical member or the electronic member, and sufficiently suppresses the peeling electrification voltage, and at the time of peeling, the optical member The surface protection film which does not damage a member or this electronic member can be provided.

The number of ionic compounds may be one, and 2 or more types may be sufficient as them.

An ionic liquid means the molten salt (ionic compound) which shows a liquid phase at 25 degreeC.

As the ionic liquid, any appropriate ionic liquid can be employed as long as the effects of the present invention are not impaired. As such an ionic liquid, Preferably, it is an ionic liquid containing a fluoro organic anion, More preferably, it is an ionic liquid composed of a fluoro organic anion and an onium cation. By employing an ionic liquid composed of a fluoroorganic anion and an onium cation as the ionic liquid, by using it in combination with a fluorine-based compound described later, typically in the manufacturing process of an optical member or an electronic member, processing, assembly, and inspection , It is a surface protection film including a pressure-sensitive adhesive layer that is adhered to the exposed surface of the optical member or the electronic member to prevent surface defects of the optical member or the electronic member during transportation, etc., and more sufficiently suppresses the peeling electrification voltage and the surface protection film which does not further damage the said optical member or this electronic member at the time of peeling can be provided.

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 in combination with a fluorine-based compound to be described later, typically, the optical member or the electronic member is processed, assembling, inspected, transported, or the like in the manufacturing process of an optical member or electronic member. It is a surface protection film comprising a pressure-sensitive adhesive layer that is adhered to the exposed surface of the optical member or the electronic member to prevent the occurrence of surface flaws, and more sufficiently suppresses the peeling electrification voltage, and at the time of peeling, the optical member or the electronic member It is possible to provide a surface protection film that does not further damage the

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), Ra represents a hydrocarbon group having 4 to 20 carbon atoms and may contain a hetero atom, and Rb and Rc are the same or different and represent hydrogen or a hydrocarbon group having 1 to 16 carbon atoms, hetero It may contain an atom. However, when the nitrogen atom contains a double bond, Rc is absent.

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

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

In the general formula (4), Z represents a nitrogen atom, a sulfur atom or a phosphorus atom, and Rl, Rm, Rn and Ro are the same or different, represent a hydrocarbon group having 1 to 20 carbon atoms, and include a hetero atom, there may be with the proviso that when Z is a sulfur atom, Ro is absent.

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

Examples of the cation represented by the general formula (1) include a pyridinium cation, a pyrrolidinium cation, a piperidinium cation, a cation having a pyrroline skeleton, 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-methylimide 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 , a 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-methylpyrazolium cation, 1-ethyl-2,3,5 -pyrazolium cations such as trimethylpyrazolium cation, 1-propyl-2,3,5-trimethylpyrazolium cation, and 1-butyl-2,3,5-trimethylpyrazolium cation; Pyrazolinium cations such as 1-ethyl-2,3,5-trimethylpyrazolium cation, 1-propyl-2,3,5-trimethylpyrazolium cation, and 1-butyl-2,3,5-trimethylpyrazolium 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. there is.

Among these, triethylmethylammonium cation, tributylethylammonium cation, trimethyldecylammonium cation, diethylmethylsulfonium cation, and dibutylethylsulfonium cation are preferable from the viewpoint that the effect of the present invention can be further expressed. 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 trifluoromethanesulfonate, pentafluoroethanesulfonate, heptafluoropropanesulfonate, nonafluorobutanesulfonate, bis(fluorosulfonyl)imide, bis(trifluoromethanesulfonyl)imide am.

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, triethylheptylammoniumbis(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, glycidyltrimethylammoniumbis(trifluoromethanesulfonyl)imide, glycidyltrimethylammoniumbis(pentafluoroethanesulfonyl)imide, diallyldimethylammoniumbis(trifluoromethanesulfonyl)imide de, diallyldimethylbis(pentafluoroethanesulfonyl)imide, lithium bis(trifluoromethanesulfonyl)imide, lithium bis(fluorosulfonyl)imide, and the like.

Among these ionic liquids, 1-hexylpyridiniumbis(fluorosulfonyl)imide, 1-ethyl-3-methylpyridinium trifluoromethanesulfonate, 1-ethyl-3- Methylpyridinium pentafluoroethanesulfonate, 1-ethyl-3-methylpyridinium heptafluoropropanesulfonate, 1-ethyl-3-methylpyridinium nonafluorobutanesulfonate, 1-butyl-3-methylpyri Dinium trifluoromethanesulfonate, 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-propylpiperidinium Bis(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( Fluorosulfonyl)imide, 1-hexyl-3-methylimidazoliumbis(fluorosulfonyl)imide, trimethylpropylammoniumbis(trifluoromethanesulfonyl)imide, lithium bis(trifluoromethane sulfonyl) 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 in general, it is described in the document "Ionic liquid - the forefront and future of development -" (published by CMC Publishing Co., Ltd.) Halide method, hydroxide method, acid ester method, complex formation method, neutralization method, etc. are used as described above.

For the halide method, the hydroxide method, the acid ester method, the complex formation method and the neutralization method, examples of the method for synthesizing the nitrogen-containing onium salt are shown below. Other sulfur-containing onium salts, phosphorus-containing onium salts, etc. It can be obtained by the same method also about an ionic liquid.

The halide method is a method performed by a reaction as shown in the reaction formulas (1) to (3). First, a tertiary amine is reacted with an alkyl halide to obtain a 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} It is made to react, and the target ionic liquid (R ₄ NA) is obtained.

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 hydroxide by ion exchange membrane electrolysis (Scheme (4)), OH-type ion exchange resin method (Scheme (5)), or _{reaction with silver oxide (Ag 2} O) (Scheme (6)) (R ₄ NOH) is obtained (as halogen, chlorine, bromine and iodine are used).

_{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 the 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)). esters of organic acids such as phonic acid and formic acid).

_{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 the reaction formula (12). It 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, etc.} there is.

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.

<A-1-4. Fluorine compounds>

As the fluorine-based compound, any appropriate fluorine-based compound can be employed as long as the effects of the present invention are not impaired. When the pressure-sensitive adhesive composition is added to the base polymer and contains both the fluorine-based compound and the ionic compound described above, typically, in the manufacturing process of an optical member or an electronic member, processing, assembly, inspection, transportation, etc. It is a surface protection film including a pressure-sensitive adhesive layer that is adhered to the exposed surface of the optical member or the electronic member in order to prevent the occurrence of surface defects of the optical member or the electronic member, and sufficiently suppresses the peeling electrification voltage, The surface protection film which does not damage this optical member or this electronic member can be provided.

One type may be sufficient as a fluorine-type compound, and 2 or more types may be sufficient as it.

As a fluorine-type compound, 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, for example.

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-based 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 alkane.

A preferred embodiment of the fluorine-containing compound is an oligomer having a fluorine-containing group, a hydrophilic group and/or a lipophilic group (“specific fluorine-based compound”). By including (using both) the ionic compound and the above "specific fluorine-based compound", the effect of the present invention can be remarkably expressed. As described above, in the pressure-sensitive adhesive composition, by coexisting an ionic compound capable of exhibiting an antistatic effect with a fluorine-based compound (preferably, a specific fluorine-based compound), a fluorine-based compound (preferably, a specific fluorine-based compound) It is estimated that it is because an ionic compound becomes unevenly distributed on the surface side (side to be joined to a to-be-adhered body) of an adhesive layer by the synergistic effect with. Typical examples of the fluorine-containing group include a fluorine-containing alkyl group (eg, CF ₃ -, etc.) and/or a fluorine-containing alkylene group (eg, -CF ₂ -CF ₂ -, etc.). A hydrophilic group is a group having hydrophilicity, and hydrophilicity is translated as "hydrophilic" in English, and is a characteristic generally known to those skilled in the art as "it has affinity for water" (e.g., McGraw-Hill Scientific and Technical Terms) References to the dictionary (revision 3rd edition, Nikkan High School Shimborax, etc.). A lipophilic group is a group having lipophilicity, and lipophilicity is translated as "lipophilic" in English, and is a characteristic generally known to those skilled in the art as "it has an affinity for oil" (e.g., McGraw-Hill). See Dictionary of Scientific and Technological Terminology (Revised 3rd Edition, Nikkan High School Shimborax, etc.).

As a "specific fluorine-type compound", since the effect of this invention can be expressed more, More preferably, it is an oligomer containing a fluorine-containing group, a hydrophilic group, and a lipophilic group. When the “specific fluorine-based compound” does not contain a hydrophilic group or the “specific fluorine-based compound” does not contain a lipophilic group, there is a fear that the effects of the present invention cannot be sufficiently exhibited.

A preferred embodiment of the fluorine-containing compound is a fluorine-containing compound having a surface tension of 26.0 mN/m to 27.0 mN/m, preferably in a 0.1% toluene solution, from the viewpoint of further exhibiting the effects of the present invention. (The surface tension of toluene is 27.9 mN/m). As described above, when the surface tension of the fluorine-containing compound in a 0.1% toluene solution is within a very narrow specific range of 26.0 mN/m to 27.0 mN/m, the effects of the present invention can be more expressed, and particularly The remarkable and unpredictable effect that both the peeling electrification voltage of glass and the peeling electrification voltage of a resin can fully be suppressed can be expressed. In particular, when the intended use of the surface protection film in the preferred embodiment of the present invention is to adhere to an exposed surface of an optical member or an electronic member, the peeling electrification voltage of the glass is also the peeling electrification of the resin. It is very important that the effect of being able to sufficiently suppress both overpowering can be expressed.

A particularly preferred embodiment of the fluorine-containing compound is an oligomer containing a fluorine-containing group, a hydrophilic group and a lipophilic group, and has a surface tension of 26.0 mN/m to 27.0 mN/m in a 0.1% toluene solution (the surface tension of toluene is 27.9 mN/m). A particularly preferred embodiment of the fluorine-containing compound is an oligomer containing a fluorine-containing group, a hydrophilic group and a lipophilic group, and has a surface tension of 26.0 mN/m to 27.0 mN/m in a 0.1% toluene solution (the surface tension of toluene is 27.9 mN/m), the effect of the present invention can be further expressed, and in particular, both the peeling electrification voltage of the glass and the peeling electrification voltage of the resin can be extremely sufficiently suppressed. can manifest. In particular, when the intended use of the surface protection film in the preferred embodiment of the present invention is to adhere to an exposed surface of an optical member or an electronic member, the peeling electrification voltage of the glass is also the peeling electrification of the resin. It is very important that the effect of being able to suppress both overpowering and extremely sufficiently can be expressed.

As a fluorine-containing compound, as a commercial item, the following are mentioned, for example.

Megapack series made by DIC Co., Ltd.:

Representatively, "Mega Park F-114", "Mega Park F-251", "Mega Park F-253", "Mega Park F-281", "Mega Park F-410", "Mega Park F-430" ”, “Mega-Park F-444”, “Mega-Park F-477”, “Mega-Park F-510”, “Mega-Park F-551-A”, “Mega-Park F-553”, “Mega-Park F-554” ”, “Megapac F-555-A”, “Mega-Park F-556”, “Mega-Park F-557”, “Mega-Park F-558”, “Mega-Park F-559”, “Mega-Park F-560” ”, “Mega-Park F-561”, “Mega-Park F-562”, “Mega-Park F-563”, “Mega-Park F-565”, “Mega-Park F-568”, “Mega-Park F-569”, 「Mega Park F-570」, 「Mega Park F-576」, 「Mega Park R-01」, 「Mega Park R-40」, 「Mega Park R-40-LM」, 「Mega Park R-41」, 「Mega Park R-41-LM」, 「Mega Park R-94」, 「Mega Park RS-56」, 「Mega Park RS-72-K」, 「Mega Park RS-75-A」, 「Mega Park RS -75-NS", "Megapac RS-78", "Megapac RS-90", etc.

AGC Semi-Chemical Co., Ltd. Sufflon series:

Representative examples include "S-242", "S-243", and "S-386".

FC series made by Sumitomo 3M Co., Ltd.:

Representative examples include "FC-4430" and "FC-4432".

Neos Co., Ltd. Fusergent series:

Representatively, "Fusergent 100", "Fusergent 100C", "Fusergent 110", "Fusergent 150", "Fusergent 150CH", "Fusergent 250", "Fusergent 400SW" and the like.

PF series made by Kitamura Chemical Sangyo Co., Ltd.:

Representatively, “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. Other examples include a copolymer of a compound having a fluorinated alkyl group in a hydroxyl group-containing compound, a fluorine-containing organic compound obtained by copolymerizing a hydroxyl group-containing compound with a fluorine-containing compound, and a fluorine-containing compound containing a hydroxyl group-containing organic compound. 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 Coating" (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.), 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", 「MegaPark RS-75」, 「MegaPark RS-76-E」, 「MegaPark RS-76-NS」, 「MegaPark RS-78」, 「MegaPark RS-90」(DIC Co., Ltd.) and the like.

Among the fluorine-containing compounds available as commercially available compounds, typical examples of the above-mentioned "oligomers having a fluorine-containing group, a hydrophilic group and/or a lipophilic group" include those manufactured by DIC Corporation,

"Megapac F-477" (fluorine-containing, hydrophilic, and lipophilic group-containing oligomer, surface tension in the case of 0.1% toluene solution = 26.4 mN/m),

"Megapac F-551-A" (surface tension in the case of using an oligomer containing a fluorine-containing group and a lipophilic group, 0.1% toluene solution = 25.6 mN/m);

"Megapac F-553" (fluorine-containing group, hydrophilic group, lipophilic group-containing oligomer, surface tension in the case of 0.1% toluene solution = 26.4 mN/m),

"Megapac F-554" (fluorine-containing group/lipophilic group-containing oligomer, surface tension in the case of 0.1% toluene solution = 25.0 mN/m),

"Megapac F-555-A" (surface tension in the case of using an oligomer containing a fluorine-containing group, a hydrophilic group, a lipophilic group, and 0.1% toluene solution = 20.4 mN/m);

"Megapac F-557" (fluorine-containing group, hydrophilic group, lipophilic group-containing oligomer, surface tension in the case of 0.1% toluene solution = 26.3 mN/m),

"Megapac F-559" (fluorine-containing group, hydrophilic group, lipophilic group-containing oligomer, surface tension in the case of 0.1% toluene solution = 26.1 mN/m),

"Megapac F-563" (fluorine-containing group/lipophilic group-containing oligomer, surface tension in the case of 0.1% toluene solution = 20.2 mN/m),

"Megapac F-569" (a fluorine-containing group/hydrophilic group-containing oligomer, surface tension in the case of 0.1% toluene solution = 19.7 mN/m),

and the like.

Among the fluorine-containing compounds available as commercially available compounds, the above-mentioned "oligomer containing a fluorine-containing group, a hydrophilic group and a lipophilic group, and the surface tension is 26.0 mN/m to 27.0 mN/m when a 0.1% toluene solution is used (the surface of toluene Tension is 27.9 mN/m), fluorine-containing compounds", representatively, manufactured by DIC Corporation,

"Megapac F-477" (fluorine-containing, hydrophilic, and lipophilic group-containing oligomer, surface tension in the case of 0.1% toluene solution = 26.4 mN/m),

"Megapac F-553" (fluorine-containing group, hydrophilic group, lipophilic group-containing oligomer, surface tension in the case of 0.1% toluene solution = 26.4 mN/m),

"Megapac F-557" (fluorine-containing group, hydrophilic group, lipophilic group-containing oligomer, surface tension in the case of 0.1% toluene solution = 26.3 mN/m),

"Megapac F-559" (fluorine-containing group, hydrophilic group, lipophilic group-containing oligomer, surface tension in the case of 0.1% toluene solution = 26.1 mN/m),

and the like.

<A-1-5. 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. As such other components, for example, a resin component, a crosslinking accelerator, a crosslinking catalyst, a silane coupling agent, a silicone-based additive such as a modified silicone oil, a tackifying resin (rosin derivative, polyterpene resin, petroleum resin, oil-soluble phenol, etc.), antioxidant , inorganic fillers, organic fillers, metal powders, colorants (pigments or dyes, etc.), thin materials, ultraviolet absorbers, antioxidants, light stabilizers, chain transfer agents, plasticizers, softeners, conductive agents, stabilizers, surface lubricants, corrosion inhibitors, heat-resistant stabilizers , a polymerization inhibitor, a lubricant, a solvent, a catalyst, and the like.

The adhesive composition may contain the modified silicone oil as another component, typically, 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, more More 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 which can fully express the effect of an antistatic property more effectively.

«A-2. Base layer≫

One layer may be sufficient as a base material layer, and two or more layers may be sufficient as it. The substrate 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, a long-chain alkyl-based additive, etc. is added to the base layer to release treatment. or a coating layer made of any suitable release agent such as silicone-based, long-chain alkyl-based or fluorine-based release agent can be provided.

As a material of a base material layer, arbitrary appropriate 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. A 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 or more in 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 heat stabilizers, sulfur-based heat-resistant stabilizers, and phenol/phosphorus-based antioxidants. The content of the antioxidant is preferably 1% by weight or less, and 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), Even 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, 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, 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, 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). , even 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.

≪≪B. Use≫≫

The surface protection film according to the embodiment of the present invention typically produces surface defects of the optical member or the electronic member during processing, assembling, inspection, transport, etc. in the manufacturing process of the optical member or the electronic member. It is a surface protection film comprising a pressure-sensitive adhesive layer that is adhered to the exposed surface of the optical member or the electronic member to prevent it, sufficiently suppresses the peeling electrification voltage, and does not damage the optical member or the electronic member at the time of peeling effect can be expressed. 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.

<Measurement of surface free energy for diiodomethane on the surface of the adhesive layer>

The surface protection film from which the separator was peeled was cut to a size of 50 mm in width and 100 mm in length, and with the surface of the adhesive layer as the upper surface, it was fixed to a contact angle meter (manufactured by Kyowa Kaimen Chemical Co., Ltd., model "CA-X"), and the adhesive 2.0 µL of water was added dropwise to the surface of the layer to measure the contact angle. Next, in the same procedure, 2.0 µL of diiodomethane was dripped, and the contact angle was measured. The surface free energy for diiodomethane on the surface of the pressure-sensitive adhesive layer was calculated from the contact angle values of the two liquids using the Owens-Wendt method.

<Measurement of peeling force from a glass plate (after leaving it to stand at a temperature of 23°C for 30 minutes)>

The adhesive layer side of the surface protection film (width 25 mm x length 140 mm) from which the separator was peeled was bonded to a glass plate (soda-lime glass, manufactured by Matsunami Glass Kogyo Co., Ltd.) with a 2 kg hand roller 1 reciprocating, and under an environmental temperature of 23 ° C. It was left for 30 minutes.

The evaluation sample obtained as described above was measured with a 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. The sample for evaluation was set in the tensile tester, and the tensile test was started. The load at the time of specifically peeling a surface protection film from the said glass plate was measured, and the average load at that time was made into the peeling force from the glass plate of a surface protection film. The conditions of the tensile test were: test environment temperature: 23°C, peel angle: 180 degrees, and peel rate (tensile rate): 300 mm/min.

<Measurement of the glass peeling withstand voltage and the acrylic plate peeling electrification voltage>

The surface protection film from which the separator was peeled was cut to a size of 70 mm in width and 100 mm in length, and a glass (soda-lime glass, manufactured by Matsunami Glass Kogyo Co., Ltd.) or an acrylic plate (acrylite, manufactured by Mitsubishi Chemical Corporation) On the surface, one edge part of the surface protection film was made to protrude 30 mm from the edge of the said glass, and it crimped|bonded with a hand roller.

After leaving this sample to stand in the environment of 23 degreeC x 50%RH for 1 day, it was set in the predetermined position of the sample holding table of height 20mm. The edge part of the surface protection film which protruded 30 mm from glass was fixed to the automatic winding machine, and it peeled so that it might become a peeling angle of 150 degrees and a peeling speed of 30 m/min. The potential on the surface of the adherend generated at this time is measured with a potential measuring device (manufactured by Shishido Seidenki Co., Ltd., model "STATIRON DZ-4") fixed at a position of 30 mm in height from the center of the adherend, and glass peeling is performed. It was set as a charging voltage or an acrylic plate peeling charging voltage. The measurement was performed in the environment of 23 degreeC and 50%RH.

<Measurement of glass residual adhesive force>

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

Separately, also about the glass plate which has not performed 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 adhesion 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 to-glass residual adhesion rate becomes an index|index of how much the adhesive component of a surface protection film transfers to the surface with respect to a to-be-adhered body, and is contaminated. The higher the value of this-to-glass residual adhesion ratio, the higher the possibility of contaminating the adherend. am.

<Measurement of haze>

The pressure-sensitive adhesive solution obtained in the following Examples and Comparative Examples was subjected to the peeling treatment side of a polyester film having a thickness of 75 μm (trade name: Diafoil MRF75, manufactured by Mitsubishi Chemical Co., Ltd.) in which one side was peeled off with silicone, the following implementation Coating was dried under the conditions described in Examples and Comparative Examples, and an adhesive layer was produced. Then, on the surface of the pressure-sensitive adhesive layer, a polyester film (trade name: Diafoil MRE75, manufactured by Mitsubishi Chemical Co., Ltd.) having a thickness of 75 μm, on which one side was peeled with silicone, was placed so that the peeling-treated side of the film was on the pressure-sensitive adhesive layer side. It was coated and aged at room temperature for 5 days. Two sheets of 50 mm x 50 mm thick paper with a hole of 20 mm x 20 mm in the center were prepared, and a single sample was adhered to one side with a hand roller 1 reciprocating, and then the other side was adhered. The sample for evaluation obtained as mentioned above was measured with "HM-150N" manufactured by Murakami Shikisai Kijutsu Genkyujo Co., Ltd.

<Explanation of fluorine-containing compounds used in Examples and Comparative Examples>

As the fluorine-containing compound, those used in Examples and Comparative Examples are as follows.

"Megapac F-477" (manufactured by DIC Co., Ltd., oligomer containing fluorine-containing groups, hydrophilic groups, and lipophilic groups, surface tension in the case of 0.1% toluene solution = 26.4 mN/m);

"Megapac F-551-A" (manufactured by DIC Corporation, an oligomer containing a fluorine-containing group and a lipophilic group, the surface tension in the case of a 0.1% toluene solution = 25.6 mN/m);

"Megapac F-553" (manufactured by DIC Co., Ltd., oligomer containing fluorine-containing groups, hydrophilic groups, and lipophilic groups, surface tension in the case of 0.1% toluene solution = 26.4 mN/m);

"Megapac F-554" (manufactured by DIC Co., Ltd., oligomer containing fluorine-containing groups and lipophilic groups, surface tension in the case of 0.1% toluene solution = 25.0 mN/m);

"Megapac F-555-A" (manufactured by DIC Co., Ltd., an oligomer containing a fluorine-containing group, a hydrophilic group, and a lipophilic group, the surface tension in the case of a 0.1% toluene solution = 20.4 mN/m);

"Megapac F-557" (DIC Co., Ltd. product, oligomer containing a fluorine-containing group, a hydrophilic group, and a lipophilic group, the surface tension in the case of a 0.1% toluene solution = 26.3 mN/m),

"Megapac F-559" (DIC Co., Ltd. product, oligomer containing a fluorine-containing group, a hydrophilic group, a lipophilic group, the surface tension in the case of using a 0.1% toluene solution = 26.1 mN/m),

"Megapac F-563" (manufactured by DIC Corporation, an oligomer containing a fluorine-containing group and a lipophilic group, the surface tension in the case of a 0.1% toluene solution = 20.2 mN/m);

"Megapac F-569" (manufactured by DIC Corporation, an oligomer containing a fluorine-containing group and a hydrophilic group, the surface tension in the case of a 0.1% toluene solution = 19.7 mN/m);

[Example 1]

As the polyol, 85 parts by weight of Preminol S3011 (manufactured by Asahi Glass Co., Ltd., Mn=10000), which is a polyol having three hydroxyl groups, Sannix GP3000, a polyol having three hydroxyl groups (manufactured by Sanyo Kasei, Mn=3000) ) 13 parts by weight, 2 parts by weight of Sannix GP1000 (manufactured by Sanyo Chemical Co., Ltd., Mn=1000), which is a polyol having three hydroxyl groups, 2 parts by weight of an isocyanate compound (Coronate HX: C/HX, manufactured by Nippon Polyurethane Co., Ltd.) 18 0.02 parts by weight of Nassem Ferric (manufactured by Nippon Chemical Industries, Ltd.) as a catalyst, 1 part by weight of Megapac F-553 (manufactured by DIC) of a fluorine-based oligomer, 1-ethyl-3-methylimida as an ionic compound 1 part by weight of zolium tri(fluoromethanesulfonyl)imide (AS110, manufactured by Daiichi Kogyo Seyaku Co., Ltd.), it diluted with ethyl acetate so that the total solid content might be 35 weight%, and the urethane-type adhesive solution was obtained. Then, the urethane-based pressure-sensitive adhesive solution is applied to a base material made of a polyester resin (trade name "T100-75S", thickness 75 μm, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying becomes 20 μm, and dried at a drying temperature of 130° C. It was cured and dried under conditions of 2 minutes. Next, the silicone-treated surface of a release sheet (trade name "MRF25", 25 µm thick, manufactured by Mitsubishi Chemical Co., Ltd.) made of a polyester resin having a thickness of 25 µm on which one surface is silicone-treated is bonded to the surface of the obtained pressure-sensitive adhesive layer. Thus, a surface protection film (1) was obtained. Aging was performed for 5 days at room temperature, and evaluation was performed. The release sheet was peeled off immediately before evaluation. The results are shown in Table 1.

[Example 2]

As shown in Table 1, the same procedure as in Example 1 was carried out, except that the fluorine-based oligomer (trade name "F-569", manufactured by DIC) was changed to 0.25 parts by weight in terms of solid content, to prepare a pressure-sensitive adhesive layer composed of the pressure-sensitive adhesive composition (2) and a surface protection film (2) was obtained. The results are shown in Table 1.

[Example 3]

As shown in Table 1, the same procedure as in Example 1 was carried out, except that the fluorine-based oligomer (trade name "F-554", manufactured by DIC) was changed to 1 part by weight in terms of solid content, to prepare a pressure-sensitive adhesive layer composed of the pressure-sensitive adhesive composition (3) and a surface protection film (3) was obtained. The results are shown in Table 1.

[Example 4]

As shown in Table 1, the same procedure as in Example 1 was carried out, except that the fluorine-based oligomer (trade name "F-553", manufactured by DIC) was changed to 0.25 parts by weight in terms of solid content, and an adhesive layer composed of the pressure-sensitive adhesive composition (4) was produced. and a surface protection film (4) was obtained. The results are shown in Table 1.

[Example 5]

As shown in Table 1, 0.25 parts by weight of the fluorine-based oligomer (trade name "F-553", manufactured by DIC) in terms of solid content and 0.5 parts by weight of an ionic compound (trade name "AS110, manufactured by Daiichi Kogyo Seyaku)" It carried out similarly to Example 1, the adhesive layer which consists of an adhesive composition (5) was produced, and the surface protection film (5) was obtained. The results are shown in Table 1.

[Example 6]

As shown in Table 1, 0.25 parts by weight of the fluorine-based oligomer (trade name "F-553", manufactured by DIC) in terms of solid content and 0.25 parts by weight of an ionic compound (trade name: "AS110, manufactured by Daiichi Kogyo Seyaku)" It carried out similarly to Example 1, the adhesive layer which consists of an adhesive composition (6) was produced, and the surface protection film (6) was obtained. The results are shown in Table 1.

[Example 7]

As shown in Table 1, it carried out similarly to Example 1, except having changed the fluorine-type oligomer (trade name "F-555-A", manufactured by DIC) to 0.25 weight part in conversion of solid content, The adhesive layer which consists of adhesive composition (7) was produced, and a surface protection film (7) was obtained. The results are shown in Table 1.

[Example 8]

As shown in Table 1, the same procedure as in Example 1 was carried out, except that the fluorine-based oligomer (trade name "F-559", manufactured by DIC) was changed to 0.25 parts by weight in terms of solid content, and an adhesive layer composed of the pressure-sensitive adhesive composition (8) was produced. and a surface protection film (8) was obtained. The results are shown in Table 1.

[Example 9]

As shown in Table 1, the same procedure as in Example 1 was carried out, except that the fluorine-based oligomer (trade name "F-477", manufactured by DIC) was changed to 1 part by weight in terms of solid content, to prepare a pressure-sensitive adhesive layer composed of the pressure-sensitive adhesive composition (9) and a surface protection film (9) was obtained. The results are shown in Table 1.

[Example 10]

As shown in Table 1, the same procedure as in Example 1 was carried out, except that the fluorine-based oligomer (trade name "F-554", manufactured by DIC) was changed to 0.25 parts by weight in terms of solid content, to prepare a pressure-sensitive adhesive layer composed of the pressure-sensitive adhesive composition (10) and a surface protection film (10) was obtained. The results are shown in Table 1.

[Example 11]

As shown in Table 1, the same procedure as in Example 1 was carried out except that the fluorine-based oligomer (trade name "F-553", manufactured by DIC) was changed to 0.1 parts by weight in terms of solid content, and an adhesive layer composed of the pressure-sensitive adhesive composition 11 was produced. and a surface protection film (11) was obtained. The results are shown in Table 1.

[Example 12]

As shown in Table 1, the same procedure as in Example 1 was carried out, except that the fluorine-based oligomer (trade name "F-477", manufactured by DIC) was changed to 0.25 parts by weight in terms of solid content, to prepare a pressure-sensitive adhesive layer composed of the pressure-sensitive adhesive composition 12 and a surface protection film (12) was obtained. The results are shown in Table 1.

[Example 13]

As shown in Table 1, 0.25 parts by weight of the fluorine-based oligomer (trade name "F-477", manufactured by DIC) in terms of solid content and 0.5 parts by weight of an ionic compound (trade name "AS110, manufactured by Daiichi Kogyo Seyaku)" It carried out similarly to Example 1, the adhesive layer which consists of the adhesive composition 13 was produced, and the surface protection film 13 was obtained. The results are shown in Table 1.

[Example 14]

As shown in Table 1, 0.25 parts by weight of the fluorine-based oligomer (trade name "F-477", manufactured by DIC) in terms of solid content and 0.25 parts by weight of an ionic compound (trade name: "AS110, manufactured by Daiichi Kogyo Seyaku)" It carried out similarly to Example 1, the adhesive layer which consists of the adhesive composition 14 was produced, and the surface protection film 14 was obtained. The results are shown in Table 1.

[Example 15]

As shown in Table 1, the same procedure as in Example 1 was carried out except that the fluorine-based oligomer (trade name "F-551-A", manufactured by DIC) was changed to 1 part by weight in terms of solid content, and the pressure-sensitive adhesive layer comprising the pressure-sensitive adhesive composition 15 was produced to obtain a surface protection film (15). The results are shown in Table 1.

[Example 16]

As shown in Table 1, the same procedure as in Example 1 was carried out, except that the fluorine-based oligomer (trade name "F-556", manufactured by DIC) was changed to 0.25 parts by weight in terms of solid content, to prepare a pressure-sensitive adhesive layer composed of the pressure-sensitive adhesive composition (16). and a surface protection film (16) was obtained. The results are shown in Table 1.

[Example 17]

As shown in Table 1, the same procedure as in Example 1 was carried out except that the fluorine-based oligomer (trade name "F-551-A", manufactured by DIC) was changed to 0.25 parts by weight in terms of solid content, and the pressure-sensitive adhesive layer comprising the pressure-sensitive adhesive composition 17 was produced, and a surface protection film (17) was obtained. The results are shown in Table 1.

[Example 18]

As shown in Table 1, the same procedure as in Example 1 was carried out, except that the fluorine-based oligomer (trade name "F-554", manufactured by DIC) was changed to 0.1 parts by weight in terms of solid content, to prepare a pressure-sensitive adhesive layer composed of the pressure-sensitive adhesive composition 18 and a surface protection film (18) was obtained. The results are shown in Table 1.

[Example 19]

As shown in Table 1, the same procedure as in Example 1 was carried out, except that the fluorine-based oligomer (trade name "F-563", manufactured by DIC) was changed to 0.25 parts by weight in terms of solid content, to prepare a pressure-sensitive adhesive layer composed of the pressure-sensitive adhesive composition 19 and a surface protection film (19) was obtained. The results are shown in Table 1.

[Example 20]

As shown in Table 1, the same procedure as in Example 1 was carried out, except that the fluorine-based oligomer (trade name "F-477", manufactured by DIC) was changed to 0.1 parts by weight in terms of solid content, to prepare a pressure-sensitive adhesive layer composed of the pressure-sensitive adhesive composition (20) and a surface protection film (20) was obtained. The results are shown in Table 1.

[Example 21]

As shown in Table 1, the same procedure as in Example 1 was carried out, except that the fluorine-based oligomer (trade name "F-553", manufactured by DIC) was changed to 2.0 parts by weight in terms of solid content, and an adhesive layer composed of the pressure-sensitive adhesive composition 21 was produced. and a surface protection film (21) was obtained. The results are shown in Table 1.

[Example 22]

As shown in Table 1, the same procedure as in Example 1 was carried out, except that the fluorine-based oligomer (trade name "F-553", manufactured by DIC) was changed to 4.0 parts by weight in terms of solid content, to prepare a pressure-sensitive adhesive layer composed of the pressure-sensitive adhesive composition 22 and a surface protection film (22) was obtained. The results are shown in Table 1.

[Example 23]

As shown in Table 1, the same procedure as in Example 1 was carried out, except that the fluorine-based oligomer (trade name "F-553", manufactured by DIC) was changed to 6.0 parts by weight in terms of solid content, to prepare a pressure-sensitive adhesive layer composed of the pressure-sensitive adhesive composition 23 and a surface protection film (23) was obtained. The results are shown in Table 1.

[Example 24]

As shown in Table 1, the same procedure as in Example 1 was carried out, except that the fluorine-based oligomer (trade name "F-477", manufactured by DIC) was changed to 2.0 parts by weight in terms of solid content, to prepare an adhesive layer composed of the pressure-sensitive adhesive composition 24 and a surface protection film (24) was obtained. The results are shown in Table 1.

[Example 25]

As shown in Table 1, the same procedure as in Example 1 was carried out, except that the fluorine-based oligomer (trade name "F-477", manufactured by DIC) was changed to 4.0 parts by weight in terms of solid content, to prepare a pressure-sensitive adhesive layer composed of the pressure-sensitive adhesive composition (25) and a surface protection film (25) was obtained. The results are shown in Table 1.

[Example 26]

As shown in Table 1, the same procedure as in Example 1 was carried out, except that the fluorine-based oligomer (trade name "F-477", manufactured by DIC) was changed to 6.0 parts by weight in terms of solid content, to prepare a pressure-sensitive adhesive layer composed of the pressure-sensitive adhesive composition 26 and a surface protection film (26) was obtained. The results are shown in Table 1.

[Example 27]

As shown in Table 1, the same procedure as in Example 4 was carried out except that the isocyanate compound (Coronate HX: C/HX, manufactured by Nippon Polyurethane Co., Ltd.) was changed to 15.9 parts by weight in terms of solid content, and the pressure-sensitive adhesive composed of the pressure-sensitive adhesive composition (27) The layer was produced and the surface protection film (27) was obtained. The results are shown in Table 1.

[Example 28]

As shown in Table 1, the same procedure as in Example 4 was carried out except that the isocyanate compound (Coronate HX: C/HX, manufactured by Nippon Polyurethane Co., Ltd.) was changed to 14.1 parts by weight in terms of solid content, and the pressure-sensitive adhesive composed of the pressure-sensitive adhesive composition (28) The layer was produced and the surface protection film (28) was obtained. The results are shown in Table 1.

[Example 29]

As shown in Table 1, the same procedure as in Example 4 was carried out, except that the isocyanate compound (Coronate HX: C/HX, manufactured by Nippon Polyurethane Co., Ltd.) was changed to 12.4 parts by weight in terms of solid content, the pressure-sensitive adhesive composed of the pressure-sensitive adhesive composition (29) The layer was produced and the surface protection film (29) was obtained. The results are shown in Table 1.

[Example 30]

As shown in Table 1, the same procedure as in Example 4 was carried out, except that the isocyanate compound (Coronate HX: C/HX, manufactured by Nippon Polyurethane Co., Ltd.) was changed to 10.6 parts by weight in terms of solid content, the pressure-sensitive adhesive composed of the pressure-sensitive adhesive composition (30) The layer was produced and the surface protection film 30 was obtained. The results are shown in Table 1.

[Example 31]

As shown in Table 1, the same procedure as in Example 4 was carried out, except that the isocyanate compound (Coronate HX: C/HX, manufactured by Nippon Polyurethane Co., Ltd.) was changed to 8.8 parts by weight in terms of solid content; The layer was produced and the surface protection film 31 was obtained. The results are shown in Table 1.

[Example 32]

As shown in Table 1, the same procedure as in Example 12 was carried out, except that the isocyanate compound (Coronate HX: C/HX, manufactured by Nippon Polyurethane Co., Ltd.) was changed to 15.9 parts by weight in terms of solid content, the pressure-sensitive adhesive comprising the pressure-sensitive adhesive composition (32) The layer was produced and the surface protection film (32) was obtained. The results are shown in Table 1.

[Example 33]

As shown in Table 1, the same procedure as in Example 12 was carried out, except that the isocyanate compound (Coronate HX: C/HX, manufactured by Nippon Polyurethane Co., Ltd.) was changed to 14.1 parts by weight in terms of solid content, and the pressure-sensitive adhesive composed of the pressure-sensitive adhesive composition (33) The layer was produced and the surface protection film (33) was obtained. The results are shown in Table 1.

[Example 34]

As shown in Table 1, the same procedure as in Example 12 was carried out except that the isocyanate compound (Coronate HX: C/HX, manufactured by Nippon Polyurethane Co., Ltd.) was changed to 12.4 parts by weight in terms of solid content; A layer was prepared and a surface protection film (34) was obtained. The results are shown in Table 1.

[Example 35]

As shown in Table 1, the same procedure as in Example 12 was carried out, except that the isocyanate compound (Coronate HX: C/HX, manufactured by Nippon Polyurethane Co., Ltd.) was changed to 10.6 parts by weight in terms of solid content, and the pressure-sensitive adhesive composed of the pressure-sensitive adhesive composition (35) The layer was produced and the surface protection film (35) was obtained. The results are shown in Table 1.

[Example 36]

As shown in Table 1, the same procedure as in Example 12 was carried out, except that the isocyanate compound (Coronate HX: C/HX, manufactured by Nippon Polyurethane Co., Ltd.) was changed to 8.8 parts by weight in terms of solid content. The layer was produced and the surface protection film (36) was obtained. The results are shown in Table 1.

[Example 37]

As shown in Table 1, the same procedure as in Example 4 was carried out, except that the fluorine-based oligomer (trade name "F-557", manufactured by DIC) was changed to 0.25 parts by weight in terms of solid content, to prepare a pressure-sensitive adhesive layer composed of the pressure-sensitive adhesive composition (37) and a surface protection film (37) was obtained. The results are shown in Table 1.

[Example 38]

As shown in Table 1, the same procedure as in Example 37 was carried out, except that the isocyanate compound (Coronate HX: C/HX, manufactured by Nippon Polyurethane Co., Ltd.) was changed to 15.9 parts by weight in terms of solid content, the pressure-sensitive adhesive composed of the pressure-sensitive adhesive composition (38) A layer was prepared and a surface protection film (38) was obtained. The results are shown in Table 1.

[Example 39]

As shown in Table 1, the same procedure as in Example 37 was carried out, except that the isocyanate compound (Coronate HX: C/HX, manufactured by Nippon Polyurethane Co., Ltd.) was changed to 14.1 parts by weight in terms of solid content, the pressure-sensitive adhesive comprising the pressure-sensitive adhesive composition (39) A layer was prepared and a surface protection film (39) was obtained. The results are shown in Table 1.

[Example 40]

As shown in Table 1, the same procedure as in Example 37 was carried out, except that the isocyanate compound (Coronate HX: C/HX, manufactured by Nippon Polyurethane Co., Ltd.) was changed to 12.4 parts by weight in terms of solid content. The layer was produced and the surface protection film 40 was obtained. The results are shown in Table 1.

[Example 41]

As shown in Table 1, the same procedure as in Example 37 was carried out, except that the isocyanate compound (Coronate HX: C/HX, manufactured by Nippon Polyurethane Co., Ltd.) was changed to 10.6 parts by weight in terms of solid content. The layer was produced and the surface protection film 41 was obtained. The results are shown in Table 1.

[Example 42]

As shown in Table 1, the same procedure as in Example 37 was carried out, except that the isocyanate compound (Coronate HX: C/HX, manufactured by Nippon Polyurethane Co., Ltd.) was changed to 8.8 parts by weight in terms of solid content, and the pressure-sensitive adhesive comprising the pressure-sensitive adhesive composition (42) The layer was produced and the surface protection film 42 was obtained. The results are shown in Table 1.

[Example 43]

As shown in Table 1, the same procedure as in Example 8 was carried out, except that the isocyanate compound (Coronate HX: C/HX, manufactured by Nippon Polyurethane Co., Ltd.) was changed to 15.9 parts by weight in terms of solid content, the pressure-sensitive adhesive comprising the pressure-sensitive adhesive composition (43) The layer was produced and the surface protection film (43) was obtained. The results are shown in Table 1.

[Example 44]

As shown in Table 1, the same procedure as in Example 8 was carried out, except that the isocyanate compound (Coronate HX: C/HX, manufactured by Nippon Polyurethane Co., Ltd.) was changed to 14.1 parts by weight in terms of solid content; The layer was produced and the surface protection film 44 was obtained. The results are shown in Table 1.

[Example 45]

As shown in Table 1, the same procedure as in Example 8 was carried out, except that the isocyanate compound (Coronate HX: C/HX, manufactured by Nippon Polyurethane Co., Ltd.) was changed to 12.4 parts by weight in terms of solid content, the pressure-sensitive adhesive comprising the pressure-sensitive adhesive composition (45) The layer was produced and the surface protection film 45 was obtained. The results are shown in Table 1.

[Example 46]

As shown in Table 1, the same procedure as in Example 8 was carried out, except that the isocyanate compound (Coronate HX: C/HX, manufactured by Nippon Polyurethane Co., Ltd.) was changed to 10.6 parts by weight in terms of solid content, the pressure-sensitive adhesive composed of the pressure-sensitive adhesive composition (46) The layer was produced and the surface protection film 46 was obtained. The results are shown in Table 1.

[Example 47]

As shown in Table 1, the same procedure as in Example 8 was carried out, except that the isocyanate compound (Coronate HX: C/HX, manufactured by Nippon Polyurethane Co., Ltd.) was changed to 8.8 parts by weight in terms of solid content, and the pressure-sensitive adhesive composition (47). The layer was produced and the surface protection film (47) was obtained. The results are shown in Table 1.

[Example 48]

100 parts by weight of urethane prepolymer A, 3 parts by weight of an isocyanate compound (Coronate HX: C/HX, manufactured by Nippon Polyurethane Co., Ltd.) as a crosslinking agent, 0.5 parts by weight of Irganox1010 (made by BASF) as an antioxidant, Megapac F-553 of a fluorine-based oligomer (manufactured by DIC) 1 part by weight, 1-ethyl-3-methylimidazolium tri(fluoromethanesulfonyl)imide (AS110, manufactured by Daiichi Kogyo Seyaku) as an ionic compound 1 part by weight, total solid content It diluted with ethyl acetate so that it might become 49 weight%, and the urethane type adhesive solution was obtained. Then, the urethane-based pressure-sensitive adhesive solution is applied to a base material made of a polyester resin (trade name "T100-75S", thickness 75 μm, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying becomes 75 μm, drying temperature 120° C., drying It was cured and dried under the conditions of a time of 3 minutes, and the adhesive layer which consists of the adhesive composition 48 was produced. Next, the silicone-treated surface of a release sheet (trade name "MRF25", 25 µm thick, manufactured by Mitsubishi Chemical Co., Ltd.) made of a polyester resin having a thickness of 25 µm on which one surface is silicone-treated is bonded to the surface of the obtained pressure-sensitive adhesive layer. Thus, a surface protection film (48) was obtained. Aging was performed for 5 days at room temperature, and evaluation was performed. The release sheet was peeled off immediately before evaluation. The results are shown in Table 1.

[Example 49]

As shown in Table 1, the same procedure as in Example 48 was carried out, except that the fluorine-based oligomer (trade name "F-477", manufactured by DIC) was changed to 1.0 parts by weight in terms of solid content, to prepare a pressure-sensitive adhesive layer comprising the pressure-sensitive adhesive composition 49 and a surface protection film (49) was obtained. The results are shown in Table 1.

[Example 50]

As shown in Table 1, the same procedure as in Example 48 was carried out, except that the fluorine-based oligomer (trade name "F-557", manufactured by DIC) was changed to 1.0 parts by weight in terms of solid content, to prepare a pressure-sensitive adhesive layer composed of the pressure-sensitive adhesive composition (50) and a surface protection film (50) was obtained. The results are shown in Table 1.

[Example 51]

As shown in Table 1, the same procedure as in Example 48 was carried out, except that the fluorine-based oligomer (trade name "F-559", manufactured by DIC) was changed to 1.0 parts by weight in terms of solid content, to prepare a pressure-sensitive adhesive layer composed of the pressure-sensitive adhesive composition (51) and a surface protection film (51) was obtained. The results are shown in Table 1.

[Comparative Example 1]

As shown in Table 1, 0.25 parts by weight of a fluorine-based oligomer (trade name "F-569", manufactured by DIC) in terms of solid content and an ionic compound (trade name: "AS110, manufactured by Daiichi Kogyo Seyaku") was carried out except that it was not used. It carried out similarly to Example 1, the adhesive layer which consists of an adhesive composition (C1) was produced, and the surface protection film (C1) was obtained. The results are shown in Table 1.

[Comparative Example 2]

As shown in Table 1, 0.25 parts by weight of fluorine-based oligomer (trade name "F-553", manufactured by DIC) in terms of solid content, and ionic compound (trade name: "AS110, manufactured by Daiichi Kogyo Seyaku") was carried out except that it was not used. It carried out similarly to Example 1, the adhesive layer which consists of an adhesive composition (C2) was produced, and the surface protection film (C2) was obtained. The results are shown in Table 1.

[Comparative Example 3]

As shown in Table 1, 0.25 parts by weight of fluorine-based oligomer (trade name "F-477", manufactured by DIC) in terms of solid content, and ionic compound (trade name "AS110, manufactured by Daiichi Kogyo Seyaku") was carried out except that It carried out similarly to Example 1, the adhesive layer which consists of an adhesive composition (C3) was produced, and the surface protection film (C3) was obtained. The results are shown in Table 1.

[Comparative Example 4]

As shown in Table 1, 0.25 parts by weight of fluorine-based oligomer (trade name "F-551-A", manufactured by DIC) in terms of solid content, except that an ionic compound (trade name "AS110, manufactured by Daiichi Kogyo Seyaku") was not used. , It carried out similarly to Example 1, the adhesive layer which consists of an adhesive composition (C4) was produced, and the surface protection film (C4) was obtained. The results are shown in Table 1.

[Comparative Example 5]

As shown in Table 1, the same procedure as in Example 1 was carried out, except that the fluorine-based oligomer (trade name "F-571", manufactured by DIC) was changed to 0.25 parts by weight in terms of solid content, to prepare an adhesive layer composed of the pressure-sensitive adhesive composition (C5) and a surface protection film (C5) was obtained. The results are shown in Table 1.

[Comparative Example 6]

As shown in Table 1, the same procedure as in Example 1 was carried out except that the fluorine-based oligomer (trade name "F-552", manufactured by DIC) was changed to 0.25 parts by weight in terms of solid content, to prepare an adhesive layer composed of the pressure-sensitive adhesive composition (C6) and a surface protection film (C6) was obtained. The results are shown in Table 1.

[Comparative Example 7]

As shown in Table 1, except not using the fluorine-type oligomer, it carried out similarly to Example 1, the adhesive layer which consists of an adhesive composition (C7) was produced, and the surface protection film (C7) was obtained. The results are shown in Table 1.

[Comparative Example 8]

As shown in Table 1, the same procedure as in Example 1 was carried out, except that no fluorine-based oligomer was used and no ionic compound (trade name "AS110, manufactured by Daiichi Kogyo Seyaku") was used, and the pressure-sensitive adhesive composition (C8). The layer was produced and the surface protection film (C8) was obtained. The results are shown in Table 1.

[Comparative Example 9]

As shown in Table 1, the same procedure as in Example 48 was carried out, except that no fluorine-based oligomer was used and no ionic compound (trade name "AS110, manufactured by Daiichi Kogyo Seyaku") was used, and the pressure-sensitive adhesive composition (C9) was used. The layer was produced and the surface protection film (C9) was obtained. The results are shown in Table 1.

[Comparative Example 10]

As shown in Table 1, the same procedure as in Example 49 was carried out, except that no fluorine-based oligomer was used and an ionic compound (trade name: "AS110, manufactured by Daiichi Kogyo Seyaku") was not used, and the pressure-sensitive adhesive composition (C10). The layer was produced and the surface protection film (C10) was obtained. The results are shown in Table 1.

[Comparative Example 11]

As shown in Table 1, the same procedure as in Example 48 was carried out, except that the fluorine-based oligomer (trade name "F-571", manufactured by DIC) was changed to 1 part by weight in terms of solid content, to prepare a pressure-sensitive adhesive layer composed of the pressure-sensitive adhesive composition (C11) and a surface protection film (C11) was obtained. The results are shown in Table 1.

[Examples 52 to 103]

For each of the surface protection films (1) to (51) obtained in Examples 1-51, the separator 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, , an optical member to which a surface protection film was adhered was obtained.

[Examples 104-155]

For each of the surface protection films (1) to (51) obtained in Examples 1-51, the separator was peeled off, and the adhesive layer side was placed on the conductive film as an electronic member (manufactured by Nitto Denko Corporation, trade name "Elecrista V270L-TFMP"). ') to obtain an electronic member to which a surface protection film was adhered.

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 (7)

It is a surface protection film comprising an adhesive layer,
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, an ionic compound and a fluorine-based compound,
The surface free energy for diiodomethane of the surface of the pressure-sensitive adhesive layer is 6mJ/m2 to 30mJ/m2,
surface protection film. The surface protection film according to claim 1, wherein the content ratio of the ionic compound to 100 parts by weight of the base polymer is 0.2 parts by weight or more. The surface protection film according to claim 1 or 2, wherein the content ratio of the fluorine-based compound to 100 parts by weight of the base polymer is 0.05 parts by weight or more. The surface protection film according to any one of claims 1 to 3, wherein the base polymer is at least one selected from a polyol, a urethane prepolymer, an acrylic resin, a rubber resin, and a silicone resin. The surface protection film according to any one of claims 1 to 4, wherein after bonding the pressure-sensitive adhesive layer included in the surface protection film to a glass plate and leaving it to stand at a temperature of 23°C for 30 minutes, the surface protection film is applied to the glass plate at a temperature of 23°C The peeling force at the time of peeling with a peeling angle of 180 degrees and a peeling rate of 300 mm/min from 0.005N/25mm - 0.1N/25mm, the surface protection film. The optical member to which the surface protection film in any one of Claims 1-5 was adhere|attached. The electronic member to which the surface protection film in any one of Claims 1-5 was adhere|attached.

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