JP6896927B1 - Surface protective film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prevent scratches on the surface of an optical member or the electronic member during processing, assembly, inspection, transportation, etc. in a manufacturing process of the optical member or the electronic member. Provided is a surface protective film containing an adhesive layer, which is attached to an exposed surface of an electronic member, and which sufficiently suppresses a peeling band voltage and does not damage the optical member or the electronic member at the time of peeling. .. A surface protective film according to an embodiment of the present invention is a surface protective film containing a pressure-sensitive adhesive layer, wherein the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer is formed from a pressure-sensitive adhesive composition, and the pressure-sensitive adhesive composition is formed. However, it contains a base polymer, an ionic compound, and a fluorine-based compound, and the surface free energy of the surface of the pressure-sensitive adhesive layer with respect to diiodomethane is 6 mJ / m2 to 30 mJ / m2. [Selection diagram] Fig. 1

Description

The present invention relates to a surface protective film.

In the manufacturing process of an optical member or an electronic member, in order to prevent the surface of the optical member or the electronic member from being damaged during processing, assembly, inspection, transportation, etc., the optical member or the electron is generally used. A surface protective film is attached to the exposed surface of the member. Such a surface protective film is peeled off from an optical member or an electronic member when the need for surface protection is eliminated (Patent Document 1).

Normally, surface protective films, optical members, and electronic members have high electrical insulation properties, and generate static electricity due to friction and peeling. Therefore, static electricity is likely to be generated when the surface protective film is peeled off from the optical member or the electronic member. In such a case, for example, if a voltage is applied to the liquid crystal with static electricity remaining, there is a concern that the orientation 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 of sucking dust and reducing workability.

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

Further, in order to impart antistatic properties to the pressure-sensitive adhesive layer itself constituting the surface protective 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 the adherend is formed. (Patent Document 4).

Japanese Unexamined Patent Publication No. 2016-17109 Japanese Unexamined Patent Publication No. 2004-223923 Japanese Unexamined Patent Publication No. 2008-255332 Japanese Unexamined Patent Publication No. 9-165460

A subject of the present invention is typically the optical for preventing scratches on the surface of the optical member or the electronic member during processing, assembly, inspection, transportation, etc. in the manufacturing process of the optical member or the electronic member. A surface protective film containing an adhesive layer that is attached to a member or an exposed surface of the electronic member, and is a surface protective film that sufficiently suppresses the peeling band voltage and does not damage the optical member or the electronic member during peeling. The purpose is to provide.

The surface protective film according to the embodiment of the present invention
A surface protective film containing an adhesive layer,
The pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer is formed from the pressure-sensitive adhesive composition.
The pressure-sensitive adhesive composition comprises 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 ionic compound to 100 parts by weight of the base polymer is 0.2 parts by weight or more.

In one embodiment, 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.

In one embodiment, the base polymer is at least one selected from polyols, urethane prepolymers, acrylic resins, rubber resins, and silicone resins.

In one embodiment, the adhesive layer contained in the surface protective film is attached to a glass plate and left at a temperature of 23 ° C. for 30 minutes, and then the surface protective film is peeled off from the glass plate at a temperature of 23 ° C. The peeling force when peeled at 180 degrees and a peeling speed of 300 mm / min is 0.005 N / 25 mm to 0.1 N / 25 mm.

The optical member according to the embodiment of the present invention is the one to which the above-mentioned surface protective film is attached.

The electronic member according to the embodiment of the present invention is the one to which the above-mentioned surface protective film is attached.

According to the present invention, typically, in the manufacturing process of an optical member or an electronic member, the optical is used to prevent scratches on the surface of the optical member or the electronic member during processing, assembly, inspection, transportation, or the like. A surface protective film containing an adhesive layer that is attached to a member or an exposed surface of the electronic member, and is a surface protective film that sufficiently suppresses the peeling band voltage and does not damage the optical member or the electronic member during peeling. Can be provided.

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

≪≪A. Surface protection film ≫≫
The surface protective film according to the embodiment of the present invention includes an adhesive layer.

The surface protective film may contain any suitable other member as long as it contains the pressure-sensitive adhesive layer, as long as the effect of the present invention is not impaired. Typically, the surface protective film of the present invention includes a base material layer and an adhesive layer.

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

In FIG. 1, the surface of the pressure-sensitive adhesive layer 2 on the opposite side of the base material layer 1 is provided with an arbitrary suitable release liner (sometimes referred to as a release sheet or separator) for protection until use or the like. It may be (not shown). Examples of the release liner include a release liner in which the surface of a base material (liner base material) such as paper or plastic film is treated with silicone, and a polyolefin resin on the surface of a base material (liner base material) such as paper or plastic film. Examples include a laminated release liner.

Examples of the plastic film as the liner base material include polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate film, and polybutylene terephthalate film. Examples thereof include a polyurethane film and an ethylene-vinyl acetate copolymer film.

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

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

The pressure-sensitive adhesive layer contained in the surface protective film has a surface free energy of 6 mJ / m ^{2 to} 30 mJ / m ² with respect to diiodomethane, more preferably 8 mJ / m ^{2 to} 30 mJ / m 2, and further preferably 10 mJ / ^{m 2.} It is m ^{2 to} 30 mJ / m ² , and particularly preferably 12 mJ / m ^{2 to} 30 mJ / m ² . If the surface free energy of the pressure-sensitive adhesive layer contained in the surface protective film with respect to diiodomethane is within the above range, the peeling band voltage is sufficiently suppressed, and the adherend (typically, an optical member or an electronic member) is removed at the time of peeling. A surface protective film that does not break can be provided. If the surface free energy of the pressure-sensitive adhesive layer contained in the surface protective film with respect to diiodomethane is too low outside the above range, the peeling band voltage may not be sufficiently suppressed. If the surface free energy of the pressure-sensitive adhesive layer contained in the surface protective film with respect to diiodomethane is too high outside the above range, the adherend may be contaminated.

The surface free energy of the pressure-sensitive adhesive layer contained in the surface protective film with respect to diiodomethane can be easily measured as described later, and the pressure-sensitive adhesive layer is designed so that the surface free energy falls within the above-mentioned predetermined range. By doing so, it is possible to provide a surface protective film that sufficiently suppresses the peeling band voltage and does not damage the adherend (typically, an optical member or an electronic member) at the time of peeling. Here, as a point of designing the above-mentioned pressure-sensitive adhesive layer, in the present invention, typically, an ionic compound and a fluorine-based compound are used in combination, and a fluorine compound is selected. Then, as the selection of the fluorine compound, for example, from among the fluorine compounds of a specific category, those having the above-mentioned surface free energy within the above-mentioned predetermined range can be selected. It is a level of action that can be carried out by a person skilled in the art without repeating excessive trial and error.

The adhesive layer contained in the surface protective film is attached to a glass plate and left at a temperature of 23 ° C. for 30 minutes, and then the surface protective film is peeled from the glass plate at a peeling angle of 180 degrees and a peeling speed of 300 mm at a temperature of 23 ° C. The peeling force when peeled at / minute is preferably 0.005N / 25mm to 0.1N / 25mm, more preferably 0.007N / 25mm to 0.08N / 25mm, and further preferably 0.01N. It is / 25 mm to 0.05 N / 25 mm, particularly preferably 0.01 N / 25 mm to 0.03 N / 25 mm, and most preferably 0.01 N / 25 mm to 0.02 N / 25 mm. If the peeling force is within the above range, it is difficult to peel off easily from the adherend, and typically, it is attached to the exposed surface of the optical member or the electronic member during the manufacturing process of the optical member or the electronic member. It is possible to provide a surface protective film that is less likely to be peeled off after the shavings and can be easily peeled off if peeling is required.

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

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

The surface protective film according to the embodiment of the present invention typically prevents scratches on the surface of the optical member or the electronic member during processing, assembly, inspection, transportation, etc. in the manufacturing process of the optical member or the electronic member. A surface protective film containing an adhesive layer, which is attached to the exposed surface of the optical member or the electronic member for the purpose of sufficiently suppressing the peeling band voltage, and the optical member or the electronic member is pressed at the time of peeling. A surface protective film that does not break.

The surface protective film according to the embodiment of the present invention has a glass peeling zone voltage of preferably 3.0 kV or less, more preferably 2.5 kV or less, still more preferably 2.0 kV or less, and particularly preferably 2.0 kV or less. It is 1.7 kV or less, and most preferably 1.5 kV or less. The method for measuring the voltage against the glass peeling zone will be described later.

The surface protective film according to the embodiment of the present invention has a peeling band voltage against the acrylic plate of preferably 4.0 kV or less, more preferably 3.5 kV or less, still more preferably 3.0 kV or less, still more preferably. Is 2.5 kV or less, particularly preferably 2.0 kV or less, and most preferably 1.5 kV or less. The method of measuring the peeling band voltage against the acrylic plate will be described later.

The surface protective 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, and particularly preferably 2.8% or less. , Most preferably 2.5% or less. If the haze of the surface protective film according to the embodiment of the present invention is within the above range, it is suitable as a surface protective film to be attached to an exposed surface of an optical member or an electronic member. In particular, if the haze of the surface protective film according to the embodiment of the present invention can be reduced to 3% or less, the inspectability of the surface protective film according to the embodiment of the present invention is further improved, which is more preferable. The haze measurement method will be described later.

The surface protective film according to the embodiment of the present invention has a residual adhesive force against glass of preferably 70% or more, more preferably 80% or more, still more preferably 85% or more, and particularly preferably 88% or more. Most preferably, it is 90% or more. This residual adhesive force against glass is an index of how much the component of the pressure-sensitive adhesive layer of the surface protective film is transferred to the surface of the adherend and contaminated. The higher the value of the residual adhesive ratio to glass, the higher the risk of contaminating the adherend. The lower the value of the residual adhesive ratio to glass, the higher the risk of contaminating the adherend. Is a low surface protection film. The method for measuring the residual adhesion to glass will be described later.

<< A-1. Adhesive layer ≫
The pressure-sensitive adhesive layer is composed of a pressure-sensitive adhesive. The pressure-sensitive adhesive is formed from a pressure-sensitive adhesive composition. That is, the pressure-sensitive adhesive formed from the pressure-sensitive adhesive composition forms a layer shape to form a pressure-sensitive adhesive layer.

The pressure-sensitive adhesive can be defined as being formed from a pressure-sensitive adhesive composition. This is because the pressure-sensitive adhesive becomes a pressure-sensitive adhesive when the pressure-sensitive adhesive composition undergoes a cross-linking reaction or the like due to heating or irradiation with ultraviolet rays, so that it is impossible to directly identify the pressure-sensitive adhesive by its structure. Since there are circumstances that are almost impractical (“impossible / impractical circumstances”), the adhesive was properly specified as a “product” by the provision of “a product formed from an adhesive composition”. It is a thing.

The pressure-sensitive adhesive layer can be formed by any suitable method. As such a method, for example, the pressure-sensitive adhesive composition is applied onto an arbitrary suitable base material, heated and dried as necessary, and cured as necessary, and the pressure-sensitive adhesive is applied on the base material. A method of forming a layer can be mentioned. Examples of such an application method include 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, and a roll brush coater. Method can be mentioned.

The thickness of the pressure-sensitive adhesive layer is preferably 0.5 μm to 150 μm, more preferably 1 μm to 100 μm, still more preferably 2 μm to 80 μm, and particularly preferably 2 μm to 80 μm, in that the effects of the present invention can be more exhibited. It is 3 μm to 50 μm, most preferably 5 μm to 30 μm.

The pressure-sensitive adhesive composition includes a base polymer, an ionic compound, and a fluorine-based compound. When the pressure-sensitive adhesive composition contains a base polymer, an ionic compound, and a fluorine-based compound, the optics are typically used in the manufacturing process of optical members and electronic members during processing, assembly, inspection, transportation, and the like. A surface protective film containing an adhesive layer, which is attached to the exposed surface of the optical member or the electronic member to prevent scratches on the surface of the member or the electronic member, and sufficiently suppresses the peeling band voltage. , A surface protective film that does not damage the optical member or the electronic member at the time of peeling can be provided.

In the present invention, the effect of the present invention can be exhibited by the pressure-sensitive adhesive composition containing both an ionic compound and a fluorine-based compound in addition to the base polymer. In particular, the effect of the present invention can be remarkably exhibited by containing (combining) both an ionic compound and a fluorine-based compound (sometimes referred to as "specific fluorine-based compound") according to a preferred embodiment described later. .. This is done by coexisting an ionic compound capable of exhibiting an antistatic effect with a fluorine-based compound (preferably a specific fluorine-based compound) in the pressure-sensitive adhesive composition, thereby causing a fluorine-based compound (preferably a specific fluorine-based compound). It is presumed that the ionic compound is unevenly distributed on the surface side (the side to be bonded to the adherend) of the pressure-sensitive adhesive layer due to the synergistic effect with the compound).

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 further preferably 99.9% by weight in terms of solid content. It is 70% by weight to 99.9% by weight, particularly preferably 75% by weight to 99.9% by weight, and most preferably 80% by weight to 99.9% by weight. If the content ratio of the base polymer in the pressure-sensitive adhesive composition is within the above range in terms of solid content, the peeling band voltage is sufficiently suppressed, and the adherend (typically, an optical member or an electronic member) is removed at the time of peeling. A surface protective film that does not break can be provided.

The content ratio of the ionic compound 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 further preferably 0.5 parts by weight. It is ~ 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 ratio of the ionic compound to 100 parts by weight of the base polymer is within the above range, the peeling band voltage is sufficiently suppressed, and the surface is not damaged during peeling (typically, an optical member or an electronic member). A protective film may be provided. If the content ratio of the ionic compound to 100 parts by weight of the base polymer is too low outside the above range, the peeling band voltage may not be sufficiently suppressed. If the content ratio of the ionic compound to 100 parts by weight of the base polymer is out of the above range and is too high, the adherend may be contaminated.

The content ratio of the fluorine-based compound to 100 parts by weight of the base polymer is preferably 0.05 parts by weight or more, more preferably 0.1 parts by weight to 5.0 parts by weight, and further preferably 0.15 parts by weight. It is ~ 3.0 parts by weight, particularly preferably 0.2 parts by weight to 2.0 parts by weight, and most preferably 0.23 parts by weight to 1.5 parts by weight. When the content ratio of the fluorine-based compound to 100 parts by weight of the base polymer is within the above range, the peeling band voltage is sufficiently suppressed and the adherend (typically, an optical member or an electronic member) is not damaged during peeling. A protective film may be provided. If the content ratio of the fluorine-based compound to 100 parts by weight of the base polymer is too low outside the above range, the peeling band voltage may not be sufficiently suppressed. If the content ratio of the fluorine-based compound to 100 parts by weight of the base polymer is too high outside the above range, the adherend may be contaminated.

<A-1-1. Base polymer>
The base polymer is preferably at least one selected from urethane-based resin, acrylic-based resin, rubber-based resin, and silicone-based resin. If the base polymer is at least one selected from urethane-based resin, acrylic-based resin, rubber-based resin, and silicone-based resin, the peeling band voltage is suppressed more sufficiently, and the adherend (typically, the adherend) at the time of peeling It is possible to provide a surface protective film that does not damage the optical member or the electronic member).

[A-1-1-1. Polyol]
The polyol preferably reacts with the polyfunctional isocyanate compound to form a urethane resin. More specifically, a urethane-based resin is preferably formed from a composition containing a polyol and a polyfunctional isocyanate compound, and more specifically, a urethane-based resin is obtained by curing a composition containing a polyol and a polyfunctional isocyanate compound. Is formed. As a method for forming a urethane-based resin by curing a composition containing a polyol and a polyfunctional isocyanate compound, any method such as a urethanization reaction method using bulk polymerization or solution polymerization is desired as long as the effects of the present invention are not impaired. Appropriate method can be adopted.

The polyol may be only one kind or two or more kinds.

The polyol preferably includes at least one selected from polyester polyols, polyether polyols, polycaprolactone polyols, polycarbonate polyols, and castor oil-based polyols. The polyol is more preferably a polyether polyol in that the effects of the present invention can be more exhibited.

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

Examples of the polyol component include ethylene glycol, diethylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, and 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 Examples thereof include -1,8-octanediol, 1,8-decanediol, octadecanediol, glycerin, trimethylolpropane, pentaerythritol, hexanetriol and polypropylene glycol.

Examples of the acid component include succinic acid, methylsuccinic acid, adipic acid, piceric acid, azelaic acid, sebacic acid, 1,12-dodecanedioic acid, 1,14-tetradecanedioic acid, dimer acid, 2-methyl-1, 4-Cyclohexanedicarboxylic acid, 2-ethyl-1,4-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, isophthalic acid, terephthalic acid, 1,4-naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid , These acid anhydrides and the like.

Examples of the polyether polyol include water, low molecular weight polyols (propylene glycol, ethylene glycol, glycerin, trimethylolpropane, pentaerythritol, etc.), bisphenols (bisphenol A, etc.), dihydroxybenzene (catechol, resorcin, hydroquinone, etc.), etc. Examples thereof include a polyether polyol obtained by addition-polymerizing an alkylene oxide such as ethylene oxide, propylene oxide, and butylene oxide. Specific examples thereof include polyethylene glycol, polypropylene glycol, polytetramethylene glycol and the like.

Examples of the polycaprolactone polyol include a caprolactone-based polyester diol obtained by ring-opening polymerization of a cyclic ester monomer such as ε-caprolactone and σ-valerolactone.

Examples of the polycarbonate polyol include a polycarbonate polyol obtained by subjecting the above-mentioned polyol component and phosgen to a polycondensation reaction; the above-mentioned polyol component and dimethyl carbonate, diethyl carbonate, diprovyl carbonate, diisopropyl carbonate, dibutyl carbonate, ethylbutylcarbonate, ethylene carbonate, and the like. Polycarbonate polyol obtained by ester exchange condensation with carbonic acid diesters such as propylene carbonate, diphenyl carbonate, dibenzyl carbonate; copolymerized polycarbonate polyol obtained by using two or more of the above polyol components in combination; the various polycarbonate polyols and carboxyl groups Polycarbonate polyol obtained by esterifying the contained compound; Polycarbonate polyol obtained by etherifying the various polycarbonate polyols and the hydroxyl group-containing compound; Obtained by performing an ester exchange reaction between the various polycarbonate polyols and the ester compound. Polycarbonate polyol; Polycarbonate polyol obtained by ester exchange reaction between various polycarbonate polyols and hydroxyl group-containing compounds; Polycarbonate-based polycarbonate polyol obtained by polycondensation reaction between various polycarbonate polyols and dicarboxylic acid compounds; Examples thereof include a copolymerized polyether polycarbonate polyol obtained by copolymerizing a polyol and an alkylene oxide.

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

The number average molecular weight Mn of the polyol is preferably 300 to 100,000, more preferably 400 to 75,000, further preferably 450 to 50,000, and particularly preferably 500 to 30,000. When the number average molecular weight Mn of the polyol is within the above range, it is more difficult to peel off from the adherend, and typically, during the manufacturing process of the optical member or the electronic member, the exposed surface of the optical member or the electronic member. It is possible to provide a surface protective film that is less likely to be peeled off after being attached to the surface and can be peeled off more easily if peeling is required.

The polyol preferably contains a polyol (A1) having three OH groups and having a number average molecular weight Mn of 300 to 100,000. The polyol (A1) may be only one kind or two or more kinds.

The content ratio of the polyol (A1) in the polyol is preferably 5% by weight or more, more preferably 25% by weight to 100% by weight, still more preferably 50% by weight to 100% by weight, and particularly preferably. It is 70% by weight to 100% by weight, most preferably 90% by weight to 100% by weight. When the content ratio of the polyol (A1) in the polyol is within the above range, it is more difficult to peel off from the adherend, and typically, during the manufacturing process of the optical member or the electronic member, the optical member or the electron. It is possible to provide a surface protective film that is less likely to be peeled off after being attached to the exposed surface of the member and can be peeled off more easily if peeling is required.

The polyol (A1) preferably contains a polyol (A1a) having three OH groups and having a number average molecular weight Mn of 8000 to 20000. The polyol (A1a) may be of only one type or of two or more types.

The content ratio 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. It is particularly preferably 75% by weight to 93% by weight, and most preferably 80% by weight to 90% by weight. When the content ratio of the polyol (A1a) in the polyol (A1) is within the above range, it is more difficult to peel off from the adherend, and typically, during the manufacturing process of the optical member or the electronic member, the optical member It is possible to provide a surface protective film which is less likely to be peeled off after being attached to the exposed surface of the electronic member and can be peeled off more easily if peeling is required.

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, and particularly preferably 9500 to 15500. , Most preferably 1000 to 15000. When the number average molecular weight Mn of the polyol (A1a) is within the above range, it is more difficult to peel off from the adherend, and typically, during the manufacturing process of the optical member or the electronic member, the optical member or the electronic member It is possible to provide a surface protective film which is less likely to be peeled off after being attached to the exposed surface of the above and which can be peeled off more easily if peeling is required.

The polyol (A1) may contain a polyol (A1b) having 3 or more OH groups and having a number average molecular weight Mn of 5000 or less. The polyol (A1b) may be only one kind or two or more kinds.

The polyol (A1b) preferably has a polyol having three OH groups (triol), a polyol having four OH groups (tetraol), a polyol having five OH groups (pentaol), and a polyol having six OH groups. At least one selected from polyols (hexaol).

The content ratio of the polyol (A1b) in the polyol (A1) is preferably 50% by weight or less, more preferably 0% by weight to 40% by weight, still more preferably 5% by weight to 30% by weight. It is particularly preferably 7% by weight to 25% by weight, and most preferably 10% by weight to 20% by weight. When the content ratio of the polyol (A1b) in the polyol (A1) is within the above range, it is more difficult to peel off from the adherend, and typically, during the manufacturing process of the optical member or the electronic member, the optical member It is possible to provide a surface protective film which is less likely to be peeled off after being attached to the exposed surface of the electronic member and can be peeled off more easily if peeling is required.

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, and most preferably 900. ~ 3300. When the number average molecular weight Mn of the polyol (A1b) is within the above range, it is more difficult to peel off from the adherend, and typically, during the manufacturing process of the optical member or the electronic member, the optical member or the electronic member It is possible to provide a surface protective film which is less likely to be peeled off after being attached to the exposed surface of the above and which can be peeled off more easily if peeling is required. If the number average molecular weight Mn of the polyol (A1b) is out of the above range, the adhesive strength may increase with time, and excellent reworkability may not be exhibited.

When 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 (hexaol). The total amount thereof is preferably 40% by weight or less, more preferably 0% by weight to 30% by weight, and further preferably 3% by weight to 20% by weight as the content ratio in the polyol (A1). Particularly preferably, it is 5% by weight to 15% by weight, and most preferably 7% by weight to 10% by weight. Among the polyols (A1), the polyol (A1b) is selected from a polyol having 4 OH groups (tetraol), a polyol having 5 OH groups (pentaol), and a polyol having 6 OH groups (hexaol). When the total amount of at least one of these is within the above range, it is more difficult to peel off from the adherend, and typically, during the manufacturing process of the optical member or the electronic member, the optical member or the said. It is possible to provide a surface protective film that is less likely to be peeled off after being attached to an exposed surface of an electronic member and can be peeled off more easily if peeling is required. Further, it can be a surface protective film having excellent transparency.

The polyol (A1b) is at least one selected from among them, a polyol having 4 OH groups (tetraol), a polyol having 5 OH groups (pentaol), and a polyol having 6 OH groups (hexaol). The content ratio of the seed 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, based on the total polyol (A1). It is the following, and most preferably 1% by weight or less. Content ratio of at least one selected from polyol (tetraol) having 4 OH groups, polyol (pentaol) having 5 OH groups, and polyol (hexaol) having 6 OH groups in the polyol (A1b). Is within the above range, it is more difficult to peel off from the adherend, and typically, after being attached to the exposed surface of the optical member or the electronic member during the manufacturing process of the optical member or the electronic member. If peeling is less likely to occur and peeling is required, a surface protective film that can be peeled more easily can be provided. Further, at least one selected from a polyol (tetraol) having 4 OH groups, a polyol having 5 OH groups (pentaol), and a polyol having 6 OH groups (hexaol) in the polyol (A1b). If the content ratio is out of the above range, the transparency of the surface protective film may decrease.

The polyol (A1) may contain a polyol (A1c) having 4 or more OH groups and having a number average molecular weight Mn of 20000 or less. The polyol (A1c) may be of only one type or of two or more types.

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. It is more preferably 50% by weight or less, particularly preferably 40% by weight or less, and most preferably 30% by weight or less. If the content ratio of the polyol (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 more difficult to peel off from the adherend, and is typically Is less likely to peel off after being attached to the exposed surface of the optical member or the electronic member during the manufacturing process of the optical member or the electronic member, and can be peeled off more easily if the peeling is required. A surface protective film may be provided. Further, it can be a surface protective film having excellent transparency.

[A-1-1-2. Urethane prepolymer]
The urethane prepolymer preferably reacts with the polyfunctional isocyanate compound to form a urethane-based resin. More specifically, a urethane resin is preferably formed from the composition containing the urethane prepolymer and the polyfunctional isocyanate compound, and more specifically, the composition containing the urethane prepolymer and the polyfunctional isocyanate compound is cured. Urethane resin is formed. As a method for forming a urethane-based resin by curing a composition containing a polyol and a polyfunctional isocyanate compound, any suitable method is used as long as it is a method for producing a urethane-based resin using a so-called "urethane prepolymer" as a raw material. Manufacturing method can be adopted.

In the description of the present invention, the "urethane prepolymer" is a "urethane prepolymer" generally referred to by those skilled in the art in the production of urethane resins, and is different from the "polyurethane" described in Section A-1-1-1. It shall be.

The urethane prepolymer may be only one kind or two or more kinds.

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

The urethane prepolymer is preferably a polyurethane polyol, more preferably a polyester polyol (a1) or a polyether polyol (a2), respectively, alone or in a mixture of (a1) and (a2), in the presence of a catalyst. It is formed by reacting with a polyfunctional isocyanate compound under or without a catalyst. The polyester polyol (a1) may be of only one type or of two or more types. The polyether polyol (a2) may be of only one type or of two or more types.

As the polyester polyol (a1), any suitable polyester polyol can be used. Examples of such a polyester polyol (a1) include a polyester polyol obtained by reacting an acid component with a glycol component. Examples of the acid component include terephthalic acid, adipic acid, azelaic acid, sebacic acid, phthalic anhydride, isophthalic acid, trimellitic acid and the like. Examples of the glycol component include ethylene glycol, propylene glycol, diethylene glycol, butylene glycol, 1,6-hexane glycol, 3-methyl-1,5-pentanediol, 3,3'-dimethylol heptane, and polyoxyethylene glycol. Examples thereof include polyoxypropylene glycol, 1,4-butanediol, neopentyl glycol, butylethylpentanediol, and polyol components such as glycerin, trimethylolpropane, and pentaerythritol. Examples of the polyester polyol (a1) also include a polyester polyol obtained by ring-opening polymerization of lactones such as polycaprolactone, poly (β-methyl-γ-valerolactone) and polyvalerolactone.

The polyester polyol (a1) can be used from a low molecular weight to a high molecular weight. As the molecular weight of the polyester polyol (a1), the number average molecular weight Mn is preferably 100 to 100,000. If the number average molecular weight Mn is less than 100, the reactivity becomes high and gelation may easily occur. If the number average molecular weight Mn exceeds 100,000, the reactivity may be lowered, and the cohesive force of the polyurethane polyol itself may be reduced. 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 suitable polyether polyol can be used. Examples of such a polyether polyol (a2) include water, propylene glycol, ethylene glycol, glycerin, trimethylolpropane and other low molecular weight polyols as initiators, and ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran and the like. Examples thereof include polyether polyols obtained by polymerizing an oxylan compound. Specific examples of such a polyether polyol (a2) include a polyether polyol having two or more functional groups, such as polypropylene glycol, polyethylene glycol, and polytetramethylene glycol.

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

A part of the polyether polyol (a2) is, if necessary, glycols such as ethylene glycol, 1,4-butanediol, neopentyl glycol, butylethylpentanediol, glycerin, trimethylolpropane, pentaerythritol, and the like. It can be used in combination by substituting polyvalent amines such as ethylenediamine, N-aminoethylethanolamine, isophoronediamine, and xylylenediamine.

As the polyether polyol (a2), only a bifunctional polyether polyol may be used, or a poly having a number average molecular weight Mn of 100 to 100,000 and having at least 3 or more hydroxyl groups in one molecule. Part or all of the ether polyol may be used. When a part or all of the polyether polyol (a2) having a number average molecular weight Mn of 100 to 100,000 and having at least 3 or more hydroxyl groups in one molecule is used, the adhesive strength and the removability Can be well-balanced. In such a polyether polyol, if the number average molecular weight Mn is less than 100, the reactivity becomes high and gelation may easily occur. Further, in such a polyether polyol, if the number average molecular weight Mn exceeds 100,000, the reactivity may be lowered, and further, the cohesive force of the polyurethane polyol itself may be reduced. The number average molecular weight Mn of such a polyether polyol is more preferably 100 to 10,000.

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

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

Examples of the organometallic compound include tin-based compounds and non-tin-based compounds.

Examples of tin-based compounds include dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin dimalate, dibutyltin dilaurate (DBTDL), dibutyltin diacetate, dibutyltin sulfide, tributyltin sulfide, tributyltin oxide, and tributyl. Examples thereof include tin acetate, triethyl tin ethoxide, tributyl tin ethoxide, dioctyl tin oxide, tributyl tin chloride, tributyl tin trichloroacetate, tin 2-ethylhexanoate and the like.

Examples of non-tin compounds include titanium 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 compounds such as iron 2-ethylhexanoate and iron acetylacetonate; Cobalt compounds such as cobalt benzoate and cobalt 2-ethylhexanoate; Zinc compounds such as zinc naphthenate and zinc 2-ethylhexanate; Zylon compounds such as zirconium naphthenate; and the like.

When a catalyst is used to obtain a polyurethane polyol, in a system in which two types of polyols, a polyester polyol and a polyether polyol, are present, the reactivity is different. Therefore, in a single catalyst system, gelation or a reaction solution may occur. The problem of turbidity is likely to occur. Therefore, by using two types of catalysts when obtaining the polyurethane polyol, the reaction rate, the selectivity of the catalyst, and the like can be easily controlled, and these problems can be solved. Examples of the combination of such two types of catalysts include tertiary amine / organic metal-based, tin-based / non-tin-based, and tin-based / tin-based, preferably tin-based / tin-based, and more preferably tin-based / tin-based. Is a combination of dibutyltin dilaurate and tin 2-ethylhexanoate. In terms of the compounding ratio, tin 2-ethylhexanoate / dibutyltin dilaurate is preferably less than 1, more preferably 0.2 to 0.6 by weight. If the compounding ratio is 1 or more, gelation may easily occur due to the balance of catalytic activity.

When a catalyst is used in obtaining the polyurethane polyol, the amount of the catalyst used is preferably 0.01% by weight to 1% by weight based on the total amount of the polyester polyol (a1), the polyether polyol (a2) and the polyfunctional isocyanate compound. It is 0.0% by weight.

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

When obtaining the polyurethane polyol, it is not necessary to use a catalyst. In that case, the reaction temperature is preferably 100 ° C. or higher, more preferably 110 ° C. or higher. Moreover, when obtaining a polyurethane polyol without a catalyst, it is preferable to react for 3 hours or more.

Examples of the method for obtaining the polyurethane polyol include 1) a method in which a polyester polyol, a polyether polyol, a catalyst and a polyfunctional isocyanate compound are charged in a flask, and 2) a method in which a polyester polyol, a polyether polyol and a catalyst are charged in a flask and the polyfunctional isocyanate is obtained. Examples thereof include a method of adding the compound by dropping it. As a method for obtaining a polyurethane polyol, the method 2) is preferable in controlling the reaction.

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

[A-1-1-3. Acrylic resin]
As the acrylic resin, any suitable acrylic resin can be adopted as long as the effects of the present invention are not impaired. The acrylic resin may be only one kind or two or more kinds.

The weight average molecular weight of the acrylic resin is preferably 300,000 to 2.5 million, more preferably 350,000 to 2 million, and further preferably 400,000 to 1.8 million in that the effects of the present invention can be more exhibited. It is particularly preferably 500,000 to 1,500,000.

The acrylic resin is preferably a (meth) acrylic acid alkyl ester having 4 to 12 carbon atoms in the alkyl group of the (component a) alkyl ester moiety, in that the effects of the present invention can be more exhibited. Ingredient) An acrylic resin formed by polymerization from a composition (B) containing at least one selected from the group consisting of (meth) acrylic acid ester having an OH group and (meth) acrylic acid. Each of (component a) and (component b) may be independently of only one type or of two or more types.

Examples of the (meth) acrylic acid alkyl ester (component a) in which the alkyl group of the alkyl ester moiety has 4 to 12 carbon atoms are n-butyl (meth) acrylic acid, isobutyl (meth) acrylic acid, and (meth). S-butyl acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2--butyl (meth) acrylate Ethylhexyl, isooctyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate And so on. Among these, n-butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate are preferable, and n-butyl acrylate and acrylic are more preferable in that the effects of the present invention can be more exhibited. 2-Ethylhexyl acid.

As at least one (b component) selected from the group consisting of (meth) acrylic acid ester having an OH group and (meth) acrylic acid, for example, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and the like. Examples thereof include (meth) acrylic acid ester having an OH group such as hydroxybutyl (meth) acrylic acid, and (meth) acrylic acid. Among these, hydroxyethyl (meth) acrylate and (meth) acrylic acid are preferable, and hydroxyethyl acrylate and acrylic acid are more preferable, in that the effects of the present invention can be more exhibited.

The composition (B) may contain a copolymerizable monomer other than the components (a) and (b). The copolymerizable monomer may be only one kind or two or more kinds. Examples of such copolymerizable monomers 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). ) And other carboxyl group-containing monomers (excluding (meth) acrylic acid); (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide. , N-Butoxymethyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide and other amide group-containing monomers; (meth) acrylate aminoethyl, (meth) acrylate dimethylaminoethyl, (meth) acrylate t-butyl Amino group-containing monomers such as aminoethyl; glycidyl (meth) acrylate, epoxy group-containing monomers such as methyl glycidyl (meth) acrylate; cyano group-containing monomers such as acrylonitrile and methacrylonitrile; N-vinyl-2-pyrrolidone, (Meta) Acryloylmorpholin, N-vinylpiperidone, N-vinylpiperazin, N-vinylpyrrole, N-vinylimidazole, vinylpyridine, vinylpyrimidine, vinyloxazole and other heterocycle-containing vinyl monomers; Group-containing monomer; Phosphate-containing monomer such as 2-hydroxyethylacryloyl phosphate; Iimide group-containing monomer such as cyclohexylmaleimide and isopropylmaleimide; isocyanate group-containing monomer such as 2-methacryloyloxyethyl isocyanate; Cyclopentyl (meth) acrylate, (Meta) acrylic acid ester having an alicyclic hydrocarbon group such as cyclohexyl (meth) acrylate and isobornyl (meth) acrylate; aromatics such as phenyl (meth) acrylate, phenoxyethyl (meth) acrylate and benzyl (meth) acrylate (Meta) acrylic acid ester having a hydrocarbon group; vinyl ester such as vinyl acetate and vinyl propionate; aromatic vinyl compound such as styrene and vinyl toluene; olefins and dienes such as ethylene, butadiene, isoprene and isobutylene; vinyl Vinyl ethers such as alkyl ethers; vinyl chloride; and the like can be mentioned.

As the copolymerizable monomer, a polyfunctional monomer may also be adopted. The polyfunctional monomer means a monomer having two or more ethylenically unsaturated groups in one molecule. As the ethylenically unsaturated group, any suitable ethylenically unsaturated group can be adopted as long as the effect of the present invention is not impaired. Examples of such an ethylenically unsaturated group include 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). 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, and neopentyl glycol. Di (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, trimethylolpropanthry (meth) acrylate, tetramethylolmethanetri (meth) acrylate, allyl Examples thereof include (meth) acrylate, vinyl (meth) acrylate, divinylbenzene, epoxy acrylate, polyester acrylate, and urethane acrylate. Such a polyfunctional monomer may be only one kind or two or more kinds.

As the copolymerizable monomer, (meth) acrylic acid alkoxyalkyl ester may also be adopted. Examples of the (meth) acrylate alkoxyalkyl ester include (meth) acrylate 2-methoxyethyl, (meth) acrylate 2-ethoxyethyl, (meth) acrylate methoxytriethylene glycol, and (meth) acrylate 3-. Examples thereof include methoxypropyl, 3-ethoxypropyl (meth) acrylate, 4-methoxybutyl (meth) acrylate, and 4-ethoxybutyl (meth) acrylate. The (meth) acrylic acid alkoxyalkyl ester may be only one kind or two or more kinds.

The content of the (meth) acrylic acid alkyl ester (component a) in which the alkyl group of the alkyl ester moiety has 4 to 12 carbon atoms is a monomer constituting the acrylic polymer in that the effects of the present invention can be more exhibited. It is preferably 30% by weight or more, more preferably 35% by weight to 99% by weight, still more preferably 40% by weight to 98% by weight, and particularly preferably 50% by weight, based on the total amount of the components (100% by weight). It is from% by weight to 95% by weight.

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 makes the acrylic polymer more effective in terms of exhibiting the effects of the present invention. It is preferably 1% by weight or more, more preferably 1% by weight to 30% by weight, still more preferably 2% by weight to 20% by weight, based on the total amount of the constituent monomer components (100% by weight). It is preferably 3% by weight to 10% by weight.

The composition (B) may contain any suitable other ingredients as long as the effects of the present invention are not impaired. Examples of such other components include polymerization initiators, chain transfer agents, solvents and the like. As the content of these other components, any appropriate content may be adopted as long as the effect of the present invention is not impaired.

As the polymerization initiator, a thermal polymerization initiator, a photopolymerization initiator (photoinitiator), or the like can be adopted depending on the type of the polymerization reaction. The polymerization initiator may be only one kind or two or more kinds.

The thermal polymerization initiator can be preferably used when obtaining an acrylic resin by solution polymerization. Examples of such a thermal polymerization initiator include an azo-based polymerization initiator, a peroxide-based polymerization initiator (for example, dibenzoyl peroxide, tert-butyl permalate, etc.), a redox-based polymerization initiator, and the like. .. Among these thermal polymerization initiators, the azo-based initiator disclosed in JP-A-2002-69411 is particularly preferable. Such an azo-based polymerization initiator is preferable because the decomposition product of the polymerization initiator does not easily remain in the acrylic resin as a portion that causes the generation of heating generated gas (out gas). Examples of the azo-based polymerization initiator include 2,2'-azobisisobutyronitrile (hereinafter, may be referred to as AIBN) and 2,2'-azobis-2-methylbutyronitrile (hereinafter, referred to as AMBN). , 2,2'-azobis (2-methylpropionic acid) dimethyl, 4,4'-azobis-4-cyanovalerian acid and the like.

The photopolymerization initiator can preferably be used when obtaining an acrylic polymer by active energy ray polymerization. Examples of the photopolymerization initiator include a benzoin ether type photopolymerization initiator, an acetophenone type photopolymerization initiator, an α-ketol type photopolymerization initiator, an aromatic sulfonyl chloride type photopolymerization initiator, and a photoactive oxime type photopolymerization initiator. Examples thereof include benzoin-based photopolymerization initiators, benzyl-based photopolymerization initiators, benzophenone-based photopolymerization initiators, ketal-based photopolymerization initiators, thioxanthone-based photopolymerization initiators, and the like.

Examples of the benzoin ether-based photopolymerization initiator include benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2,2-dimethoxy-1,2-diphenylethane-1-one, and anisole. Examples include methyl ether. Examples of the acetophenone-based photopolymerization initiator include 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenyl ketone, 4-phenoxydichloroacetophenone, and 4- (t-butyl). Examples include dichloroacetophenone. Examples of the α-ketol-based photopolymerization initiator include 2-methyl-2-hydroxypropiophenone and 1- [4- (2-hydroxyethyl) phenyl] -2-methylpropan-1-one. .. Examples of the aromatic sulfonyl chloride-based photopolymerization initiator include 2-naphthalene sulfonyl chloride. Examples of the photoactive oxime-based photopolymerization initiator include 1-phenyl-1,1-propanedione-2- (o-ethoxycarbonyl) -oxime. Examples of the benzoin-based photopolymerization initiator include benzoin and the like. Examples of the benzyl-based photopolymerization initiator include benzyl and the like. Examples of the benzophenone-based photopolymerization initiator include benzophenone, benzoylbenzoic acid, 3,3'-dimethyl-4-methoxybenzophenone, polyvinylbenzophenone, α-hydroxycyclohexylphenyl ketone and the like. Examples of the ketal-based photopolymerization initiator include benzyldimethyl ketal and the like. Examples of the thioxanthone-based photopolymerization initiator include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, and dodecylthioxanthone.

When the base polymer is an acrylic resin, the pressure-sensitive adhesive composition may contain a cross-linking agent. By using a cross-linking agent, the cohesive force of the pressure-sensitive adhesive can be improved, and the effect of the present invention can be further exhibited. The cross-linking agent may be only one kind or two or more kinds.

Examples of the cross-linking agent include a polyfunctional isocyanate-based cross-linking agent, an epoxy-based cross-linking agent, a melamine-based cross-linking agent, a peroxide-based cross-linking agent, a urea-based cross-linking agent, a metal alkoxide-based cross-linking agent, a metal chelate-based cross-linking agent, and a metal salt. Examples thereof include a system cross-linking agent, a carbodiimide-based cross-linking agent, an oxazoline-based cross-linking agent, an aziridine-based cross-linking agent, and an amine-based cross-linking agent. Among these, at least one selected from the group consisting of a polyfunctional isocyanate-based cross-linking agent and an epoxy-based cross-linking agent is preferable in that the effects of the present invention can be more exhibited.

Examples of the polyfunctional isocyanate-based cross-linking agent include lower aliphatic polyisocyanates such as 1,2-ethylene diisocyanate, 1,4-butylene diisocyanate, and 1,6-hexamethylene diisocyanate; cyclopentylene diisocyanate, cyclohexylene diisocyanate, and the like. Alicyclic polyisocyanates such as isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylene diisocyanate; 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, etc. Aromatic polyisocyanates and the like. Examples of the polyfunctional isocyanate-based cross-linking agent include trimethylolpropane / tolylene diisocyanate adduct (manufactured by Nippon Polyurethane Industry Co., Ltd., trade name "Coronate L") and trimethylolpropane / hexamethylene diisocyanate adduct (Nippon Polyurethane Industry Co., Ltd.). Company-made, product name "Coronate HL"), product name "Coronate HX" (Nippon Polyurethane Industry Co., Ltd.), trimethylolpropane / xylylene diisocyanate adduct (manufactured by Mitsui Chemicals Co., Ltd., product name "Takenate 110N"), etc. Commercial products are also included.

Examples of the epoxy-based cross-linking agent (polyfunctional epoxy compound) include N, N, N', N'-tetraglycidyl-m-xylene diamine, diglycidyl aniline, and 1,3-bis (N, N-diglycidyl amino). Methyl) cyclohexane, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, sorbitol polyglycidyl ether, Gglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, polyglycerol polyglycidyl ether, sorbitan polyglycidyl ether, trimethylolpropane polyglycidyl ether, diglycidyl adipate, o-phthalic acid diglycidyl ester, triglycidyl-tris (2- In addition to hydroxyethyl) isocyanurate, resorcin diglycidyl ether, and bisphenol-S-diglycidyl ether, epoxy resins having two or more epoxy groups in the molecule can be mentioned. Examples of the epoxy-based cross-linking agent include commercially available products such as the trade name "Tetrad C" (manufactured by Mitsubishi Gas Chemical Company, Inc.).

As the content of the cross-linking agent in the pressure-sensitive adhesive composition, any appropriate content can be adopted as long as the effect of the present invention is not impaired. Such a content is preferably 0.05 parts by weight to 20 parts by weight with respect to the solid content (100 parts by weight) of the acrylic resin, for example, in that the effect of the present invention can be more exhibited. , More preferably 0.1 parts by weight to 18 parts by weight, further preferably 0.5 parts by weight to 15 parts by weight, and particularly preferably 0.5 parts by weight to 10 parts by weight.

[A-1-1-4. Rubber resin]
The rubber-based resin is a rubber-based resin used in any suitable rubber-based pressure-sensitive adhesive, such as a known rubber-based pressure-sensitive adhesive described in JP-A-2015-074771 and the like, as long as the effects of the present invention are not impaired. Resin can be used. These may be only one kind or two or more kinds.

[A-1-1-5. Silicone resin]
The silicone-based resin is a silicone-based resin used in any suitable silicone-based pressure-sensitive adhesive, such as a known silicone-based pressure-sensitive adhesive described in JP-A-2014-047280, for example, as long as the effects of the present invention are not impaired. Resin can be used. These may be only one kind or two or more kinds.

<A-1-2. Urethane resin>
As described above, the polyol as the base polymer preferably reacts with the polyfunctional isocyanate compound to become a urethane resin. More specifically, a urethane-based resin is preferably formed from a composition containing a polyol and a polyfunctional isocyanate compound, and more specifically, a urethane-based resin is obtained by curing a composition containing a polyol and a polyfunctional isocyanate compound. Is formed. As a method for forming a urethane-based resin by curing a composition containing a polyol and a polyfunctional isocyanate compound, any method such as a urethanization reaction method using bulk polymerization or solution polymerization is desired as long as the effects of the present invention are not impaired. Appropriate method can be adopted.

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

That is, one preferred embodiment of the urethane-based resin is a urethane-based resin formed from a 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 polyfunctional isocyanate compound may be only one kind or two or more kinds.

As the polyfunctional isocyanate compound, any suitable polyfunctional isocyanate compound that can be used in the urethanization reaction can be adopted. Examples of such a 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, and dodeca. Examples thereof include methylene diisocyanate and 2,4,4-trimethylhexamethylene diisocyanate.

Examples of the polyfunctional alicyclic isocyanate compound include 3-isocyanate methyl-3,5,5-trimethylcyclohexylisocyanate, 1,3-cyclopentanediisocyanate, 1,3-cyclohexanediisocyanate, and 1,4-cyclohexane. Diisocyanate, isophorone diisocyanate, methyl-2,4-cyclohexanediisocyanate, methyl-2,6-cyclohexanediisocyanate, 4,4'-methylenebis (cyclohexylisocyanate), 1,4-bis (isocyanatemethyl) cyclohexane, 1,4-bis Examples thereof include (isocyanate methyl) cyclohexane, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated tolylene diisocyanate, and hydrogenated tetramethylxylylene diisocyanate.

Examples of the polyfunctional aromatic diisocyanate compound include 1,3-phenylenediocyanate, 1,4-phenylenediocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, and 2,2'-diphenylmethane. 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-naphthalenediocyanate, 4,4', 4 "-triphenylmethane triisocyanate, dianisidine diisocyanate, xylylene diisocyanate and the like can be mentioned.

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, Examples thereof include 4-diethylbenzene, 1,4-tetramethylxylylene diisocyanate, and 1,3-tetramethylxylylene diisocyanate.

Examples of the polyfunctional isocyanate compound include a trimethylolpropane adduct compound of various polyfunctional isocyanate compounds as described above, a biuret compound reacted with water, and a trimer having an isocyanurate ring. Moreover, you may use these together.

The equivalent ratio of NCO group to OH group in the polyol and the polyfunctional isocyanate compound is preferably 5.0 or less, more preferably 0.1 to 3.0, and further preferably 0.1 to 3.0 as the NCO group / OH group. It is 0.2 to 2.5, more preferably 0.3 to 2.5, still more preferably 0.3 to 2.0, and particularly preferably 0.5 to 2.0, most preferably. It is preferably 0.5 to 1.8. When the equivalent ratio of NCO group / OH group is within the above range, it is difficult to easily peel off from the adherend, and typically, the optical member or the electronic member is exposed during the manufacturing process of the optical member or the electronic member. It is possible to provide a surface protective film that is less likely to be peeled off after being attached to the surface and can be easily peeled off if peeling is required. Further, if the equivalent ratio of NCO group / OH group is within the above range, haze can be reduced. In particular, if the haze can be reduced to 3% or less, the inspectability of the surface protective film according to the embodiment of the present invention will be further improved.

The content ratio of the polyfunctional isocyanate compound is preferably 1.0% by weight to 30% by weight, more preferably 1.5% by weight to 27% by weight, and further, the content ratio of the polyfunctional isocyanate compound is preferably 1.0% by weight to 30% by weight, more preferably 1.5% by weight to 27% by weight, based on the polyol. It is preferably 2.0% by weight to 25% by weight, more preferably 2.3% by weight to 23% by weight, still more preferably 2.3% by weight to 18% by weight, and particularly preferably 2.5% by weight. It is from% to 18% by weight, most preferably 2.5% to 16% by weight. When the content ratio of the polyfunctional isocyanate compound is within the above range, it is difficult to easily peel off from the adherend, and typically, during the manufacturing process of the optical member or the electronic member, the exposed surface of the optical member or the electronic member. It is possible to provide a surface protective film that is less likely to be peeled off after being attached to the surface and can be easily peeled off if peeling is required. Further, if the content ratio of the polyfunctional isocyanate compound is within the above range, haze can be reduced. In particular, if the haze can be reduced to 3% or less, the inspectability of the surface protective film according to the embodiment of the present invention will be further improved.

A catalyst is preferably used to cure the composition containing the polyol and the polyfunctional isocyanate compound. Examples of such a catalyst include organometallic compounds and tertiary amine compounds. The catalyst may be only one type or two or more types.

Examples of the organic metal compound include iron compounds, tin compounds, titanium compounds, zirconium compounds, lead compounds, cobalt compounds, zinc compounds and the like. Among these, iron-based compounds and tin-based compounds are preferable in terms of reaction rate and pot life of the pressure-sensitive adhesive layer.

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

Examples of tin-based compounds include dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin maleate, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin sulfide, tributyltin methoxyde, tributyltin acetate, and triethyltinethoxydo. Examples thereof include tributyltin ethoxydo, dioctyltin oxide, dioctyltin dilaurate, tributyltin chloride, tributyltin trichloroacetate, tin 2-ethylhexanoate and the like.

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

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

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

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, 1,8-diazabisik mouth- (5,4,5) -undecene-7 and the like.

The amount of the catalyst is preferably 0.005% by weight to 1.00% by weight, more preferably 0.01% by weight to 0.75% by weight, still more preferably 0.01% by weight, based on the polyol. % To 0.50% by weight, particularly preferably 0.01% by weight to 0.20% by weight. When the amount of the catalyst is within the above range, it is difficult to easily peel off from the adherend, and typically, it is attached to the exposed surface of the optical member or the electronic member during the manufacturing process of the optical member or the electronic member. It is possible to provide a surface protective film that is less likely to be peeled off later and can be easily peeled off if peeling is required.

The composition containing the polyol and the polyfunctional isocyanate compound may contain any suitable other components as long as the effects of the present invention are not impaired. Examples of such other components include antioxidants, ultraviolet absorbers, light stabilizers, resin components, tackifiers, crosslink retardants, inorganic fillers, organic fillers, metal powders, pigments, and foil-like substances. , Softeners, anti-aging agents, conductive agents, surface lubricants, leveling agents, corrosion inhibitors, heat-stabilizing agents, polymerization inhibitors, lubricants, solvents and the like.

Among these other components, it is a preferable embodiment to include a deterioration inhibitor such as an antioxidant, an ultraviolet absorber, and a light stabilizer. By including the deterioration inhibitor in the pressure-sensitive adhesive composition, adhesive residue is prevented from remaining on the adherend even if the formed pressure-sensitive adhesive layer is attached to the adherend and then stored in a heated state. It can be excellent in sex. The deterioration inhibitor may be only one kind or two or more kinds. As the deterioration inhibitor, an antioxidant is particularly preferable.

Examples of the antioxidant include a radical chain inhibitor and a peroxide decomposing agent.

Examples of the radical chain inhibitor include phenolic antioxidants and amine-based antioxidants.

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

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

Examples of the monophenolic antioxidant include 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-4-ethylphenol, and stear-β- ( 3,5-Di-t-butyl-4-hydroxyphenyl) propionate and the like can be mentioned.

Examples of the bisphenol-based antioxidant include 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2,2'-methylenebis (4-ethyl-6-t-butylphenol), and 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 and the like can be mentioned.

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) propionate] methane , Bis [3,3'-bis- (4'-hydroxy-3'-t-butylphenyl) butyl acid] glycol ester, 1,3,5-tris (3', 5'-di-t-butyl) -4'-Hydroxybenzyl) -S-triazine-2,4,6- (1H, 3H, 5H) trione, tocophenol and the like can be mentioned.

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

Examples of the phosphorus-based antioxidant include triphenylphosphine, diphenylisodecylphosphite, phenyldiisodecylphosphite and the like.

Examples of the ultraviolet absorber include benzophenone-based ultraviolet absorbers, benzotriazole-based ultraviolet absorbers, salicylic acid-based ultraviolet absorbers, oxalic acid anilide-based ultraviolet absorbers, cyanoacrylate-based ultraviolet absorbers, and triazine-based ultraviolet absorbers. Be done.

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

Examples of the benzotriazole-based ultraviolet absorber include 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-5'-tert-butylphenyl) benzotriazole, 2- ( 2'-Hydroxy-3', 5'-di-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2 -(2'-Hydroxy-3', 5'-di-tert-butylphenyl) 5-chlorobenzotriazole, 2- (2'-hydroxy-3', 5'-di-tert-amylphenyl) benzotriazole, 2- (2'-Hydroxy-4'-octoxyphenyl) benzotriazole, 2- [2'-hydroxy-3'-(3 ", 4", 5 ", 6",-tetrahydrophthalimidemethyl ) -5'-Methylphenyl] benzotriazole, 2,2'methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazole-2-yl) phenol], 2- (2'-Hydroxy-5'-metaacryloxyphenyl) -2H-benzotriazole and the like can be mentioned.

Examples of the salicylic acid-based ultraviolet absorber include phenylsalicylate, p-tert-butylphenylsalicylate, and p-octylphenylsalicylate.

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

Examples of the light stabilizer include a hindered amine-based light stabilizer and an ultraviolet stabilizer.

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

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

[A-1-2-2. Urethane-based resin formed from a composition containing a urethane prepolymer and a polyfunctional isocyanate compound]
The polyfunctional isocyanate compound may be only one kind or two or more kinds.

As the polyfunctional isocyanate compound, any suitable polyfunctional isocyanate compound that can be used in the urethanization reaction can be adopted. Examples of such a polyfunctional isocyanate compound include the “polyfunctional isocyanate compound” described in Section A-1-2.

The composition containing the urethane prepolymer and the polyfunctional isocyanate compound may contain any suitable other components as long as the effects of the present invention are not impaired. Examples of such other components include antioxidants, ultraviolet absorbers, light stabilizers, resin components, tackifiers, crosslink retardants, inorganic fillers, organic fillers, metal powders, pigments, and foil-like substances. , Softeners, anti-aging agents, conductive agents, surface lubricants, leveling agents, corrosion inhibitors, heat-stabilizing agents, polymerization inhibitors, lubricants, solvents and the like.

Among these other components, it is a preferable embodiment to include a deterioration inhibitor such as an antioxidant, an ultraviolet absorber, and a light stabilizer. By including the deterioration inhibitor in the pressure-sensitive adhesive composition, adhesive residue is prevented from remaining on the adherend even if the formed pressure-sensitive adhesive layer is attached to the adherend and then stored in a heated state. It can be excellent in sex. The deterioration inhibitor may be only one kind or two or more kinds. As the deterioration inhibitor, an antioxidant is particularly preferable. For details of antioxidants, UV absorbers and light stabilizers, the description in Section A-1-2-1 may be incorporated.

The equivalent ratio of NCO group to OH group in the urethane prepolymer and the polyfunctional isocyanate compound is preferably 5.0 or less, more preferably 0.01 to 3.0, and further preferably 0.01 to 3.0 as the NCO group / OH group. It is preferably 0.02 to 2.0, more preferably 0.03 to 2.0, still more preferably 0.03 to 1.9, and particularly preferably 0.05 to 1.9. , 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 easily peel off from the adherend, and typically, the optical member or the electronic member is exposed during the manufacturing process of the optical member or the electronic member. It is possible to provide a surface protective film that is less likely to be peeled off after being attached to the surface and can be easily peeled off if peeling is required. Further, if the equivalent ratio of NCO group / OH group is within the above range, haze can be reduced. In particular, if the haze can be reduced to 3% or less, the inspectability of the surface protective film according to the embodiment of the present invention will be further improved.

The content ratio of the polyfunctional isocyanate compound is preferably 0.01% by weight to 30% by weight, more preferably 0.05% by weight to 25% by weight, based on the urethane prepolymer. , More preferably 0.1% by weight to 25% by weight, further preferably 0.5% by weight to 25% by weight, still more preferably 0.5% by weight to 23% by weight, and particularly preferably 1 It is from% to 23% by weight, most preferably from 1% to 21% by weight. When the content ratio of the polyfunctional isocyanate compound is within the above range, it is difficult to easily peel off from the adherend, and typically, during the manufacturing process of the optical member or the electronic member, the exposed surface of the optical member or the electronic member. It is possible to provide a surface protective film that is less likely to be peeled off after being attached to the surface and can be easily peeled off if peeling is required. Further, if the content ratio of the polyfunctional isocyanate compound is within the above range, haze can be reduced. In particular, if the haze can be reduced to 3% or less, the inspectability of the surface protective film according to the embodiment of the present invention will be further improved.

<A-1--3. Ionic compounds>
As the ionic compound, any suitable ionic compound can be adopted as long as the effects of the present invention are not impaired. Such an ionic compound is preferably an ionic liquid, and more preferably an ionic liquid containing a fluoroorganic anion. By containing both an ionic compound and a fluorine-based compound described later in addition to the base polymer, the pressure-sensitive adhesive composition is typically processed, assembled, inspected, and processed in the manufacturing process of an optical member or an electronic member. A surface protective film containing an adhesive layer, which is attached to an exposed surface of the optical member or the electronic member to prevent scratches on the surface of the optical member or the electronic member during transportation, and is peeled off. It is possible to provide a surface protective film that sufficiently suppresses the band voltage and does not damage the optical member or the electronic member at the time of peeling.

The ionic compound may be only one kind or two or more kinds.

The ionic liquid means a molten salt (ionic compound) that exhibits a liquid at 25 ° C.

As the ionic liquid, any suitable ionic liquid can be adopted as long as the effects of the present invention are not impaired. Such an ionic liquid is preferably an ionic liquid containing a fluoroorganic anion, and more preferably an ionic liquid composed of a fluoroorganic anion and an onium cation. By adopting 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, Surface protection including an adhesive layer, which is attached to the exposed surface of the optical member or the electronic member to prevent scratches on the surface of the optical member or the electronic member during processing, assembly, inspection, transportation, etc. It is possible to provide a surface protective film which is a film and which suppresses the peeling band voltage more sufficiently and does not further damage the optical member and the electronic member at the time of peeling.

As the onium cation that can form an ionic liquid, any suitable onium cation can be adopted as long as the effect of the present invention is not impaired. 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 and using them in combination with a fluorine-based compound described later, the optical member is typically used in the manufacturing process of an optical member or an electronic member during processing, assembly, inspection, transportation, or the like. A surface protective film containing an adhesive layer, which is attached to the optical member or the exposed surface of the electronic member to prevent scratches on the surface of the electronic member, and more sufficiently suppresses the peeling band voltage. It is possible to provide a surface protective film that does not further damage the optical member or the electronic member at the time of peeling.

The onium cation that can form an ionic liquid is preferably at least one selected from cations having structures represented by the general formulas (1) to (5).

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

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

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

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

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

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

Specific examples of the cation represented by the general formula (1) include 1-ethylpyridinium cation, 1-butylpyridinium cation, 1-hexylpyridinium cation, 1-ethyl-3-methylpyridinium cation, and 1-butyl. -3-Methylpyridinium cation, 1-hexyl-3-methylpyridinium cation, 1-butyl-4-methylpyridinium cation, 1-octyl-4-methylpyridinium cation, 1-butyl-3,4-dimethylpyridinium cation, Pyridinium cations such as 1,1-dimethylpyrrolidinium cation; 1-ethyl-1-methylpyrrolidinium cation, 1-methyl-1-propylpyrrolidinium cation, 1-methyl-1-butylpyrrolidinium cation, 1-Methyl-1-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-butylpyrrolidinium cation, 1,1-dibutylpyrrolidinium cation and other pyrrolidinium cations; 1-propylpiperidinium cation, 1-pentylpi Peridinium 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-propyl-1-butylpiperidinium cation, Piperidinium cations such as 1,1-dimethylpiperidinium cation, 1,1-dipropylpiperidinium cation, 1,1-dibutylpiperidinium cation; 2-methyl-1-pyrrolinium cation; 1-d Examples thereof include tyl-2-phenylindole cation; 1,2-dimethylindole cation; 1-ethylcarbazole cation; and the like.

Among these, 1-ethylpyridinium cation, 1-butylpyridinium cation, 1-hexylpyridinium cation, 1-ethyl-3-methylpyridinium cation, 1 -Pyridinium cations such as butyl-3-methylpyridinium cation, 1-hexyl-3-methylpyridinium cation, 1-butyl-4-methylpyridinium cation, 1-octyl-4-methylpyridinium cation; 1-ethyl-1- Methylpyrrolidinium cation, 1-methyl-1-propylpyrrolidinium cation, 1-methyl-1-butylpyrrolidinium cation, 1-methyl-1-pentylpyrrolidinium cation, 1-methyl-1-hexyl Pyrrolidinium cation, 1-methyl-1-heptylpyrrolidinium cation, 1-ethyl-1-propylpyrrolidinium cation, 1-ethyl-1-butylpyrrolidinium cation, 1-ethyl-1-pentylpyrrolidi Pyrrolidinium cations such as nium cation, 1-ethyl-1-hexylpyrrolidinium cation, 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-1-pentylpiperidinium cation, 1-ethyl-1- Hexylpiperidinium cations, 1-ethyl-1-heptylpiperidinium cations, piperidinium cations such as 1-propyl-1-butylpiperidinium cations; and the like; more preferably 1-hexyl. Pyridinium cation, 1-ethyl-3-methylpyridinium cation, 1-butyl-3-methylpyridinium cation, 1-octyl-4-methylpyridinium cation, 1-methyl-1-propylpyrrolidinium cation, 1-methyl-1 -A 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 1,3-dimethylimidazolium cation, 1,3-diethylimidazolium cation, 1-ethyl-3-methylimidazolium cation, and 1-butyl. -3-Methylimidazolium cation, 1-hexyl-3-methylimidazolium cation, 1-octyl-3-methylimidazolium cation, 1-decyl-3-methylimidazolium cation, 1-dodecyl-3-methylimidazolium cation Rium cation, 1-tetradecyl-3-methylimidazolium cation, 1,2-dimethyl-3-propylimidazolium cation, 1-ethyl-2,3-dimethylimidazolium cation, 1-butyl-2,3-dimethylimidazolium cation Imidazolium cations such as lithium cations, 1-hexyl-2,3-dimethylimidazolium cations; 1,3-dimethyl-1,4,5,6-tetrahydropyrimidinium cations, 1,2,3-trimethyl- 1,4,5,6-tetrahydropyrimidinium cation, 1,2,3,4-tetramethyl-1,4,5,6-tetrahydropyrimidinium cation, 1,2,3,5-tetramethyl- Tetrahydropyrimidinium cations such as 1,4,5,6-tetrahydropyrimidinium cations; 1,3-dimethyl-1,4-dihydropyrimidinium cations, 1,3-dimethyl-1,6-dihydropyrimidi Nium cation, 1,2,3-trimethyl-1,4-dihydropyrimidinium cation, 1,2,3-trimethyl-1,6-dihydropyrimidinium cation, 1,2,3,4-tetramethyl- Dihydropyrimidinium cations such as 1,4-dihydropyrimidinium cation, 1,2,3,4-tetramethyl-1,6-dihydropyrimidinium cation; and the like.

Among these, 1,3-dimethylimidazolium cation, 1,3-diethylimidazolium cation, 1-ethyl-3-methylimidazolium cation, 1-ethyl-3-methylimidazolium cation are preferable in that the effect of the present invention can be further exhibited. −Butyl-3-methylimidazolium cation, 1-hexyl-3-methylimidazolium cation, 1-octyl-3-methylimidazolium cation, 1-decyl-3-methylimidazolium cation, 1-dodecyl-3- It is an imidazolium cation such as methyl imidazolium cation, 1-tetradecyl-3-methyl imidazolium cation, more preferably 1-ethyl-3-methyl imidazolium cation, 1-hexyl-3-methyl imidazolium cation. is there.

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

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

Examples of the cation represented by the general formula (4) include a tetraalkylammonium cation, a trialkylsulfonium cation, a tetraalkylphosphonium cation, and a part of the above alkyl group is replaced with an alkenyl group, an alkoxyl group, or an epoxy group. Examples include those that have been used.

Specific examples of the cation represented by the general formula (4) include tetramethylammonium cation, tetraethylammonium cation, tetrabutylammonium cation, tetrapentylammonium cation, tetrahexylammonium cation, tetraheptylammonium cation, and triethylmethylammonium. Cation, tributylethylammonium cation, trimethylpropylammonium cation, trimethyldecylammonium cation, N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium cation, glycidyltrimethylammonium cation, trimethylsulfonium cation, triethylsulfonium cation , Tributylsulfonium cation, trihexylsulfonium cation, diethylmethylsulfonium cation, dibutylethylsulfonium cation, dimethyldecylsulfonium cation, tetramethylphosphonium cation, tetraethylphosphonium cation, tetrabutylphosphonium cation, tetrahexylphosphonium cation, tetraoctylphosphonium cation, triethyl Examples thereof include methylphosphonium cations, tributylethylphosphonium cations, trimethyldecylphosphonium cations and diallyldimethylammonium cations.

Among these, triethylmethylammonium cation, tributylethylammonium cation, trimethyldecylammonium cation, diethylmethylsulfonium cation, dibutylethylsulfonium cation, dimethyldecylsulfonium cation, are preferable in that the effect of the present invention can be further exhibited. Asymmetric tetraalkylammonary cations such as triethylmethylphosphonium cations, tributylethylphosphonium cations, and trimethyldecylphosphonium cations, trialkylsulfonium cations, tetraalkylphosphonium cations, and N, N-diethyl-N-methyl-N- (2-methoxy). Ethyl) ammonium cation, glycidyl trimethyl ammonium cation, diallyl dimethyl ammonium cation, N, N-dimethyl-N-ethyl-N-propyl ammonium cation, N, N-dimethyl-N-ethyl-N-butyl ammonium cation, N, N -Dimethyl-N-ethyl-N-pentylammonary ammonium cation, N, N-dimethyl-N-ethyl-N-hexylammonary cation, N, N-dimethyl-N-ethyl-N-heptylammonary ammonium cation, N, N-dimethyl -N-ethyl-N-nonylammonium cation, N, N-dimethyl-N, N-dipropylammonary cation, N, N-diethyl-N-propyl-N-butylammonary cation, N, N-dimethyl-N- Propyl-N-pentyl ammonium cation, N, N-dimethyl-N-propyl-N-hexyl ammonium cation, N, N-dimethyl-N-propyl-N-heptyl ammonium 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-propylammonary cation, N, N-diethyl-N-methyl-N-pentylammonary cation, N, N-diethyl-N-methyl-N -Heptylammonium cation, N, N-diethyl-N-propyl-N-pentylammonium cation, triethylpropylammonium cation, triethylpentylammonium Cations, triethylheptylammonium cations, N, N-dipropyl-N-methyl-N-ethylammonary cations, N, N-dipropyl-N-methyl-N-pentylammonary cations, N, N-dipropyl-N-butyl-N -Hexylammonium cation, N, N-dipropyl-N, N-dihexylammonium cation, N, N-dibutyl-N-methyl-N-pentylammonary cation, N, N-dibutyl-N-methyl-N-hexylammonium cation , Trioctylmethylammonium cation, N-methyl-N-ethyl-N-propyl-N-pentylammonium cation and the like, more preferably trimethylpropylammonium cation.

As the fluoroorganic anion that can form an ionic liquid, any suitable fluoroorganic anion can be adopted as long as the effects of the present invention are not impaired. Such fluoroorganic anions may be completely fluorinated (perfluoro) or partially fluorinated.

Examples of such fluoroorganic anions include fluorinated arylsulfonates, perfluoroalkanesulfonates, bis (fluorosulfonyl) imides, bis (perfluoroalkanesulfonyl) imides, cyanoperfluoroalkanesulfonylamides, and bis (cyano). Perfluoroalkanesulfonylmethides, cyano-bis- (perfluoroalkanesulfonyl) methides, tris (perfluoroalkanesulfonyl) methides, trifluoroacetates, perfluoroalkanes, tris (perfluoroalkanesulfonyl) methides, (perfluoroalkanes) Sulfonyl) Trifluoroacetamide and the like.

Among these fluoroorganic anions, perfluoroalkyl sulfonate, bis (fluorosulfonyl) imide, and bis (perfluoroalkanesulfonyl) imide are more preferable, and more specifically, for example, trifluoromethanesulfonate and pentafluoroethane. They are sulfonate, heptafluoropropane sulfonate, nonaflate butane sulfonate, bis (fluorosulfonyl) imide, and bis (trifluoromethanesulfonyl) imide.

As a specific example of the ionic liquid, it can be appropriately selected and used from the combination of the above-mentioned cationic component and the above-mentioned anionic component. Specific examples of such an ionic liquid include 1-hexylpyridinium bis (fluorosulfonyl) imide, 1-ethyl-3-methylpyridinium trifluoromethanesulfonate, 1-ethyl-3-methylpyridinium pentafluoroethanesulfonate, and the like. 1-Ethyl-3-methylpyridinium heptafluoropropanesulfonate, 1-ethyl-3-methylpyridinium nonafluorobutane sulfonate, 1-butyl-3-methylpyridinium trifluoromethanesulfonate, 1-butyl-3-methylpyridinium bis (trifluoromethane) Sulfonyl) imide, 1-butyl-3-methylpyridinium bis (pentafluoroethanesulfonyl) imide, 1-octyl-4-methylpyridinium bis (fluorosulfonyl) imide, 1,1-dimethylpyrrolidinium bis (trifluoromethanesulfonyl) Imide, 1-methyl-1-ethylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-propylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-propylpyrrolidinium bis (1-methyl-1-propylpyrrolidinium bis) Fluorosulfonyl) imide, 1-methyl-1-butylpyrrolidiniumbis (trifluoromethanesulfonyl) imide, 1-methyl-1-pentylpyrrolidiniumbis (trifluoromethanesulfonyl) imide, 1-methyl-1-hexylpyrroli Diniumbis (trifluoromethanesulfonyl) imide, 1-methyl-1-heptylpyrrolidiniumbis (trifluoromethanesulfonyl) imide, 1-ethyl-1-propylpyrrolidiniumbis (trifluoromethanesulfonyl) imide, 1-ethyl -1-butylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-ethyl-1-pentylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-ethyl-1-hexylpyrrolidinium bis (trifluoromethanesulfonyl) Imide, 1-ethyl-1-heptylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1,1-dipropylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-propyl-1-butylpyrrolidinium bis (1-propyl-1-butylpyrrolidinium bis) Trifluoromethanesulfonyl) imide, 1,1-dibutylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-propyl piperidinium bis (trifluoromethanesul) Honyl) imide, 1-pentylpiperidinium bis (trifluoromethanesulfonyl) imide, 1,1-dimethylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-ethylpiperidinium bis (trifluoromethanesulfonyl) Imide, 1-methyl-1-propyl piperidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-propyl piperidinium bis (fluorosulfonyl) imide, 1-methyl-1-butyl piperidinium bis (trifluo) Lomethanesulfonyl) imide, 1-methyl-1-pentylpiperidiniumbis (trifluoromethanesulfonyl) imide, 1-methyl-1-hexylpiperidiniumbis (trifluoromethanesulfonyl) imide, 1-methyl-1-hepti Lupiperidinium bis (trifluoromethanesulfonyl) imide, 1-ethyl-1-propylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-ethyl-1-butylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-ethyl -1-Pentylpiperidiniumbis (trifluoromethanesulfonyl) imide, 1-ethyl-1-hexylpiperidiniumbis (trifluoromethanesulfonyl) imide, 1-ethyl-1-heptylpiperidiniumbis (trifluoromethanesulfonyl) imide ) Imide, 1,1-dipropyl piperidinium bis (trifluoromethanesulfonyl) imide, 1-propyl-1-butyl piperidinium bis (trifluoromethanesulfonyl) imide, 1,1-dibutyl piperidinium bis (trifluoromethane) Sulfonyl) imide, 1,1-dimethylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-ethylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-propylpyrrolidinium Bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-butylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-pentylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl -1-hexylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-heptylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-propylpyrrolidinium bis (penta) Fluoroetan Sulfonyl) imide, 1-ethyl-1-butylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-pentylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-hexyl Pyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-heptylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1,1-dipropylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-propyl-1-butylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1,1-dibutylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-propylpiperidinium bis (pentafluoroethanesulfonyl) imide , 1-Pentylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1,1-dimethylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-ethylpiperidinium bis (pentafluoroethanesulfonyl) Imide, 1-methyl-1-propylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-butylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-pentylpiperidinium Bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-hexylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-heptylpiperidiniumbis (pentafluoroethanesulfonyl) imide, 1 -Ethyl-1-propylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-butylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-pentylpiperidinium bis (penta) Fluoroethanesulfonyl) imide, 1-ethyl-1-hexylpiperidiniumbis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-heptylpiperidiniumbis (pentafluoroethanesulfonyl) imide, 1,1- Dipropylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-propyl-1-butylpiperidiniumbis (pentafluoroethanesulfonyl) imide, 1,1-dibutylpiperidiniumbis (pentafluoroethanesulfonyl) imide, 1-Ethyl-3-methylimidazoli Umtrifluoroacetate, 1-ethyl-3-methylimidazolium heptafluorobutyrate, 1-ethyl-3-methylimidazolium trifluoromethanesulfonate, 1-ethyl-3-methylimidazolium heptafluoropropanesulfonate, 1-ethyl- 3-Methyl imidazolium nonafluorobutane sulfonate, 1-ethyl-3-methyl imidazolium bis (trifluoromethanesulfonyl) imide, 1-ethyl-3-methyl imidazolium bis (fluorosulfonyl) imide, 1-ethyl-3-methyl Imidazolium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-3-methylimidazolium tris (trifluoromethanesulfonyl) methide, 1-butyl-3-methylimidazolium trifluoroacetate, 1-butyl-3-methylimidazolium Heptafluorobutyrate, 1-butyl-3-methylimidazolium trifluoromethanesulfonate, 1-butyl-3-methylimidazolium perfluorobutane sulfonate, 1-butyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide, 1 −Hexyl-3-methylimidazolium trifluoromethanesulfonate, 1-hexyl-3-methylimidazolium bis (fluorosulfonyl) imide, 1,2-dimethyl-3-propylimidazolium bis (trifluoromethanesulfonyl) imide, 1- Ethyl-2,3,5-trimethylpyrazolium bis (trifluoromethanesulfonyl) imide, 1-propyl-2,3,5-trimethylpyrazolium bis (trifluoromethanesulfonyl) imide, 1-butyl-2,3 5-trimethylpyrazolium bis (trifluoromethanesulfonyl) imide, 1-ethyl-2,3,5-trimethylpyrazolium bis (pentafluoroethanesulfonyl) imide, 1-propyl-2,3,5-trimethylpyrazo Riumbis (pentafluoroethanesulfonyl) imide, 1-butyl-2,3,5-trimethylpyrazolium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-2,3,5-trimethylpyrazolium (trifluoromethane) Sulfonyl) trifluoroacetamide, 1-propyl-2,3,5-trimethylpyrazolium (trifluoromethanesulfonyl) trifluoroacetamide, 1-butyl-2,3,5-trimethylpyrazolium (trifluoro) Methansulfonyl) trifluoroacetamide, trimethylpropylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-ethyl-N-propylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-ethyl- N-butylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-ethyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-ethyl-N-hexyl ammonium bis ( Trifluoromethanesulfonyl) imide, N, N-dimethyl-N-ethyl-N-heptyl ammoniumbis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-ethyl-N-nonylammonyl bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N, N-dipropylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-propyl-N-butylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N -Propyl-N-pentylammonyl bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-propyl-N-hexyl ammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-propyl-N-heptyl Ammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-butyl-N-hexyl ammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-butyl-N-heptyl ammonium bis (trifluoromethanesulfonyl) ) Imide, N, N-dimethyl-N-pentyl-N-hexyl ammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N, N-dihexyl ammonium bis (trifluoromethanesulfonyl) imide, trimethylheptyl ammonium bis (trifluoromethanesulfonyl) Trifluoromethanesulfonyl) imide, N, N-diethyl-N-methyl-N-propylammonium bis (trifluoromethanesulfonyl) imide, N, N-diethyl-N-methyl-N-pentylammonyl bis (trifluoromethanesulfonyl) imide, N, N-diethyl-N-methyl-N, N-heptylammonium bis (trifluoromethanesulfonyl) imide, N, N-diethyl-N-propyl-N-pentyluan Moniumbis (trifluoromethanesulfonyl) imide, triethylpropylammonbis (trifluoromethanesulfonyl) imide, triethylpentylammonbis (trifluoromethanesulfonyl) imide, triethylheptylammoniumbis (trifluoromethanesulfonyl) imide, N, N-dipropyl-N-methyl -N-Ethylammonium bis (trifluoromethanesulfonyl) imide, N, N-dipropyl-N-methyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, N, N-dipropyl-N-butyl-N-hexyl ammonium bis (Trifluoromethanesulfonyl) imide, N, N-dipropyl-N, N-dihexyl ammonium bis (trifluoromethanesulfonyl) imide, N, N-dibutyl-N-methyl-N-pentyl ammonium bis (trifluoromethanesulfonyl) imide, N , N-dibutyl-N-methyl-N-hexylammonium bis (trifluoromethanesulfonyl) imide, trioctylmethylammonium bis (trifluoromethanesulfonyl) imide, N-methyl-N-ethyl-N-propyl-N-pentylammonium Bis (trifluoromethanesulfonyl) imide, 1-butylpyridinium (trifluoromethanesulfonyl) trifluoroacetamide, 1-butyl-3-methylpyridinium (trifluoromethanesulfonyl) trifluoroacetamide, 1-ethyl-3-methylimidazolium (trifluoromethane) Sulfonyl) trifluoroacetamide, tetrahexylammonium bis (trifluoromethanesulfonyl) imide, diallyldimethylammonium trifluoromethanesulfonate, diallyldimethylammonium bis (trifluoromethanesulfonyl) imide, diallyldimethylammonium bis (pentafluoroethanesulfonyl) imide, N, N -Diethyl-N-methyl-N- (2-methoxyethyl) ammonium trifluoromethanesulfonate, N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium bis (trifluoromethanesulfonyl) imide, N, N -Diethyl-N-methyl-N- (2-methoxyethyl) ammonium bis (pentafluoroethanesulfonyl) imide, glycidyltrimethylammonium trifluoromethanesulfonate, glycidyltrimethylammo Niumbis (trifluoromethanesulfonyl) imide, glycidyltrimethylammonium bis (pentafluoroethanesulfonyl) imide, diallyldimethylammonium bis (trifluoromethanesulfonyl) imide, diallyldimethylbis (pentafluoroethanesulfonyl) imide, lithium bis (trifluoromethanesulfonyl) Examples thereof include imide and lithium bis (fluorosulfonyl) imide.

Among these ionic liquids, more preferably 1-hexylpyridinium bis (fluorosulfonyl) imide, 1-ethyl-3-methylpyridinium trifluoromethanesulfonate, 1-ethyl-3-methylpyridinium pentafluoroethanesulfonate, 1- Ethyl-3-methylpyridinium heptafluoropropanesulfonate, 1-ethyl-3-methylpyridinium nonafluorobutane sulfonate, 1-butyl-3-methylpyridinium trifluoromethanesulfonate, 1-butyl-3-methylpyridinium bis (trifluoromethanesulfonyl) Imide, 1-octyl-4-methylpyridinium bis (fluorosulfonyl) imide, 1-methyl-1-propylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-propylpyrrolidinium bis (fluorosulfonyl) Imide, 1-methyl-1-propylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-propylpiperidinium bis (fluorosulfonyl) imide, 1-ethyl-3-methylimidazolium trifluoromethanesulfonate, 1-Ethyl-3-methylimidazolium heptafluoropropanesulfonate, 1-ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide, 1-ethyl-3-methylimidazolium bis (fluorosulfonyl) imide, 1-hexyl -3-Methylimidazolium bis (fluorosulfonyl) imide, trimethylpropylammonium bis (trifluoromethanesulfonyl) imide, lithium bis (trifluoromethanesulfonyl) imide, lithium bis (fluorosulfonyl) imide.

As the ionic liquid, a commercially available one may be used, but it can also be synthesized as described below. The method for synthesizing an ionic liquid is not particularly limited as long as the desired ionic liquid can be obtained, but in general, the document "Ionic liquid-the forefront and future of development-" (CMC Publishing Co., Ltd.) The halide method, hydroxide method, acid ester method, complex formation method, neutralization method and the like as described in (Issued) are used.

The halide method, hydroxide method, acid ester method, complex formation method, and neutralization method are shown below by taking a nitrogen-containing onium salt as an example, but other sulfur-containing onium salts and phosphorus-containing onium salts are shown below. Other ionic liquids such as, etc. can also be obtained by the same method.

The halide method is a method carried out by a reaction as shown in the reaction formulas (1) to (3). First, a halide is obtained by reacting a tertiary amine with an alkyl halide (reaction formula (1), chlorine, bromine, or iodine is used as the halogen).

An acid (HA) or salt (MA, M is ammonium, lithium, sodium, potassium, etc.) having ^{an anion structure (A −} ) of an ionic liquid intended for the obtained halide, and a cation forming a salt with the desired anion. ) is reacted with an objective ionic liquid (R 4 _NA) is obtained.

The hydroxide method is a method carried out by a reaction as shown in the reaction formulas (4) to (8). First halide _(R 4 NX) ion-exchange membrane method electrolysis (reaction equation (4)), OH-type ion exchange resin method (reaction equation (5)) or silver oxide _(Ag 2 O) and of the reaction (reaction formula ( In 6)), a hydroxide (R ₄ NOH) is obtained (chlorine, bromine, and iodine are used as halogens).

By using the reaction of reaction formula as above halogenation process (7) - (8) The obtained hydroxide, the ionic liquid (R 4 _NA) to obtain the objective.

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

By using the reaction of as above halogenation process reaction formulas (10) to (11) The obtained ester product, the ionic liquid (R 4 _NA) to obtain the objective. Further, a direct ionic liquid can be obtained by using methyltrifluoromethanesulfonate, methyltrifluoroacetate or the like as the acid ester.

The neutralization method is a method performed by a reaction as shown in the reaction formula (12). Reacting tertiary amines with organic acids 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} Can be obtained by

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

<A-1-4. Fluorine compounds>
As the fluorine-based compound, any suitable fluorine-based compound can be adopted as long as the effects of the present invention are not impaired. When the pressure-sensitive adhesive composition contains both a fluorine-based compound and the above-mentioned ionic compound in addition to the base polymer, it is typically processed, assembled, inspected, and processed in the manufacturing process of an optical member or an electronic member. A surface protective film containing an adhesive layer, which is attached to an exposed surface of the optical member or the electronic member to prevent scratches on the surface of the optical member or the electronic member during transportation, and is peeled off. It is possible to provide a surface protective film that sufficiently suppresses the band voltage and does not damage the optical member or the electronic member at the time of peeling.

The fluorine-based compound may be only one kind or two or more kinds.

Examples of the fluorine-based compound include at least one selected from a fluorine-containing compound, a hydroxyl group-containing fluorine-based compound, and a crosslinkable functional group-containing fluorine-based compound.

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 fluoroC1-C10 alkanes such as fluoromethane, fluoroethane, fluoropropane, fluoroisopropane, fluorobutane, fluoroisobutane, fluorot-butane, fluoropentane, and fluorohexane. Be done.

A preferred embodiment of the fluorine-containing compound is an oligomer having a fluorine-containing group and a hydrophilic group and / or a lipophilic group (“specific fluorine-based compound”). By including (combining) both the ionic compound and the above-mentioned "specific fluorine-based compound", the effect of the present invention can be remarkably exhibited. As described above, this is done by allowing an ionic compound capable of exhibiting an antistatic effect to coexist with a fluorine-based compound (preferably a specific fluorine-based compound) in the pressure-sensitive adhesive composition, thereby causing the fluorine-based compound (preferably). It is presumed that the ionic compound is unevenly distributed on the surface side (the side to be bonded to the adherend) of the pressure-sensitive adhesive layer due to the synergistic effect with the specific fluorine-based compound). Typical examples of the fluorine-containing group include a fluorine-containing alkyl group (for example, CF _3-, etc.) and / or a fluorine-containing alkylene group (for example, -CF _{2- CF 2-,} etc.). A hydrophilic group is a group having hydrophilicity, and hydrophilicity is a property generally known to those skilled in the art as having a translation of "hydrophilic" in English and "affinity with water". (For example, see McGraw-Hill Science and Technology Glossary (Revised 3rd Edition, Nikkan Kogyo Shimbun). A lipophilic group is a group having lipophilicity, and lipophilicity is a property generally known to those skilled in the art as having "lipophilic" in English and "affinity with oil". (See, for example, McGraw-Hill Science and Technology Glossary (Revised 3rd Edition, Nikkan Kogyo Shimbun)).

The "specific fluorine-based compound" is more preferably an oligomer containing a fluorine-containing group, a hydrophilic group, and a lipophilic group in that the effects of the present invention can be more exhibited. If the "specific fluorine-based compound" does not contain a hydrophilic group or the "specific fluorine-based compound" does not contain a lipophilic group, the effects of the present invention may not be sufficiently exhibited.

A preferred embodiment of the fluorine-containing compound is fluorine having a surface tension of 26.0 mN / m to 27.0 mN / m when a 0.1% toluene solution is used, in that the effects of the present invention can be more exhibited. It is a contained compound (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 an extremely narrow specific range of 26.0 mN / m to 27.0 mN / m, the effect of the present invention is more exhibited. In particular, it is possible to exhibit a remarkable and unexpected effect that both the peeling zone voltage against glass and the peeling zone voltage against resin can be sufficiently suppressed. In particular, assuming an application to be attached to an exposed surface of an optical member or an electronic member, which is a planned application of the surface protective film in a preferred embodiment of the present invention, the peeling band voltage against the glass is also against the resin. It is extremely important that the effect that the peeling band voltage of the above can be sufficiently suppressed can be exhibited.

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. In a 0.1% toluene solution. It is 0 mN / m (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. In a 0.1% toluene solution. If it is 0 mN / m (the surface tension of toluene is 27.9 mN / m), the effect of the present invention can be further exhibited. It can exhibit a very noticeable and unexpected effect that it can be sufficiently suppressed. In particular, assuming an application to be attached to an exposed surface of an optical member or an electronic member, which is a planned application of the surface protective film in a preferred embodiment of the present invention, the peeling band voltage against the glass is also against the resin. It is extremely important that the effect that the peeling band voltage of the above can be suppressed extremely sufficiently can be exhibited.

Examples of commercially available fluorine-containing compounds include the following.

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

Surflon series manufactured by AGC Seimi Chemical Co., Ltd .:
Representatively, "S-242", "S-243", "S-386" and the like.

FC series manufactured by Sumitomo 3M Ltd .:
Representatively, "FC-4430", "FC-4432" and the like.

Futergent series made by Neos Co., Ltd .:
Typical examples are "Futagent 100", "Futagent 100C", "Futagent 110", "Futagent 150", "Futagent 150CH", "Futagent 250", "Futagent 400SW" and the like.

PF series manufactured by Kitamura Chemical Industry 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 the hydroxyl group-containing fluoropolymer, for example, a conventionally known resin can be used. For example, International Publication No. 94/06870 Pamphlet, JP-A-8-12921, JP-A-10-72569, JP-A-4-275379 Examples thereof include hydroxyl group-containing fluororesins described in Japanese Patent Publication No. 97/11130 Pamphlet, International Publication No. 96/26254 Pamphlet and the like. Examples of other hydroxyl group-containing fluororesins include fluoroolefins described in JP-A-8-231919, JP-A-10-265731, JP-A-10-204374, and JP-A-8-12922. Examples include polymers. Other examples include a copolymer of a compound having an alkyl group fluorinated in a hydroxyl group, a fluorine-containing organic compound in which a fluorine-containing compound is copolymerized with a hydroxyl group, and a fluorine-containing compound containing a hydroxyl group-containing organic compound. Examples of commercially available products such as hydroxyl group-containing fluorine compounds include the trade name "Lumiflon" (manufactured by Asahi Glass Co., Ltd.), the trade name "Cefral Coat" (manufactured by Central Glass Co., Ltd.), and the trade name "Zaflon". (Manufactured by Toagosei Co., Ltd.), trade name "Zefle" (manufactured by Daikin Industries, Ltd.), etc. can be 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 and a compound having a fluorinated alkyl group in the crosslinkable functional group-containing compound. Examples thereof include a polymer, a fluorine-containing organic compound obtained by copolymerizing a fluorine-containing compound with a crosslinkable functional group-containing compound, and a fluorine-containing compound containing a crosslinkable functional group-containing compound. As such a crosslinkable functional group-containing fluorine-based compound, commercially available products include, for example, trade names "Mega Fvck F-570", "Mega Fvck RS-55", "Mega Fvck RS-56", "Mega Fvck". RS-72-K ”,“ Mega Fvck RS-75 ”,“ Mega Fvck RS-76-E ”,“ Mega Fvck RS-76-NS ”,“ Mega Fvck RS-78 ”,“ Mega Fvck RS-90 ” (Manufactured by DIC Co., Ltd.) and the like.

Among the fluorine-containing compounds available as commercially available products, those corresponding to the above-mentioned "oligomers having a fluorine-containing group and a hydrophilic group and / or a lipophilic group" are typically DIC Co., Ltd. Made of
"Megafuck F-477" (fluorine-containing group / hydrophilic group / lipophilic group-containing oligomer, surface tension in the case of 0.1% toluene solution = 26.4 mN / m),
"Megafuck F-551-A" (fluorine-containing group / lipophilic group-containing oligomer, surface tension in the case of 0.1% toluene solution = 25.6 mN / m),
"Megafuck 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),
"Megafuck F-554" (fluorine-containing group / lipophilic group-containing oligomer, surface tension in the case of 0.1% toluene solution = 25.0 mN / m),
"Megafuck F-555-A" (fluorine-containing group / hydrophilic group / lipophilic group-containing oligomer, surface tension in 0.1% toluene solution = 20.4 mN / m),
"Megafuck 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),
"Megafuck 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),
"Megafuck F-563" (fluorine-containing group / lipophilic group-containing oligomer, surface tension in the case of 0.1% toluene solution = 20.2 mN / m),
"Megafuck F-569" (fluorine-containing group / hydrophilic group-containing oligomer, surface tension in the case of 0.1% toluene solution = 19.7 mN / m),
And so on.

Among the fluorine-containing compounds available as commercially available products, the above-mentioned "oligoform containing a fluorine-containing group, a hydrophilic group and a lipophilic group, which has a surface tension of 26.0 mN when made into a 0.1% toluene solution". As a compound corresponding to "a fluorine-containing compound having a surface tension of 27.9 mN / m of toluene having a surface tension of 27.9 mN / m / m to 27.0 mN / m", a representative product of DIC Co., Ltd.
"Megafuck F-477" (fluorine-containing group / hydrophilic group / lipophilic group-containing oligomer, surface tension in the case of 0.1% toluene solution = 26.4 mN / m),
"Megafuck 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),
"Megafuck 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),
"Megafuck 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 so on.

<A-1-5. Other ingredients>
The pressure-sensitive adhesive composition may contain any suitable other ingredients as long as the effects of the present invention are not impaired. Examples of such other components include resin components, cross-linking accelerators, cross-linking catalysts, silane coupling agents, silicone-based additives such as modified silicone oils, tackifying resins (rosin derivatives, polyterpene resins, petroleum resins, oils). (Soluble phenol, etc.), anti-aging agents, inorganic fillers, organic fillers, metal powders, colorants (pigments, dyes, etc.), foils, UV absorbers, antioxidants, light stabilizers, chain transfer agents, plasticizers Examples thereof include agents, softeners, conductive agents, stabilizers, surface lubricants, corrosion inhibitors, heat-resistant stabilizers, polymerization inhibitors, lubricants, solvents, catalysts and the like.

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

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

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

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

Examples of the polyether-modified silicone oil include side-chain type polyether-modified silicone oil and both-terminal type polyether-modified silicone oil. Among these, the double-ended type polyether-modified silicone oil is preferable in that the effect of the antistatic property can be sufficiently and more effectively exhibited.

≪A-2. Base layer ≫
The base material layer may be only one layer or two or more layers. The base material layer may be a stretched one.

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

For the purpose of forming a wound body that can be easily rewound on the surface of the base material layer to which the pressure-sensitive adhesive layer is not attached, for example, fatty acid amide, polyethyleneimine, and a long-chain alkyl-based additive are added to the base material layer. Etc. can be added to perform the mold release treatment, or a coat layer made of any suitable release agent such as silicone-based, long-chain alkyl-based, and fluorine-based can be provided.

As the material of the base material, any suitable material may be adopted depending on the application. For example, plastic, paper, metal film, non-woven fabric and the like can be mentioned. Preferably, it is plastic. That is, the base material layer is preferably a plastic film. The base material layer may be composed of one kind of material, or may be made of two or more kinds of materials. For example, it may be composed of two or more kinds of plastics.

Examples of the plastic include polyester-based resin, polyamide-based resin, and polyolefin-based resin. Examples of the polyester-based resin include polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate. Examples of the polyolefin-based resin include homopolymers of olefin monomers and copolymers of olefin monomers. Specific examples of the polyolefin-based resin include homopolypropylene; a block-based, random-based, and graft-based propylene-based copolymer containing an ethylene component as a copolymer; a reactor TPO; low density, high density, and linear. Low-density, ultra-low-density, etc. ethylene-based copolymers; ethylene / propylene copolymer, ethylene / vinyl acetate copolymer, ethylene / methyl acrylate copolymer, ethylene / ethyl acrylate copolymer, ethylene / acrylic acid Examples thereof include butyl copolymers, ethylene / methacrylic acid copolymers, ethylene-based copolymers such as ethylene / methyl methacrylate copolymers; and the like.

The substrate layer may contain any suitable additives, if desired. Examples of additives that can be contained in the base material layer include antioxidants, ultraviolet absorbers, light stabilizers, antistatic agents, fillers, pigments and the like. The type, number, and amount of additives that can be contained in the base material layer can be appropriately set according to the purpose. In particular, when the material of the base material layer is plastic, it is preferable to contain some of the above additives for the purpose of preventing deterioration and the like. From the viewpoint of improving weather resistance and the like, the additives are particularly preferably antioxidants, ultraviolet absorbers, light stabilizers and fillers.

As the antioxidant, any suitable antioxidant may be employed. Examples of such antioxidants include phenol-based antioxidants, phosphorus-based processing heat stabilizers, lactone-based processing heat stabilizers, sulfur-based heat-resistant stabilizers, phenol-phosphorus-based antioxidants, and the like. The content ratio of the antioxidant is preferably 1% by weight or less, more preferably 1% by weight or less, based on the base resin of the base material layer (when the base material layer is a blend, the blend is the base resin). It is 0.5% by weight or less, more preferably 0.01% by weight to 0.2% by weight.

As the ultraviolet absorber, any suitable ultraviolet absorber may be adopted. Examples of such an ultraviolet absorber include a benzotriazole-based ultraviolet absorber, a triazine-based ultraviolet absorber, and a benzophenone-based ultraviolet absorber. The content ratio of the ultraviolet absorber is preferably 2% by weight or less with respect to the base resin forming the base material layer (when the base material layer is a blended product, the blended product is the base resin), and more. It is preferably 1% by weight or less, and more preferably 0.01% by weight to 0.5% by weight.

As the light stabilizer, any suitable light stabilizer can be adopted. Examples of such a light stabilizer include a hindered amine-based light stabilizer and a benzoate-based light stabilizer. The content ratio of the light stabilizer is preferably 2% by weight or less with respect to the base resin forming the base material layer (when the base material layer is a blended product, the blended product is the base resin), and more. It is preferably 1% by weight or less, and more preferably 0.01% by weight to 0.5% by weight.

As the filler, any suitable filler may be adopted. Examples of such a filler include an inorganic filler and the like. Specific examples of the inorganic filler include carbon black, titanium oxide, zinc oxide and the like. The content ratio of the filler is preferably 20% by weight or less, more preferably 20% by weight or less, based on the base resin forming the base material layer (when the base material layer is a blend, the blend is the base resin). Is 10% by weight or less, more preferably 0.01% by weight to 10% by weight.

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

≪≪ B. Applications ≫≫
The surface protective film according to the embodiment of the present invention typically prevents scratches on the surface of the optical member or the electronic member during processing, assembly, inspection, transportation, etc. in the manufacturing process of the optical member or the electronic member. A surface protective film containing an adhesive layer, which is attached to the exposed surface of the optical member or the electronic member for the purpose of sufficiently suppressing the peeling band voltage, and the optical member or the electronic member is pressed at the time of peeling. The effect of not being damaged can be exhibited. Therefore, it can be suitably used for surface protection of optical members and electronic members. The optical member of the present invention is the one to which the surface protective film of the present invention is attached. The electronic member of the present invention is the one to which the surface protective film of the present invention is attached.

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples. The tests and evaluation methods in the examples and the like are as follows. In addition, when it is described as "part", it means "part by weight" unless there is a special note, and when it is described as "%", it means "% by weight" unless there is a special note.

<Measurement of surface free energy for diiodomethane on the surface of the adhesive layer>
The surface protective film from which the separator has been peeled off is cut into a size of 50 mm in width and 100 mm in length, and fixed to a contact angle meter (manufactured by Kyowa Interface Science Co., Ltd., model "CA-X") with the surface of the adhesive layer facing up. 2.0 μL of water was dropped on the surface of the pressure-sensitive adhesive layer, and the contact angle was measured. Next, in the same procedure, 2.0 μL of diiodomethane was added dropwise and the contact angle was measured. From the values of the contact angles of the above two liquids, the surface free energy of the surface of the pressure-sensitive adhesive layer with respect to diiodomethane was calculated using the Owns-Wendt method.

<Measurement of peeling force from the glass plate (after leaving at a temperature of 23 ° C for 30 minutes)>
The adhesive layer side of the surface protective film (width 25 mm x length 140 mm) from which the separator has been peeled off is attached to a glass plate (soda lime glass, manufactured by Matsunami Glass Ind. Co., Ltd.) with a 2 kg hand roller once and again, and the environment is 23 ° C. It was left at a temperature for 30 minutes.
The evaluation sample obtained as described above was measured with a tensile tester. As the tensile tester, a trade name "Autograph AG-Xplus HS 6000 mm / min high-speed model (AG-50NX plus)" manufactured by Shimadzu Corporation was used. The evaluation sample was set in the tensile tester, and the tensile test was started. Specifically, the load when the surface protective film was peeled from the glass plate was measured, and the average load at that time was taken as the peeling force of the surface protective film from the glass plate. The conditions of the tensile test were a test environment temperature: 23 ° C., a peeling angle: 180 degrees, and a peeling speed (tensile speed): 300 mm / min.

<Measurement of glass peeling withstand voltage and acrylic plate peeling band voltage>
Cut the surface protective film from which the separator has been peeled off to a size of 70 mm in width and 100 mm in length, and put it on the surface of glass (soda lime glass, manufactured by Matsunami Glass Ind.) Or acrylic plate (Acrylite, manufactured by Mitsubishi Chemical Co., Ltd.). The surface protective film was pressure-bonded with a hand roller so that one end of the surface protective film protruded 30 mm from the edge of the glass.
This sample was left in an environment of 23 ° C. × 50% RH for 1 day, and then set in a predetermined position on a sample fixing table having a height of 20 mm. The end of the surface protective film protruding 30 mm from the glass was fixed to an automatic winder and peeled so as to have a peeling angle of 150 ° and a peeling speed of 30 m / min. The potential on the surface of the adherend generated at this time is measured by a potential measuring instrument (manufactured by Shishido Electrostatic Co., Ltd., model "STATIRON DZ-4") fixed at a height of 30 mm from the center of the adherend. , Glass peeling band voltage or acrylic plate peeling band voltage. The measurement was performed in an environment of 23 ° C. and 50% RH.

<Measurement of residual adhesive force against glass>
A surface protective film was attached to the entire surface of a glass plate (made by Matsunami Glass, 1.35 mm x 10 cm x 10 cm) with a hand roller, and stored for 24 hours in an atmosphere of a temperature of 23 ° C. and a humidity of 55% RH. The surface protective film was peeled off at a speed of 3 m / min, and the No. 19 mm width was cut into a length of 150 mm. A 31B tape (manufactured by Nitto Denko Corporation, substrate thickness: 25 μm) was attached by one reciprocating 2.0 kg roller in an atmosphere of a temperature of 23 ° C. and a humidity of 55% RH. After curing for 30 minutes in an atmosphere with a temperature of 23 ° C and a humidity of 55% RH, a tensile tester (trade name "Autograph AG-Xplus HS 6000 mm / min high-speed model (AG-50NX plus)" manufactured by Shimadzu Corporation) Was peeled off at a peeling angle of 180 degrees and a tensile speed of 300 mm / min, and the adhesive strength was measured.
Similarly, for a glass plate that has not been subjected to the above treatment, a 19 mm wide No. The adhesive strength of the 31B tape was measured, and the residual adhesive ratio was calculated by the following formula.
Residual adhesive ratio (%) = (No. 31B adhesive force to the glass plate after peeling the surface protective film / No. 31B adhesive force to the glass plate) × 100
This residual adhesive ratio to glass is an index of how much the pressure-sensitive adhesive component of the surface protective film is transferred to the surface of the adherend and contaminated. The higher the value of the residual adhesive ratio to glass, the higher the risk of contaminating the adherend. The lower the value of the residual adhesive ratio to glass, the higher the risk of contaminating the adherend. Is a low surface protection film.

<Measurement of haze>
The adhesive solution obtained in the following Examples and Comparative Examples was applied to the peeled surface of a polyester film (trade name: Diafoil MRF75, manufactured by Mitsubishi Chemical Corporation) having a thickness of 75 μm, one side of which was peeled with silicone. A pressure-sensitive adhesive layer was prepared by coating and drying under the conditions described in Examples and Comparative Examples. Next, a polyester film (trade name: Diafoil MRE75, manufactured by Mitsubishi Chemical Co., Ltd.) having a thickness of 75 μm, one side of which has been peeled off with silicone, is applied to the surface of the pressure-sensitive adhesive layer, and the peel-treated side of the film is on the pressure-sensitive adhesive layer side. The film was coated in this manner and aged at room temperature for 5 days. Two sheets of 50 mm × 50 mm thick paper with a hole of 20 mm × 20 mm were prepared, and one sample was attached to one of them with one reciprocating hand roller, and then the other was attached. The evaluation sample obtained as described above was measured with "HM-150N" manufactured by Murakami Color Technology Research Institute.

<Explanation of Fluorine-Containing Compounds Used in Examples and Comparative Examples>
The fluorine-containing compounds used in Examples and Comparative Examples are as follows.
"Megafuck F-477" (manufactured by DIC Co., Ltd., fluorine-containing group / hydrophilic group / lipophilic group-containing oligomer, surface tension in 0.1% toluene solution = 26.4 mN / m),
"Megafuck F-551-A" (manufactured by DIC Corporation, fluorine-containing group / lipophilic group-containing oligomer, surface tension in the case of 0.1% toluene solution = 25.6 mN / m),
"Megafuck F-553" (manufactured by DIC Co., Ltd., fluorine-containing group / hydrophilic group / lipophilic group-containing oligomer, surface tension in 0.1% toluene solution = 26.4 mN / m),
"Megafuck F-554" (manufactured by DIC Corporation, fluorine-containing group / lipophilic group-containing oligomer, surface tension in the case of 0.1% toluene solution = 25.0 mN / m),
"Megafuck F-555-A" (manufactured by DIC Co., Ltd., fluorine-containing group / hydrophilic group / lipophilic group-containing oligomer, surface tension in 0.1% toluene solution = 20.4 mN / m),
"Megafuck F-557" (manufactured by DIC Co., Ltd., fluorine-containing group / hydrophilic group / lipophilic group-containing oligomer, surface tension in 0.1% toluene solution = 26.3 mN / m),
"Megafuck F-559" (manufactured by DIC Co., Ltd., fluorine-containing group / hydrophilic group / lipophilic group-containing oligomer, surface tension in 0.1% toluene solution = 26.1 mN / m),
"Megafuck F-563" (manufactured by DIC Corporation, fluorine-containing group / lipophilic group-containing oligomer, surface tension in the case of 0.1% toluene solution = 20.2 mN / m),
"Megafuck F-569" (manufactured by DIC Corporation, fluorine-containing group / hydrophilic group-containing oligomer, surface tension in the case of 0.1% toluene solution = 19.7 mN / m),

[Example 1]
As a polyol, 85 parts by weight of Preminol S3011 (Mn = 10000, manufactured by Asahi Glass Co., Ltd.), which is a polyol having three hydroxyl groups, and Sanniks GP3000 (Mn = 3000, manufactured by Sanyo Kasei Co., Ltd.), which is a polyol having three hydroxyl groups, 13 By weight, 2 parts by weight of Sanniks GP1000 (Mn = 1000, manufactured by Sanyo Kasei Co., Ltd.), which is a polyol having three hydroxyl groups, and 18 parts by weight of an isocyanate compound (Coronate HX: C / HX, manufactured by Nippon Polyurethane Co., Ltd.) as a cross-linking agent. As a catalyst, 0.02 parts by weight of Nasem ferrous iron (manufactured by Nippon Kagaku Sangyo Co., Ltd.), 1 part by weight of megafuck F-553 (manufactured by DIC) of a fluorine-based oligomer, 1-ethyl-3-methyl as an ionic compound. 1 part by weight of imidazolium tri (fluoromethanesulfonyl) imide (AS110, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was diluted with ethyl acetate so that the total solid content was 35% by weight to obtain a urethane-based pressure-sensitive adhesive solution. Then, the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 μm, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 20 μm, and the drying temperature is 130 ° C. , The drying time was 2 minutes, and the mixture was cured and dried. Next, the surface of the obtained pressure-sensitive adhesive layer was treated with silicone on one surface of a release sheet made of a polyester resin having a thickness of 25 μm (trade name “MRF25”, thickness 25 μm, manufactured by Mitsubishi Chemical Corporation). The surfaces were bonded together to obtain a surface protective film (1). Aging was performed at room temperature for 5 days for evaluation. The release sheet was peeled off immediately before the 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, and the pressure-sensitive adhesive composition was carried out. An adhesive layer made of (2) was prepared to obtain a surface protective film (2). 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, and the pressure-sensitive adhesive composition (3). ) Was prepared to obtain a surface protective film (3). 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 the pressure-sensitive adhesive composition was carried out. An adhesive layer made of (4) was prepared to obtain a surface protective film (4). The results are shown in Table 1.

[Example 5]
As shown in Table 1, 0.25 parts by weight of a fluorine-based oligomer (trade name "F-553", manufactured by DIC) in terms of solid content, and an ionic compound (trade name "AS110, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 0. The same procedure as in Example 1 was carried out except that the weight was changed to 5 parts by weight, a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition (5) was prepared, and a surface protective film (5) was obtained. The results are shown in Table 1. ..

[Example 6]
As shown in Table 1, 0.25 parts by weight of a fluorine-based oligomer (trade name "F-553", manufactured by DIC) in terms of solid content, and an ionic compound (trade name "AS110, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 0. The same procedure as in Example 1 was carried out except that the weight was changed to 25 parts by weight, a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition (6) was prepared, and a surface protective film (6) was obtained. The results are shown in Table 1. ..

[Example 7]
As shown in Table 1, the same procedure as in Example 1 was carried out except that the fluorine-based oligomer (trade name “F-555-A”, manufactured by DIC) was changed to 0.25 parts by weight in terms of solid content, and the pressure-sensitive adhesive was applied. An adhesive layer made of the composition (7) was prepared to obtain a surface protective film (7). 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 the pressure-sensitive adhesive composition was carried out. An adhesive layer made of (8) was prepared to obtain a surface protective film (8). 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, and the pressure-sensitive adhesive composition (9) was carried out. ) Was prepared to obtain a surface protective film (9). 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, and the pressure-sensitive adhesive composition was carried out. An adhesive layer made of (10) was prepared to obtain a surface protective film (10). 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 the pressure-sensitive adhesive composition was carried out. An adhesive layer made of (11) was prepared to obtain a surface protective film (11). 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, and the pressure-sensitive adhesive composition was carried out. An adhesive layer made of (12) was prepared to obtain a surface protective film (12). The results are shown in Table 1.

[Example 13]
As shown in Table 1, 0.25 parts by weight of a fluorine-based oligomer (trade name "F-477", manufactured by DIC) in terms of solid content, and an ionic compound (trade name "AS110, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 0. The same procedure as in Example 1 was carried out except that the weight was changed to 5 parts by weight, a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition (13) was prepared, and a surface protective film (13) was obtained. The results are shown in Table 1. ..

[Example 14]
As shown in Table 1, 0.25 parts by weight of a fluorine-based oligomer (trade name "F-477", manufactured by DIC) in terms of solid content, and an ionic compound (trade name "AS110, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 0. The same procedure as in Example 1 was carried out except that the weight was changed to 25 parts by weight, a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition (14) was prepared, and a surface protective 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 composition was carried out. An adhesive layer made of (15) was prepared to obtain a surface protective 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, and the pressure-sensitive adhesive composition was carried out. An adhesive layer made of (16) was prepared to obtain a surface protective film (16). 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 was applied. A pressure-sensitive adhesive layer made of the composition (17) was prepared to obtain a surface protective film (17). 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, and the pressure-sensitive adhesive composition was carried out. An adhesive layer made of (18) was prepared to obtain a surface protective film (18). 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, and the pressure-sensitive adhesive composition was carried out. An adhesive layer made of (19) was prepared to obtain a surface protective film (19). 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, and the pressure-sensitive adhesive composition was carried out. An adhesive layer made of (20) was prepared to obtain a surface protective film (20). 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 the pressure-sensitive adhesive composition was carried out. An adhesive layer made of (21) was prepared to obtain a surface protective film (21). 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, and the pressure-sensitive adhesive composition was carried out. An adhesive layer made of (22) was prepared to obtain a surface protective film (22). 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, and the pressure-sensitive adhesive composition was carried out. An adhesive layer made of (23) was prepared to obtain a surface protective film (23). 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, and the pressure-sensitive adhesive composition was carried out. An adhesive layer made of (24) was prepared to obtain a surface protective film (24). 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, and the pressure-sensitive adhesive composition was carried out. An adhesive layer made of (25) was prepared to obtain a surface protective film (25). 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, and the pressure-sensitive adhesive composition was carried out. An adhesive layer made of (26) was prepared to obtain a surface protective film (26). 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 Industry Co., Ltd.) was changed to 15.9 parts by weight in terms of solid content, and the pressure-sensitive adhesive composition was carried out. An adhesive layer made of (27) was prepared to obtain a surface protective film (27). 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 Industry Co., Ltd.) was changed to 14.1 parts by weight in terms of solid content, and the pressure-sensitive adhesive composition was carried out. An adhesive layer made of (28) was prepared to obtain a surface protective film (28). 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 Industry Co., Ltd.) was changed to 12.4 parts by weight in terms of solid content, and the pressure-sensitive adhesive composition was carried out. An adhesive layer made of (29) was prepared to obtain a surface protective film (29). 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 Industry Co., Ltd.) was changed to 10.6 parts by weight in terms of solid content, and the pressure-sensitive adhesive composition was carried out. An adhesive layer made of (30) was prepared to obtain a surface protective film (30). 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 Industry Co., Ltd.) was changed to 8.8 parts by weight in terms of solid content, and the pressure-sensitive adhesive composition was carried out. An adhesive layer made of (31) was prepared to obtain a surface protective film (31). 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 Industry Co., Ltd.) was changed to 15.9 parts by weight in terms of solid content, and the pressure-sensitive adhesive composition was carried out. An adhesive layer made of (32) was prepared to obtain a surface protective film (32). 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 Industry Co., Ltd.) was changed to 14.1 parts by weight in terms of solid content, and the pressure-sensitive adhesive composition was carried out. An adhesive layer made of (33) was prepared to obtain a surface protective film (33). 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 Industry Co., Ltd.) was changed to 12.4 parts by weight in terms of solid content, and the pressure-sensitive adhesive composition was carried out. An adhesive layer made of (34) was prepared to obtain a surface protective film (34). 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 Industry Co., Ltd.) was changed to 10.6 parts by weight in terms of solid content, and the pressure-sensitive adhesive composition was carried out. An adhesive layer made of (35) was prepared to obtain a surface protective film (35). 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 Industry Co., Ltd.) was changed to 8.8 parts by weight in terms of solid content, and the pressure-sensitive adhesive composition was carried out. An adhesive layer made of (36) was prepared to obtain a surface protective film (36). 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, and the pressure-sensitive adhesive composition was carried out. An adhesive layer made of (37) was prepared to obtain a surface protective film (37). 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 Industry Co., Ltd.) was changed to 15.9 parts by weight in terms of solid content, and the pressure-sensitive adhesive composition was carried out. An adhesive layer made of (38) was prepared to obtain a surface protective film (38). 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 Industry Co., Ltd.) was changed to 14.1 parts by weight in terms of solid content, and the pressure-sensitive adhesive composition was carried out. An adhesive layer made of (39) was prepared to obtain a surface protective film (39). 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 Industry Co., Ltd.) was changed to 12.4 parts by weight in terms of solid content, and the pressure-sensitive adhesive composition was carried out. An adhesive layer made of (40) was prepared to obtain a surface protective film (40). 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 Industry Co., Ltd.) was changed to 10.6 parts by weight in terms of solid content, and the pressure-sensitive adhesive composition was carried out. An adhesive layer made of (41) was prepared to obtain a surface protective film (41). 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 Industry Co., Ltd.) was changed to 8.8 parts by weight in terms of solid content, and the pressure-sensitive adhesive composition was carried out. An adhesive layer made of (42) was prepared to obtain a surface protective film (42). 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 Industry Co., Ltd.) was changed to 15.9 parts by weight in terms of solid content, and the pressure-sensitive adhesive composition was carried out. An adhesive layer made of (43) was prepared to obtain a surface protective film (43). 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 Industry Co., Ltd.) was changed to 14.1 parts by weight in terms of solid content, and the pressure-sensitive adhesive composition was carried out. An adhesive layer made of (44) was prepared to obtain a surface protective film (44). 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 Industry Co., Ltd.) was changed to 12.4 parts by weight in terms of solid content, and the pressure-sensitive adhesive composition was carried out. An adhesive layer made of (45) was prepared to obtain a surface protective film (45). 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 Industry Co., Ltd.) was changed to 10.6 parts by weight in terms of solid content, and the pressure-sensitive adhesive composition was carried out. An adhesive layer made of (46) was prepared to obtain a surface protective film (46). 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 Industry Co., Ltd.) was changed to 8.8 parts by weight in terms of solid content, and the pressure-sensitive adhesive composition was carried out. An adhesive layer made of (47) was prepared to obtain a surface protective film (47). The results are shown in Table 1.

[Example 48]
100 parts by weight of urethane prepolymer A, 3 parts by weight of isocyanate compound (Coronate HX: C / HX, manufactured by Nippon Polyurethane Co., Ltd.) as a cross-linking agent, 0.5 parts by weight of Irganox1010 (manufactured by BASF) as an antioxidant, and a fluorine-based oligomer. Megafuck F-553 (manufactured by DIC) 1 part by weight, 1-ethyl-3-methylimidazolium tri (fluoromethanesulfonyl) imide (AS110, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) as an ionic compound, 1 part by weight of the whole It was diluted with ethyl acetate so that the solid content was 49% by weight to obtain a urethane-based pressure-sensitive adhesive solution. Then, the urethane adhesive solution is applied to a base material made of polyester resin (trade name "T100-75S", thickness 75 μm, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying is 75 μm, and the drying temperature is 120 ° C. , Cure and dry under the condition of drying time of 3 minutes to prepare a pressure-sensitive adhesive layer composed of the pressure-sensitive adhesive composition (48). Next, the surface of the obtained pressure-sensitive adhesive layer was treated with silicone on one surface of a release sheet made of a polyester resin having a thickness of 25 μm (trade name “MRF25”, thickness 25 μm, manufactured by Mitsubishi Chemical Corporation). The surfaces were bonded together to obtain a surface protective film (48). Aging was performed at room temperature for 5 days for evaluation. The release sheet was peeled off immediately before the 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 part by weight in terms of solid content, and the pressure-sensitive adhesive composition was carried out. An adhesive layer made of (49) was prepared to obtain a surface protective film (49). 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 part by weight in terms of solid content, and the pressure-sensitive adhesive composition was carried out. An adhesive layer made of (50) was prepared to obtain a surface protective film (50). 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 part by weight in terms of solid content, and the pressure-sensitive adhesive composition was carried out. An adhesive layer made of (51) was prepared to obtain a surface protective film (51). The results are shown in Table 1.

[Comparative Example 1]
As shown in Table 1, a fluorine-based oligomer (trade name "F-569", manufactured by DIC) is used in an amount of 0.25 parts by weight in terms of solid content, and an ionic compound (trade name "AS110, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) is used. A pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition (C1) was prepared in the same manner as in Example 1 except that the surface protective film (C1) was obtained. The results are shown in Table 1.

[Comparative Example 2]
As shown in Table 1, a fluorine-based oligomer (trade name "F-553", manufactured by DIC) is used in an amount of 0.25 parts by weight in terms of solid content, and an ionic compound (trade name "AS110, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) is used. A pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition (C2) was prepared in the same manner as in Example 1 except that the surface protective film (C2) was obtained. The results are shown in Table 1.

[Comparative Example 3]
As shown in Table 1, a fluorine-based oligomer (trade name "F-477", manufactured by DIC) is used in an amount of 0.25 parts by weight in terms of solid content, and an ionic compound (trade name "AS110, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) is used. A pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition (C3) was prepared in the same manner as in Example 1 except that the surface protective 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 a fluorine-based oligomer (trade name "F-551-A", manufactured by DIC) in terms of solid content, and an ionic compound (trade name "AS110, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)" In the same manner as in Example 1, a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition (C4) was prepared to obtain a surface protective film (C4). 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, and the pressure-sensitive adhesive composition was carried out. An adhesive layer made of (C5) was prepared to obtain a surface protective film (C5). 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, and the pressure-sensitive adhesive composition was carried out. An adhesive layer made of (C6) was prepared to obtain a surface protective film (C6). The results are shown in Table 1.

[Comparative Example 7]
As shown in Table 1, a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition (C7) was prepared in the same manner as in Example 1 except that a fluorine-based oligomer was not used, and a surface protective 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 an ionic compound (trade name "AS110, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) was not used" without using a fluorine-based oligomer, and the pressure-sensitive adhesive composition (C8) was used. A pressure-sensitive adhesive layer made of the above was prepared to obtain a surface protective film (C8). 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 the fluorine-based oligomer was not used and the ionic compound (trade name “AS110, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) was not used), and the pressure-sensitive adhesive composition (C9) was used. A pressure-sensitive adhesive layer made of the above was prepared to obtain a surface protective film (C9). 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 an ionic compound (trade name "AS110, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) was not used" without using a fluorine-based oligomer, and the pressure-sensitive adhesive composition (C10) was used. A pressure-sensitive adhesive layer made of the above was prepared to obtain a surface protective film (C10). 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, and the pressure-sensitive adhesive composition (C11) was carried out. ) Was prepared to obtain a surface protective film (C11). The results are shown in Table 1.

[Examples 52 to 103]
For each of the surface protective films (1) to (51) obtained in Examples 1 to 51, the separator was peeled off, and the pressure-sensitive adhesive layer side was a polarizing plate (manufactured by Nitto Denko KK, trade name) which is an optical member. TEG1465DUHC ") was attached to obtain an optical member to which a surface protective film was attached.

[Examples 104 to 155]
For each of the surface protective films (1) to (51) obtained in Examples 1 to 51, the separator was peeled off, and the adhesive layer side was a conductive film (manufactured by Nitto Denko KK, trade name) which is an electronic member. It was attached to "Electrica V270L-TFMP") to obtain an electronic member to which a surface protective film was attached.

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

1 Base material layer 2 Adhesive layer 10 Surface protective film

Claims (7)

A surface protective film containing an adhesive layer,
The pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer is formed from the pressure-sensitive adhesive composition.
The pressure-sensitive adhesive composition comprises a base polymer, a polyfunctional isocyanate, an ionic compound, and a fluorine-based compound.
The base polymer is at least one selected from polyols and urethane prepolymers.
The equivalent ratio of NCO group to OH group in the polyol and the polyfunctional isocyanate compound is 1.8 or less.
Haze is 3% or less,
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 .
Surface protective film. The surface protective 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 protective 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 protective film according to any one of claims 1 to 3, wherein the content ratio of the polyfunctional isocyanate compound to the polyol is 16% by weight or less. The adhesive layer contained in the surface protective film is attached to a glass plate and left at a temperature of 23 ° C. for 30 minutes, and then the surface protective film is peeled from the glass plate at a peeling angle of 180 degrees and a peeling speed of 300 mm / at a temperature of 23 ° C. The surface protective film according to any one of claims 1 to 4, wherein the peeling force when peeled off in minutes is 0.005 N / 25 mm to 0.1 N / 25 mm. An optical member to which the surface protective film according to any one of claims 1 to 5 is attached. An electronic member to which the surface protective film according to any one of claims 1 to 5 is attached.

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