TWI756887B - surface protection film - Google Patents

Abstract

The present invention provides a surface protection film which sufficiently suppresses peeling electrostatic voltage and does not damage the optical member or the electronic member during peeling. The surface protection film is typically a surface protection film containing an adhesive layer, which is In the manufacturing steps of the optical member or the 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., it is attached to the exposed surface of the optical member or the electronic member. The surface protection film of the embodiment of the present invention includes an adhesive layer, and the adhesive constituting the adhesive layer is formed of an adhesive composition, and the adhesive composition includes a base polymer, an ionic compound and a fluorine-based compound, The surface free energy of the surface of the adhesive layer to diiodomethane is 6 mJ/m ² to 30 mJ/m ² .

Description

surface protection film

The present invention relates to a surface protection film.

In the manufacturing steps of optical components or electronic components, in order to prevent the surface of the optical component or the electronic component from being damaged during processing, assembly, inspection, transportation, etc., the surface is usually attached to the exposed surface of the optical component or the electronic component. protective film. When surface protection is no longer necessary, such a surface protection film is peeled off from an optical member or an electronic member (Patent Document 1).

Generally, surface protection films and optical members or electronic members have high electrical insulating properties, and static electricity is generated due to friction or peeling. Therefore, static electricity is easily generated even when the surface protective film is peeled off from an optical member or an electronic member. In such a case, for example, if a voltage is applied to the liquid crystal in a state where static electricity remains, the alignment loss of the liquid crystal molecules will occur, or a panel defect will occur. In addition, the presence of static electricity can also be a factor that attracts dust or reduces workability.

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

In addition, in order to impart antistatic properties to the adhesive layer itself constituting the surface protective film, a method has been adopted in which the adhesive layer contains an alkali metal salt or an ionic compound such as an ionic liquid that functions as an antistatic agent, and transfers to the adherend (Patent Document 4).

[Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2016-17109

[Patent Document 2] Japanese Patent Laid-Open No. 2004-223923

[Patent Document 3] Japanese Patent Laid-Open No. 2008-255332

[Patent Document 4] Japanese Patent Laid-Open No. 9-165460

An object of the present invention is to provide a surface protection film that sufficiently suppresses peeling electrostatic voltage and does not damage the optical member or the electronic member during peeling, typically a surface protection film containing an adhesive layer , which is attached to the exposed surface of the optical component or the electronic component in order to prevent the surface of the optical component or the electronic component from being damaged during processing, assembly, inspection, transportation, etc. during the manufacturing steps of the optical component or electronic component .

The surface protection film of the embodiment of the present invention includes an adhesive layer, and the adhesive constituting the adhesive layer is formed of an adhesive composition, and the adhesive composition includes a base polymer, an ionic compound and a fluorine-based compound, The surface free energy of the surface of the adhesive layer to diiodomethane is 6mJ/m ² -30mJ/m ² .

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

In one embodiment, the content ratio of the 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 the group consisting of polyols, urethane prepolymers, acrylic resins, rubber-based resins, and silicone-based resins.

In one embodiment, the above-mentioned adhesive layer included in the above-mentioned surface protection film is attached to a glass plate, and placed at a temperature of 23° C. for 30 minutes, and then the surface protection film is held at a temperature of 23° C. at a peeling angle of 180 degrees and The peeling speed was 300 mm/min from the glass plate, and the peeling force at this time was 0.005 N/25 mm to 0.1 N/25 mm.

The optical member which concerns on embodiment of this invention sticks the said surface protection film.

The electronic component which concerns on embodiment of this invention is what was bonded with the said surface protection film.

According to the present invention, it is possible to provide a method that sufficiently suppresses the peeling electrostatic voltage without causing the peeling The surface protection film of the optical member or the electronic member is damaged, and the surface protection film is typically a surface protection film containing an adhesive layer. In the manufacturing process of the optical member or the electronic member, in order to prevent the optical member or the The surface of the electronic component is damaged during processing, assembly, inspection, transportation, etc., and is attached to the exposed surface of the optical component or the electronic component.

1: substrate layer

2: Adhesive layer

10: Surface protection film

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

≪≪A.Surface protection film≫≫

The surface protective film of the embodiment of the present invention includes an adhesive layer.

The surface protective film only needs to include an adhesive layer, and may include any appropriate other members within a range that does not impair the effects of the present invention. Typically, the surface protective film of the present invention includes a substrate layer and an adhesive layer.

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

In FIG. 1, any suitable release liner (sometimes also called release sheet or separator) (not shown) can be provided on the surface of the adhesive layer 2 opposite to the base material layer 1 for use protected before. As a release liner, for example, a table of substrates (liner substrates) such as paper and plastic films can be mentioned. Silicone-treated release liner on the surface, release liner obtained by laminating the surface of a substrate (liner substrate) such as paper or plastic film with a polyolefin-based resin, etc.

Examples of the plastic film used as the backing base material include polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, and vinyl chloride copolymer. Film, polyethylene terephthalate film, polybutylene terephthalate film, polyurethane film, ethylene-vinyl acetate copolymer film, etc.

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, 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, particularly preferably 20 μm to 300 μm.

The surface free energy of the adhesive layer included in the surface protection film to the diiodomethane is 6mJ/m ² ~30mJ/m ² , more preferably 8mJ/m ² ~30mJ/m ² , and more preferably 10mJ/m ² ~30mJ/m ² , preferably 12mJ/m ² ~30mJ/m ² . If the surface free energy of the adhesive layer contained in the surface protection film to diiodomethane is within the above-mentioned range, it is possible to provide a product that can sufficiently suppress the peeling electrostatic voltage without causing the adherend (representatively, Optical components or electronic components) damaged surface protective film. If the surface free energy with respect to diiodomethane of the adhesive layer contained in the surface protection film deviates from the above-mentioned range and is too low, there is a possibility that the peeling electrostatic voltage cannot be sufficiently suppressed. If the surface free energy to diiodomethane of the adhesive layer included in the surface protection film deviates from the above range and is too high, there is a risk of contamination of the adherend.

Furthermore, the surface free energy of the adhesive layer included in the surface protection film with respect to diiodomethane can be easily measured as described below, by designing the adhesive layer in such a way that the surface free energy is within the above-specified range, It is possible to provide a surface protection film that sufficiently suppresses peeling electrostatic voltage and does not damage an adherend (typically, an optical member or an electronic member) during peeling. Here, with the above-mentioned adhesive layer as a design point, typically in the present invention, there is an option to use an ionic compound, a fluorine-based compound, and a fluorine compound in combination. In addition, the selection of the fluorine compound includes, for example, selecting a fluorine compound whose surface free energy is within the predetermined range from among the fluorine compounds in a specific category. Such a selection can be carried out without excessive trial and error by the industry. .

As for the adhesive layer included in the surface protection film, after sticking it on the glass plate, it was left at a temperature of 23°C for 30 minutes, and then at a temperature of 23°C with a peeling angle of 180 degrees and a peeling speed of 300 mm/min, the surface protection film was Peeling from the glass plate, the peeling force is preferably 0.005N/25mm~0.1N/25mm, more preferably 0.007N/25mm~0.08N/25mm, and more preferably 0.01N/25mm~0.05N/25mm, The most preferable range is 0.01N/25mm~0.03N/25mm, and the best is 0.01N/25mm~0.02N/25mm. If the peeling force is within the above-mentioned range, it is possible to provide a situation in which easy peeling from the adherend is unlikely to occur. The surface protection film is not easy to peel off after the exposed surface of the component, and can be easily peeled off when peeling is required.

The surface protective film can be produced by any appropriate method. Such a production method can be carried out according to any appropriate production method, such as the following method. method; (2) a method of transferring and adhering the adhesive layer formed by coating the solution of the material for forming the adhesive layer or the hot-melt solution on the separator to the base material layer; (3) the material for forming the adhesive layer A method of extruding onto a substrate layer and forming a coating; (4) A method of extruding the substrate layer and the adhesive layer in two or more layers; (5) Laminating a single layer of adhesive on the substrate layer and (6) two or more layers of the adhesive layer and substrate layer-forming materials such as films or lamination layers are laminated method.

As the coating method, for example, a roll coater method, a notch coater method, a die nozzle coater method, a reverse coater method, a screen printing method, a gravure coater method, etc. can be used. .

The surface protection film of the embodiment of the present invention is a surface protection film which sufficiently suppresses the peeling electrostatic voltage and does not damage the optical member or the electronic member during peeling, and the surface protection film is typically a film containing an adhesive layer. Surface protective film, which is attached to the optical member or the 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. during the manufacturing steps of the optical member or electronic member the exposed face.

The peeling electrostatic voltage to glass of the surface protective film according to the embodiment of the present invention is preferably 3.0 kV or less, more preferably 2.5 kV or less, still more preferably 2.0 kV or less, particularly preferably 1.7 kV or less, and most preferably 1.5 kV the following. The measurement method of the peeling electrostatic voltage with respect to glass will be described below.

The peeling electrostatic voltage to the acrylic resin sheet of the surface protection film according to the embodiment of the present invention is preferably 4.0 kV or less, more preferably 3.5 kV or less, still more preferably 3.0 kV or less, still more preferably 2.5 kV or less, especially Preferably, it is 2.0kV or less, and most preferably, it is 1.5kV or less. The measurement method of the peeling electrostatic voltage with respect to an acrylic resin board will be described later.

The haze of the surface protective film of the embodiment of the present invention is preferably 5% or less, more preferably 4% or less, still more preferably 3% or less, particularly preferably 2.8% or less, and most preferably 2.5% or less. If the haze of the surface protective film of the embodiment of the present invention is in the above-mentioned range, it is suitable for use as a surface protective film attached to the exposed surface of an optical member or an electronic member. In particular, if the haze of the surface protective film of the embodiment of the present invention can be reduced to 3% or less, the inspection property of the surface protective film of the embodiment of the present invention will be further improved, which is more preferable. The measurement method of the haze will be described below.

The residual adhesion to glass of the surface protective film of the embodiment of the present invention is preferably 70% or more, more preferably 80% or more, more preferably 85% or more, particularly preferably 88% or more, and most preferably 90% above. The residual adhesive force to the glass is an indicator of how much the components of the adhesive layer of the surface protection film are transferred to the surface of the adherend and whether it causes pollution. The higher the value of the residual adhesion rate to the glass, the lower the possibility that the surface protective film will contaminate the adherend, and the lower the value of the residual adhesion rate to the glass, the surface protective film will contaminate the adherend the higher the probability. The measurement method of the residual adhesion rate to glass will be described below.

≪A-1. Adhesive layer≫

The adhesive layer is composed of an adhesive. The adhesive is formed from the adhesive composition. That is, it becomes an adhesive agent layer by making the adhesive agent formed from an adhesive agent composition into a layer shape.

Adhesives can be defined as those formed from the adhesive composition. The reason for this is that, for the adhesive, since the adhesive composition will undergo a cross-linking reaction due to heating or ultraviolet irradiation, etc., and become an adhesive, it is impossible to directly specify the adhesive according to the structure of the adhesive, and there are completely incompatible adhesives. The actual situation ("impossible/impractical situation"), therefore, the adhesive is safely specified as "thing" by the "former from the adhesive composition" rule.

The adhesive layer can be formed by any suitable method. Such a method includes, for example, a method of applying an adhesive composition on any appropriate substrate, heating and drying as necessary, and curing as necessary, and forming an adhesive layer on the substrate. As such a coating method, for example, a gravure roll coater, a reverse roll coater, a touch roll coater, a dip roll coater, a bar coater, a knife coater, a gas Knife coater, spray coater, notch wheel coater, direct coater, roller brush coater and other methods.

Regarding the thickness of the adhesive layer, in terms of further exhibiting the effects of the present invention, it is preferably 0.5 μm to 150 μm, more preferably 1 μm to 100 μm, further preferably 2 μm to 80 μm, particularly preferably 3 μm to 50 μm, The best is 5μm~30μm.

The adhesive composition includes a base polymer, an ionic compound, and a fluorine-based compound. By including the base polymer, the ionic compound and the fluorine-based compound in the adhesive composition, it is possible to provide a method that sufficiently suppresses the peeling electrostatic voltage without causing damage to the optical member or the electronic member during peeling The surface protection film, the surface protection film is typically a surface protection film comprising an adhesive layer, in the manufacturing steps of optical components or electronic components, in order to prevent the surface of the optical component or the electronic component from being processed and assembled , inspection, transportation, etc., and stick to the exposed surface of the optical component or the electronic component.

In this invention, the effect of this invention can be exhibited by making an adhesive composition contain both an ionic compound and a fluorine-type compound in addition to a base polymer. In particular, the effect of the present invention can be remarkably exhibited by including (combining) both an ionic compound and a fluorine-based compound (sometimes referred to as a "specific fluorine-based compound") of a preferred embodiment described below. . The reason for this is presumed to be that by coexisting an ionic compound that can exhibit an antistatic effect with a fluorine-based compound (preferably a specific fluorine-based compound) in the adhesive composition, the The synergistic effect of the specific fluorine-based compound) makes the ionic compound segregated on the surface side of the adhesive layer (the side attached to the adherend).

The content ratio of the base polymer in the adhesive composition is preferably 60% by weight to 99.9% by weight, more preferably 65% by weight to 99.9% by weight, and more preferably 70% by weight in terms of solid content. ~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 adhesive composition is within the above-mentioned range in terms of solid content, it is possible to provide a device that can sufficiently suppress the peeling electrostatic voltage without causing the adherend (typically, Optical components or electronic components) damaged surface protective film.

The content ratio of the ionic compound to 100 parts by weight of the base polymer is preferably 0.2 weight parts It is more preferably 0.3 parts by weight to 5.0 parts by weight, more preferably 0.5 parts by weight to 3.0 parts by weight, particularly preferably 0.7 parts by weight to 2.0 parts by weight, and most preferably 0.8 parts by weight to 1.5 parts by weight. When the content ratio of the ionic compound with respect to 100 parts by weight of the base polymer is within the above-mentioned range, it is possible to provide a method that sufficiently suppresses the peeling electrostatic voltage without causing the adherend (typically, an optical member or electronic components) damaged surface protective film. If the content ratio of the ionic compound to 100 parts by weight of the base polymer deviates from the above-mentioned range and is too low, there is a possibility that the peeling electrostatic voltage cannot be sufficiently suppressed. If the content ratio of the ionic compound with respect to 100 parts by weight of the base polymer deviates from the above range and is too high, there is a possibility of contamination of the adherend.

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, still more preferably 0.15 parts by weight to 3.0 parts by weight, and particularly preferably 0.2 parts by weight parts to 2.0 parts by weight, preferably 0.23 parts by weight to 1.5 parts by weight. If the content ratio of the fluorine-based compound to 100 parts by weight of the base polymer is within the above-mentioned range, it is possible to provide a method that sufficiently suppresses the peeling electrostatic voltage without causing the adherend (typically, an optical member or an electronic member) to be peeled off. components) damaged surface protective film. If the content ratio of the fluorine-based compound to 100 parts by weight of the base polymer deviates from the above range and is too low, there is a possibility that the peeling electrostatic voltage cannot be sufficiently suppressed. If the content ratio of the fluorine-based compound to 100 parts by weight of the base polymer deviates from the above range and is too high, there is a possibility of contamination of the adherend.

<A-1-1. Base polymer>

The base polymer is preferably at least one selected from polyols, urethane prepolymers, acrylic resins, rubber-based resins, and silicone-based resins. If the base polymer is at least one selected from polyols, urethane prepolymers, acrylic resins, rubber-based resins, and silicone-based resins, a A surface protection film which suppresses peeling electrostatic voltage more fully and makes the adherend (typically, an optical member or an electronic member) less likely to be damaged during peeling.

[A-1-1-1. Polyol]

The polyol is preferably reacted with a polyfunctional isocyanate compound to form a urethane resin. More specifically, it is preferable to form a urethane resin from a composition containing a polyhydric alcohol and a polyfunctional isocyanate compound. Specifically, the composition containing a polyhydric alcohol and a polyfunctional isocyanate compound is hardened to form an amine group. Formate resin. As a method of hardening a composition containing a polyol and a polyfunctional isocyanate compound to form a urethane-based resin, any appropriate method such as block polymerization or solution can be adopted within the range not impairing the effects of the present invention The urethane reaction method of polymerization etc., etc.

Only one type of polyol may be used, or two or more types may be used.

As the polyol, at least one selected from the group consisting of polyester polyol, polyether polyol, polycaprolactone polyol, polycarbonate polyol, and castor oil-based polyol can be preferably used. As the polyol, a polyether polyol is more preferable in that the effect of the present invention can be more exhibited.

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

Examples of polyol components include ethylene glycol, diethylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, and 3-methyl-1,5-pentanediol. alcohol, 2-butyl-2-ethyl-1,3-propanediol, 2,4-Diethyl-1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 2- Methyl-1,8-octanediol, 1,8-decanediol, octadecanediol, glycerin, trimethylolpropane, pentaerythritol, hexanetriol, polypropylene glycol, etc.

Examples of the acid component include succinic acid, methylsuccinic acid, adipic acid, pimelic acid, azelaic acid, sebacic acid, 1,12-dodecanedioic acid, 1,14-tetradecanedioic acid Alkanedioic 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-naphthalene dicarboxylic acid, 4,4'-biphenyl dicarboxylic acid, acid anhydrides thereof, and the like.

Examples of polyether polyols include polyether polyols prepared by using water, low molecular weight polyols (propylene glycol, ethylene glycol, glycerol, trimethylolpropane, pentaerythritol, etc.), bisphenols (bisphenols, etc.) Phenol A, etc.), dihydroxybenzene (catechol, resorcinol, hydroquinone, etc.), etc., are used as starting agents, and alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, etc. obtained by addition polymerization. Specifically, polyethylene glycol, polypropylene glycol, poly-1,4-butanediol, etc. are mentioned, for example.

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

The polycarbonate polyols include, for example, polycarbonate polyols obtained by polycondensing the above-mentioned polyol components with phosgene; Diethyl carbonate, dipropyl carbonate, diisopropyl carbonate, dibutyl carbonate, ethylbutyl carbonate, ethylene carbonate, propylene carbonate, diphenyl carbonate, dibenzyl carbonate, etc. Polycarbonate polyols obtained by transesterification condensation of carbonic acid diesters; Copolycarbonate polyols obtained by using two or more of the above-mentioned polyol components; Esterification of the above-mentioned various polycarbonate polyols with carboxyl-containing compounds Polycarbonate polyols obtained by the reaction of the above-mentioned polycarbonate polyols; polycarbonate polyols obtained by carrying out etherification reaction of the above-mentioned various polycarbonate polyols with hydroxyl-containing compounds; transesterification of the above-mentioned various polycarbonate polyols with ester compounds Polycarbonate polyol obtained by reaction; polycarbonate polyol obtained by transesterification reaction of the above-mentioned various polycarbonate polyols and hydroxyl-containing compounds; polycondensation of the above-mentioned various polycarbonate polyols and dicarboxylic acid compounds The polyester-based polycarbonate polyol obtained by the reaction; the copolyether-based polycarbonate polyol obtained by copolymerizing the above-mentioned various polycarbonate polyols and alkylene oxide.

As a castor oil type polyol, the castor oil type polyol obtained by making a castor oil fatty acid react with the said polyol component is mentioned, for example. Specifically, for example, castor oil-based polyols obtained by reacting castor oil fatty acid and polypropylene glycol can be mentioned.

The number average molecular weight Mn of the polyol is preferably 300-100,000, more preferably 400-75,000, further preferably 450-50,000, particularly preferably 500-30,000. If the number-average molecular weight Mn of the polyol is within the above-mentioned range, it is less likely to peel off the adherend easily. The exposed surface of the optical member or the electronic member is less likely to be peeled off later, and a surface protective film that can be peeled off more easily when peeling is required.

The polyol is preferably a polyol (A1) having three OH groups and a number-average molecular weight Mn of 300 to 100,000. Only one type of polyol (A1) may be used, or two or more types may be used.

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, further preferably 50% by weight to 100% by weight, and particularly preferably 70% by weight to 70% by weight. 100% by weight, preferably 90% by weight to 100% by weight. If the content ratio of the polyol (A1) in the polyol is within the above-mentioned range, it is possible to provide a situation where it is less likely to easily peel off from the adherend, and typically, in the manufacturing steps of optical members or electronic members , a surface protective film that is less likely to peel off after being attached to the exposed surface of the optical component or the electronic component, and can be peeled off more easily when peeling is required.

The polyol (A1) preferably contains a polyol (A1a) having three OH groups and a number average molecular weight Mn of 8,000 to 20,000. Only one type of polyol (A1a) may be used, or two or more types may be used.

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, further preferably 70% by weight to 95% by weight, particularly preferably 75% by weight % by weight to 93% by weight, preferably 80% by weight to 90% by weight. If the content ratio of the polyol (A1a) in the polyol (A1) is within the above-mentioned range, it is possible to provide a situation where the peeling from the adherend is less likely to occur, and typically, in the case of an optical member or an electronic member In the manufacturing step, the surface protective film that is less likely to be peeled off after being attached to the exposed surface of the optical component or the electronic component, and can be peeled off more easily when peeling is required.

The number average molecular weight Mn of the polyol (A1a) is 8000~20000, preferably 8000~18000, more preferably 8500~17000, further preferably 9000~16000, particularly preferably 9500~15500, and most preferably 10000~15000 . If the number average molecular weight Mn of the polyol (A1a) is in the Within the above range, a situation that is less likely to be easily peeled off from the adherend can be provided. Typically, in the manufacturing process of the optical member or the electronic member, it is attached to the exposed surface of the optical member or the electronic member. A surface protection film that is less likely to peel off later and can be peeled off more easily when peeling is required.

The polyol (A1) may contain a polyol (A1b) having three or more OH groups and having a number average molecular weight Mn of 5,000 or less. Only one type of polyol (A1b) may be used, or two or more types may be used.

The polyol (A1b) is preferably selected from the group consisting of polyols having 3 OH groups (triols), polyols having 4 OH groups (tetraols), polyols having 5 OH groups (pentanols), At least one of polyols (hexaols) with 6 OH groups.

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, further preferably 5% by weight to 30% by weight, particularly preferably 7% by weight % by weight to 25% by weight, preferably 10% by weight to 20% by weight. If the content ratio of the polyol (A1b) in the polyol (A1) is within the above-mentioned range, it is possible to provide a situation in which peeling from the adherend is less likely to occur, and typically, in optical members or electronic members In the manufacturing step, the surface protective film that is less likely to be peeled off after being attached to the exposed surface of the optical component or the electronic component, and can be peeled off more easily when peeling is required.

The number average molecular weight Mn of the polyol (A1b) is preferably 500-5000, more preferably 600-4500, further preferably 700-4000, particularly preferably 800-3500, and most preferably 900-3300. If the number-average molecular weight Mn of the polyol (A1b) is within the above range, it can provide a more stable It is easy to peel off from the adherend. Typically, in the manufacturing steps of optical components or electronic components, it is less likely to peel off after being attached to the exposed surface of the optical component or the electronic component, and when necessary A surface protection film that can be peeled off more easily. If the number-average molecular weight Mn of the polyol (A1b) deviates from the above-mentioned range, there is a fear that the time-dependent increase in adhesive force in particular becomes high, and there is a possibility that the excellent secondary processability cannot be expressed.

The polyol (A1b) is at least one selected from the group consisting of polyols having 4 OH groups (tetraols), polyols having 5 OH groups (pentanols), and polyols having 6 OH groups (hexaols) In one case, the total amount thereof is based on the content ratio in the polyol (A1), preferably 40% by weight or less, more preferably 0% by weight to 30% by weight, and more preferably 3% by weight ~20% by weight, particularly preferably 5% by weight to 15% by weight, and most preferably 7% by weight to 10% by weight. If in the polyol (A1), the polyol (A1b) is selected from the group consisting of a polyol (tetraol) having 4 OH groups, a polyol (pentaol) having 5 OH groups, and a polyol having 6 OH groups In the case of at least one of (hexaol), when the total amount thereof is within the above-mentioned range, it is possible to provide a situation in which it is less likely to easily peel off from the adherend, and typically, in optical or electronic components In the manufacturing step, the surface protective film that is less likely to be peeled off after being attached to the exposed surface of the optical component or the electronic component, and can be peeled off more easily when peeling is required. Moreover, it can become a surface protective film excellent in transparency.

Regarding the polyol (A1b), at least one selected from the group consisting of polyols having 4 OH groups (tetraols), polyols having 5 OH groups (pentanols), and polyols having 6 OH groups (hexaols) The content ratio of one is preferably less than 10 wt %, more preferably 7 wt % or less, more preferably 5 wt % or less, particularly preferably 3 wt % or less, with respect to the entire polyol (A1), most preferably It is 1 weight% or less. If the polyol (A1b) is selected from polyols (tetraols) with 4 OH groups, with 5 OH groups If the content ratio of at least one of the polyol (pentaol) having 6 OH groups and the polyol (hexaol) having 6 OH groups is within the above range, a situation that is less likely to be easily peeled off from the adherend can be provided, Typically, in the manufacturing process of an optical member or an electronic member, it is less likely to peel off after being attached to the exposed surface of the optical member or the electronic member, and can be peeled off more easily when peeling is required. . Also, if the polyol (A1b) is selected from the group consisting of a polyol having 4 OH groups (tetraol), a polyol having 5 OH groups (pentaol), and a polyol having 6 OH groups (hexaol) When the content ratio of at least one of them deviates from the above-mentioned range, the transparency of the surface protective film may be lowered.

The polyol (A1) may contain a polyol (A1c) having four or more OH groups and having a number average molecular weight Mn of 20,000 or less. Only one type of polyol (A1c) may be used, or two or more types may be used.

In the polyol (A1), the content ratio of the polyol (A1c) having 4 or more OH groups and the number average molecular weight Mn of 20,000 or less is preferably less than 70% by weight, more preferably 60% by weight or less, and more It is preferably 50% by weight or less, more 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 the number-average molecular weight Mn of 20,000 or less in the polyol (A1) is within the above-mentioned range, it is possible to provide a product that is less likely to easily separate from the adherend. In the case of peeling, typically, in the manufacturing step of an optical member or an electronic member, it is less likely to peel off after being attached to the exposed surface of the optical member or the electronic member, and it can be peeled off more easily when peeling is required. surface protective film. Moreover, it can become a surface protective film excellent in transparency.

[A-1-1-2. Urethane Prepolymer]

The urethane prepolymer is preferably reacted with a polyfunctional isocyanate compound to form a urethane resin. More specifically, it is preferable to form a urethane resin from a composition containing a urethane prepolymer and a polyfunctional isocyanate compound. The composition of the polyfunctional isocyanate compound hardens to form a urethane resin. As a method of hardening a composition containing a polyol and a polyfunctional isocyanate compound to form a urethane resin, any appropriate production method can be adopted, as long as a so-called "urethane prepolymer" is used as a raw material. What is necessary is just to manufacture a urethane resin.

Furthermore, in the description of the present invention, "urethane prepolymer" refers to what is commonly called "urethane prepolymer" in the manufacture of urethane resin, and A- The "polyol" described in Item 1-1-1 is different.

Only one type of urethane prepolymer may be used, or two or more types may be used.

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

The urethane prepolymer is preferably a polyurethane polyol, more preferably the polyester polyol (a1) or the polyether polyol (a2) is used alone, or as (a1) and (a1) In the form of mixture of a2), it is formed by reacting with a polyfunctional isocyanate compound in the presence or absence of a catalyst. Only one type of polyester polyol (a1) may be used, or two or more types may be used. Only one type of polyether polyol (a2) may be used, or two or more types may be used.

As the polyester polyol (a1), any appropriate polyester polyol can be used. as such polyester The polyol (a1) includes, for example, a polyester polyol obtained by reacting an acid component and a diol component. As an acid component, terephthalic acid, adipic acid, azelaic acid, sebacic acid, phthalic anhydride, isophthalic acid, trimellitic acid, etc. are mentioned, for example. As a glycol component, for example, ethylene glycol, propylene glycol, diethylene glycol, butanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 3,3'- Dimethylolheptane, polyoxyethylene glycol, polyoxypropylene glycol, 1,4-butanediol, neopentyl glycol, butylethylpentanediol; as polyol components, glycerin, trihydroxy Methyl propane, pentaerythritol, etc. As the polyester polyol (a1), in addition to the above, those obtained by ring-opening polymerization of lactones such as polycaprolactone, poly(β-methyl-γ-valerolactone), and polyvalerolactone can be used. Polyester polyols, etc.

As the molecular weight of the polyester polyol (a1), a low molecular weight to a high molecular weight can be used. 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 may become high, and there is a possibility that gelation is likely to occur. When the number average molecular weight Mn exceeds 100,000, there is a possibility that the reactivity will become low and the cohesive force of the polyurethane polyol itself will become small. The usage-amount of the polyester polyol (a1) is preferably 0 mol % to 90 mol % in the polyol constituting the polyurethane polyol.

(oxirane)化合物聚合而獲得之聚醚多元醇。作為此種聚醚多元醇(a2)，具體而言，可列舉例如聚丙二醇、聚乙二醇、聚1,4-丁二醇等官能基數為2以上之聚醚多元醇。 As the polyether polyol (a2), any appropriate polyether polyol can be used. As such polyether polyol (a2), for example, ethylene oxide, epoxy Oxygen such as propane, butylene oxide, tetrahydrofuran

(oxirane) polyether polyol obtained by polymerizing compounds. Specific examples of such polyether polyol (a2) include polyether polyols having 2 or more functional groups, such as polypropylene glycol, polyethylene glycol, and poly-1,4-butanediol.

As the molecular weight of the polyether polyol (a2), a low molecular weight to a high molecular weight can be used. 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 may become high, and there is a possibility that gelation is likely to occur. When the number average molecular weight Mn exceeds 100,000, there is a possibility that the reactivity will become low and the cohesive force of the polyurethane polyol itself will become small. The usage-amount of the polyether polyol (a2) is preferably 0 mol % to 90 mol % in the polyol constituting the polyurethane polyol.

Regarding the polyether polyol (a2), a part of it may be replaced with ethylene glycol, 1,4-butanediol, neopentyl glycol, butylethylpentanediol, glycerin, trimethylolpropane, and pentaerythritol as necessary Diols such as ethylenediamine, N-aminoethylethanolamine, isophoronediamine, and polyamines such as xylylenediamine are used in combination.

As the polyether polyol (a2), only a bifunctional polyether polyol may be used, or a part or all of a polyether polyol having a number-average molecular weight Mn of 100 to 100,000 and having at least three or more hydroxyl groups in one molecule may be used. . As the polyether polyol (a2), if a part or all of a polyether polyol 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 force and the releasability can be balanced. good. In such a polyether polyol, when the number average molecular weight Mn is less than 100, the reactivity becomes high and there is a possibility that gelation is likely to occur. Moreover, in such a polyether polyol, when the number average molecular weight Mn exceeds 100,000, there is a possibility that the reactivity will become low and the cohesion force of the polyurethane polyol itself will become small. The number average molecular weight Mn of this polyether polyol is more preferably 100-10,000.

As a catalyst that can be used when obtaining a polyurethane polyol, any appropriate one can be used. catalyst. As such a catalyst, a tertiary amine compound, an organometallic compound, etc. are mentioned, for example.

As a tertiary amine type compound, triethylamine, triethylenediamine, 1, 8- diazabicyclo (5,4,0)-undecene-7 (DBU) etc. are mentioned, for example.

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

Examples of tin-based compounds include dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin dimaleate, dibutyltin dilaurate (DBTDL), dibutyltin diacetate, dibutyltin sulfide, Tributyltin sulfide, tributyltin oxide, tributyltin acetate, triethyltin ethoxide, tributyltin ethoxide, dioctyltin oxide, tributyltin chloride, tributyltin trichloroacetate, tin 2-ethylhexanoate, etc.

Examples of non-tin-based compounds include titanium-based compounds such as dibutyltitanium dichloride, tetrabutyl titanate, and butoxytitanium trichloride; lead oleate, lead 2-ethylhexanoate, Lead compounds such as 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; naphthenic acid Zinc-based compounds such as zinc and zinc 2-ethylhexanoate; zirconium-based compounds such as zirconium naphthenate.

In the case of using a catalyst to obtain a polyurethane polyol, if a system of two polyols, a polyester polyol and a polyether polyol, is present, the reactivity will be different, so In the system of a single catalyst, the problem of gelation or turbidity of the reaction solution is easy to occur. Therefore, by using two catalysts when obtaining a polyurethane polyol, it becomes easy to control a reaction rate, selectivity of a catalyst, etc., and these problems can be solved. As a combination of such two catalysts, for example, tertiary amine/organometallic, tin/non-tin, tin/tin, preferably tin/tin, more preferably dilauric acid A combination of dibutyltin and tin 2-ethylhexanoate. Regarding the above-mentioned compounding ratio of the combination of dibutyltin dilaurate and tin 2-ethylhexanoate, in terms of weight ratio, tin 2-ethylhexanoate/dibutyltin dilaurate is preferably less than 1, more preferably 0.2 ~0.6. When the compounding ratio is 1 or more, there is a possibility that gelation is likely to occur due to the balance of catalyst activity.

In the case of using a catalyst when obtaining a polyurethane polyol, the amount of the catalyst used is relative to the total amount of the polyester polyol (a1), the polyether polyol (a2) and the polyfunctional isocyanate compound , preferably 0.01% by weight to 1.0% by weight.

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

When obtaining a polyurethane polyol, a catalyst may not be used. In this 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 make it react for 3 hours or more.

As a method for obtaining a polyurethane polyol, for example, 1) Polyester polyol The method of adding alcohol, polyether polyol, catalyst, and polyfunctional isocyanate compound into the flask; 2) The method of adding polyester polyol, polyether polyol, and catalyst to the flask and then adding the polyfunctional isocyanate compound dropwise. As a method of obtaining a polyurethane polyol, the method of 2) is preferable in terms of controlling the reaction.

In obtaining the polyurethane polyol, any suitable solvent can be used. As such a solvent, methyl ethyl ketone, ethyl acetate, toluene, xylene, acetone, etc. are mentioned, for example. Among these solvents, toluene is preferred.

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

As the acrylic resin, any appropriate acrylic resin can be used within a range that does not impair the effects of the present invention. Only one type of acrylic resin may be used, or two or more types may be used.

The weight-average molecular weight of the acrylic resin is preferably 300,000 to 2,500,000, more preferably 350,000 to 2,000,000, and further preferably 400,000 to 1,800,000, in terms of better performance of the effects of the present invention, The best is 500,000 to 1.5 million.

The acrylic resin is preferably an alkyl (meth)acrylate having 4 to 12 carbon atoms in the alkyl group including the alkyl ester moiety of (component a), in terms of exhibiting the effects of the present invention. , and (b component) at least one selected from the group consisting of (meth)acrylate and (meth)acrylic acid having an OH group, the composition (B) is an acrylic resin formed by polymerization. (a component) and (b component) each independently may be only 1 type, and may be 2 or more types.

The alkyl group (meth)acrylate (component a) having 4 to 12 carbon atoms in the alkyl ester moiety includes, for example, n-butyl (meth)acrylate and isobutyl (meth)acrylate. , 2nd butyl (meth)acrylate, 3rd butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, (meth)acrylic acid Octyl ester, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, ( Isodecyl meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate, and the like. Among them, n-butyl (meth)acrylate and 2-ethylhexyl (meth)acrylate are preferred, and n-butyl acrylate and 2- Ethylhexyl ester.

As at least one (b component) selected from the group consisting of (meth)acrylate and (meth)acrylic acid having an OH group, for example, hydroxyethyl (meth)acrylate, (meth)acrylic acid may be mentioned. (meth)acrylates having OH groups, such as hydroxypropyl ester and hydroxybutyl (meth)acrylate, (meth)acrylic acid, and the like. Among them, hydroxyethyl (meth)acrylate and (meth)acrylic acid are preferred, and hydroxyethyl acrylate and acrylic acid are more preferred in terms of the effect of the present invention.

啉、N-乙烯基哌啶酮、N-乙烯基哌

、N-乙烯基吡咯、N-乙烯基咪唑、乙烯基吡啶、乙烯基嘧啶、乙烯基

唑等含雜環之乙烯系單體；乙烯基磺酸鈉等含磺酸基單體；2-羥乙基丙烯醯基磷酸酯等含磷酸基單體；環己基馬來醯亞胺、異丙基馬來醯亞胺等含亞胺基單體；異氰酸2-甲基丙烯醯氧基乙酯等含異氰酸酯基單體；(甲基)丙烯酸環戊酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸異

基酯等具有脂環式烴基之(甲基)丙烯酸酯；(甲基)丙烯酸苯酯、(甲基)丙烯酸苯氧基乙酯、(甲基)丙烯酸苄酯等具有芳香族烴基之(甲基)丙烯酸酯；乙酸乙烯酯、丙酸乙烯酯等乙烯酯；苯乙烯、乙烯基甲苯等芳香族乙烯系化合物；乙烯、丁二烯、異戊二烯、異丁烯等烯烴類或二烯類；乙烯基烷基醚等乙烯醚類；氯乙烯。 The composition (B) may contain comonomers other than (a) component and (b) component. Only one type of copolymerizable monomer may be used, or two or more types may be used. Examples of such copolymerizable monomers include itaconic acid, maleic acid, fumaric acid, crotonic acid, methacrylic acid, and acid anhydrides thereof (for example, acid anhydrides such as maleic anhydride and itaconic anhydride) carboxyl group-containing monomers) and other carboxyl group-containing monomers (excluding (meth)acrylic acid); (meth)acrylamide, N,N-dimethyl (meth)acrylamide, N-methylol (methyl) base) acrylamide, N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, etc. Amino-based monomers; amino-group-containing monomers such as aminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, and tert-butylaminoethyl (meth)acrylate; ( Epoxy group-containing monomers such as glycidyl meth)acrylate and methyl glycidyl (meth)acrylate; cyano group-containing monomers such as acrylonitrile or methacrylonitrile; N-vinyl-2-pyrrolidone , (meth)acrylonitrile

Linen, N-vinylpiperidone, N-vinylpiperidine

, N-vinylpyrrole, N-vinylimidazole, vinylpyridine, vinylpyrimidine, vinyl

Heterocycle-containing vinyl monomers such as azoles; sulfonic acid group-containing monomers such as sodium vinyl sulfonate; phosphoric acid group-containing monomers such as 2-hydroxyethyl acryl phosphate; Isocyanate group-containing monomers such as propylmaleimide; isocyanate group-containing monomers such as 2-methacryloyloxyethyl isocyanate; (meth)acrylate cyclopentyl, (meth)acrylate ring Hexyl ester, (meth)acrylic acid iso

(meth)acrylates with alicyclic hydrocarbon groups, such as base esters; (meth)acrylates with aromatic hydrocarbon groups such as phenyl (meth)acrylate, phenoxyethyl (meth)acrylate, benzyl (meth)acrylate, etc. base) acrylates; vinyl esters such as vinyl acetate and vinyl propionate; aromatic vinyl compounds such as styrene and vinyl toluene; olefins or dienes such as ethylene, butadiene, isoprene, isobutylene, etc.; Vinyl ethers such as vinyl alkyl ethers; vinyl chloride.

As a copolymerizable monomer, a polyfunctional monomer can also be used. The polyfunctional monomer system refers to a monomer having two or more ethylenically unsaturated groups in one molecule. As the ethylenically unsaturated group, any appropriate ethylenically unsaturated group can be used within a range not impairing the effects of the present invention. Examples of such ethylenically unsaturated groups include radically polymerizable functional groups such as vinyl groups, propenyl groups, isopropenyl groups, vinyl ether groups (vinyloxy groups), and allyl ether groups (allyloxy groups). base. As the polyfunctional monomer, for example, hexanediol di(meth)acrylate, butanediol di(meth)acrylate, (poly)ethylene glycol di(meth)acrylate, (poly) Propylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate Esters, Trimethylolpropane Tri(meth)propylene acid ester, tetramethylolmethane tri(meth)acrylate, allyl(meth)acrylate, vinyl(meth)acrylate, divinylbenzene, epoxy acrylate, polyester acrylate, acrylate amine Formate etc. Only one type of such a polyfunctional monomer may be sufficient as it, and two or more types may be sufficient as it.

As a comonomer, (meth)acrylic-acid alkoxyalkyl ester can also be used. Examples of alkoxyalkyl (meth)acrylates include 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, and methoxy (meth)acrylate. triethylene glycol, 3-methoxypropyl (meth)acrylate, 3-ethoxypropyl (meth)acrylate, 4-methoxybutyl (meth)acrylate, (methyl) 4-ethoxybutyl acrylate, etc. Only one type of alkoxyalkyl (meth)acrylate may be used, or two or more types may be used.

Regarding the content of the alkyl (meth)acrylate (component a) having 4 to 12 carbon atoms in the alkyl group of the alkyl ester moiety, the effect of the present invention can be more exhibited than the content of the acrylic polymer constituting the The total amount of monomer components (100% by weight) is preferably 30% by weight or more, more preferably 35% by weight to 99% by weight, and more preferably 40% by weight to 98% by weight, especially 50% by weight to 98% by weight. 95% by weight.

Regarding the content of at least one (component b) selected from the group consisting of (meth)acrylate and (meth)acrylic acid having an OH group, the effect of the present invention can be more exhibited than the The total amount of monomer components (100% by weight) of the acrylic polymer is preferably 1% by weight or more, more preferably 1% by weight to 30% by weight, more preferably 2% by weight to 20% by weight, and particularly preferably 3% by weight % by weight to 10% by weight.

The composition (B) may contain any appropriate other components within a range that does not impair the effects of the present invention. As such other components, a polymerization initiator, a chain transfer agent, a solvent, etc. are mentioned, for example. Regarding the content of these other components, any appropriate content can be adopted within a range not impairing the effects of the present invention.

As the polymerization initiator, a thermal polymerization initiator or a photopolymerization initiator (photoinitiator), etc. can be used according to the kind of polymerization reaction. Only one type of polymerization initiator may be used, or two or more types may be used.

The thermal polymerization initiator can preferably be used when obtaining an acrylic resin by solution polymerization. Examples of such thermal polymerization initiators include azo-based polymerization initiators, peroxide-based polymerization initiators (for example, dibenzyl peroxide, tert-butyl peroxide maleate) etc.), redox-based polymerization initiators, etc. Among these thermal polymerization initiators, the azo initiator disclosed in Japanese Patent Laid-Open No. 2002-69411 is particularly preferred. Such an azo-based polymerization initiator is preferable in that the decomposed product of the polymerization initiator is unlikely to remain in the acrylic resin as a part that causes the generation of gas (outgas) generated by heating. As the azo-based polymerization initiator, 2,2'-azobisisobutyronitrile (hereinafter, sometimes referred to as AIBN), 2,2'-azobis-2-methylbutyronitrile (hereinafter, may be mentioned) , sometimes referred to as AMBN), 2,2'-azobis(2-methylpropionic acid) dimethyl ester, 4,4'-azobis-4-cyanovaleric acid, etc.

系光聚合起始劑等等。 The photopolymerization initiator can preferably be used when an acrylic polymer is obtained by active energy ray polymerization. As a photopolymerization initiator, for example, a benzoin ether-based photopolymerization initiator, an acetophenone-based photopolymerization initiator, an α-keto alcohol-based photopolymerization initiator, an aromatic sulfonyl chloride-based photopolymerization initiator can be mentioned. Starter, photoactive oxime-based photopolymerization initiator, benzoin-based photopolymerization initiator, benzoin-based photopolymerization initiator, benzophenone-based photopolymerization initiator, ketal-based photopolymerization initiator , 9-oxysulfur

Department of photopolymerization initiator and so on.

系光聚合起始劑，可列舉例如：9-氧硫

、2-氯9-氧硫

、2-甲基9-氧硫

、2,4-二甲基9-氧硫

、異丙基9-氧硫

、2,4-二異丙基9-氧硫

、十二烷基9-氧硫

等。 Examples of benzoin ether-based photopolymerization initiators include benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and 2,2-dimethoxy-1,2-diphenyl. Ethan-1-one, anisole, etc. Examples of the acetophenone-based photopolymerization initiator include 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, and 1-hydroxycyclohexylbenzene ketone, 4-phenoxydichloroacetophenone, 4-(tert-butyl)dichloroacetophenone, etc. Examples of the α-ketoalcohol-based photopolymerization initiator include 2-methyl-2-hydroxypropiophenone, 1-[4-(2-hydroxyethyl)phenyl]-2-methylpropane-1 - Ketones etc. As an aromatic sulfonyl chloride-based photopolymerization initiator, 2-naphthalenesulfonyl chloride, etc. are mentioned, for example. As a photoactive oxime-based photopolymerization initiator, 1-phenyl-1,1-propanedione-2-(o-ethoxycarbonyl)-oxime etc. are mentioned, for example. As a benzoin type photopolymerization initiator, benzoin etc. are mentioned, for example. As a benzil-based photopolymerization initiator, for example, benzil and the like can be mentioned. Examples of benzophenone-based photopolymerization initiators include benzophenone, benzoic acid, 3,3'-dimethyl-4-methoxybenzophenone, polyethylene diphenyl Methyl ketone, α-hydroxycyclohexyl phenyl ketone, etc. As a ketal type photopolymerization initiator, benzalkonium dimethyl ketal etc. are mentioned, for example. as 9-oxosulfur

Photopolymerization initiator, for example: 9-oxysulfur

, 2-chloro-9-oxosulfur

, 2-methyl 9-oxothio

, 2,4-dimethyl 9-oxothio

, isopropyl 9-oxothio

, 2,4-diisopropyl 9-oxothio

, dodecyl 9-oxysulfur

Wait.

Furthermore, when the base polymer is an acrylic resin, the adhesive composition may contain a crosslinking agent. By using the cross-linking agent, the cohesive force of the adhesive can be improved, and the effect of the present invention can be better exhibited. Only one type of crosslinking agent may be used, or two or more types may be used.

唑啉系交聯劑、氮丙啶系交聯劑、胺系交聯劑等。其中，就更能表現本發明之效果之方面而言，較佳為選自由多官能異氰酸酯系交聯劑及環氧系交聯劑所組成之群中之至少一種。 As the crosslinking agent, a polyfunctional isocyanate-based crosslinking agent, an epoxy-based crosslinking agent, a melamine-based crosslinking agent, a peroxide-based crosslinking agent may be mentioned, and further, a urea-based crosslinking agent, a metal alkane may be mentioned. Oxide-based cross-linking agent, metal chelate-based cross-linking agent, metal salt-based cross-linking agent, carbodiimide-based cross-linking agent,

oxazoline-based cross-linking agent, aziridine-based cross-linking agent, amine-based cross-linking agent, etc. Among them, at least one kind selected from the group consisting of a polyfunctional isocyanate-based crosslinking agent and an epoxy-based crosslinking agent is preferable from the viewpoint that the effect of the present invention can be more exhibited.

Examples of polyfunctional isocyanate-based crosslinking agents include lower aliphatic polymers such as ethylene 1,2-diisocyanate, 1,4-butylene diisocyanate, and 1,6-hexamethylene diisocyanate. Isocyanates; cyclopentylene diisocyanate, cyclohexylene diisocyanate, isophorone diisocyanate, hydrogenated toluene diisocyanate, hydrogenated xylene diisocyanate and other alicyclic polyisocyanates; 2,4-toluene diisocyanate, 2 , Aromatic polyisocyanates such as 6-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, etc. Examples of polyfunctional isocyanate-based crosslinking agents include trimethylolpropane/toluene diisocyanate adducts (products named "Coronate L" manufactured by Nippon Polyurethane Industrial Co., Ltd.), trimethylolpropane / Hexamethylene diisocyanate adduct (product named "Coronate HL" manufactured by Nippon Polyurethane Industrial Co., Ltd.), product named "Coronate HX" (Nippon Polyurethane Industrial Co., Ltd.), trimethylol Commercial products such as propane/xylylene diisocyanate adduct (product called "Takenate 110N" manufactured by Mitsui Chemicals Co., Ltd.).

As an epoxy-based crosslinking agent (polyfunctional epoxy compound), for example: N,N,N',N'-tetrakis Glycidyl m-xylylenediamine, diglycidyl aniline, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, 1,6-hexanediol diglycidyl ether, neopentyl Glycol Diglycidyl Ether, Ethylene Glycol Diglycidyl Ether, Propylene Glycol Diglycidyl Ether, Polyethylene Glycol Diglycidyl Ether, Polypropylene Glycol Diglycidyl Ether, Sorbitol Polyglycidyl Ether, Glycerol Polyglycidyl Ether ether, pentaerythritol polyglycidyl ether, polyglycerol polyglycidyl ether, sorbitan polyglycidyl ether, trimethylolpropane polyglycidyl ether, diglycidyl adipate, diglycidyl phthalate , triglycidyl-tris (2-hydroxyethyl) isocyanurate, resorcinol diglycidyl ether, bisphenol-S-diglycidyl ether, in addition, there are 2 or more in the molecule. Epoxy-based epoxy resins, etc. As the epoxy-based crosslinking agent, commercially available products such as a product named "Tetrad C" (manufactured by Mitsubishi Gas Chemical Co., Ltd.) can also be mentioned.

Regarding the content of the crosslinking agent in the adhesive composition, any appropriate content can be adopted within a range that does not impair the effects of the present invention. As such a content, for example, from the viewpoint that the effect of the present invention can be more exhibited, with respect to the solid content (100 parts by weight) of the acrylic resin, preferably 0.05 parts by weight to 20 parts by weight, more preferably 0.1 Parts by weight to 18 parts by weight, more preferably 0.5 parts by weight to 15 parts by weight, particularly preferably 0.5 parts by weight to 10 parts by weight.

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

As the rubber-based resin, any suitable rubber-based adhesive such as the known rubber-based adhesive described in Japanese Patent Laid-Open No. 2015-074771 and the like can be used within a range that does not impair the effects of the present invention. Rubber-based resin. Only 1 type may be sufficient as these, and 2 or more types may be sufficient as them.

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

As the silicone-based resin, any appropriate silicone-based adhesive, such as a known silicone-based adhesive described in Japanese Patent Laid-Open No. 2014-047280 and the like, can be used within a range that does not impair the effects of the present invention. Silicone resin used in Only 1 type may be sufficient as these, and 2 or more types may be sufficient as them.

<A-1-2. Urethane resin>

As described above, the polyol as the base polymer is preferably reacted with a polyfunctional isocyanate compound to form a urethane resin. More specifically, it is preferable to form a urethane resin from a composition containing a polyhydric alcohol and a polyfunctional isocyanate compound. Specifically, the composition containing a polyhydric alcohol and a polyfunctional isocyanate compound is hardened to form an amine group. Formate resin. As a method of hardening a composition containing a polyol and a polyfunctional isocyanate compound to form a urethane-based resin, any appropriate method such as block polymerization or solution can be adopted within the range not impairing the effects of the present invention The urethane reaction method of polymerization etc., etc.

Moreover, as mentioned above, it is preferable that the urethane prepolymer which is a base polymer reacts with a polyfunctional isocyanate compound, and becomes a urethane resin. More specifically, it is preferable to form a urethane resin from a composition containing a urethane prepolymer and a polyfunctional isocyanate compound. The composition of the polyfunctional isocyanate compound hardens to form a urethane resin. As a method of hardening a composition containing a polyol and a polyfunctional isocyanate compound to form a urethane-based resin, any appropriate production method can be adopted as long as a so-called "urethane prepolymer" is used as the What is necessary is just to manufacture a urethane-type resin using a raw material.

That is, a preferable 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 resin is a urethane resin formed from a composition containing a urethane prepolymer and a polyfunctional isocyanate compound.

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

Only one type of polyfunctional isocyanate compound may be used, or two or more types may be used.

As the polyfunctional isocyanate compound, any appropriate polyfunctional isocyanate compound that can be used in the urethane reaction can be used. As such a polyfunctional isocyanate compound, a polyfunctional aliphatic isocyanate compound, a polyfunctional alicyclic isocyanate, a polyfunctional aromatic isocyanate compound, a polyfunctional aromatic aliphatic isocyanate compound etc. are mentioned, for example.

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

As the polyfunctional alicyclic isocyanate compound, for example: 3-isocyanato isocyanate Acid methyl-3,5,5-trimethylcyclohexyl ester, 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, isophor Erone diisocyanate, methyl-2,4-cyclohexanediisocyanate, methyl-2,6-cyclohexanediisocyanate, 4,4'-methylenebis(cyclohexylisocyanate), 1,4- Bis(isocyanatomethyl)cyclohexane, 1,4-bis(isocyanatomethyl)cyclohexane, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated tolylene diisocyanate , Hydrogenated tetramethylxylylene diisocyanate, etc.

As the polyfunctional aromatic diisocyanate compound, for example, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 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'-biphenyl diisocyanate, 1,5-naphthalene diisocyanate, 4,4',4"-triphenylmethane triisocyanate, Lianda Anisidine diisocyanate, xylylene diisocyanate, etc.

As the polyfunctional aromatic aliphatic isocyanate compound, for example, ω,ω'-diisocyanate-1,3-dimethylbenzene, ω,ω'-diisocyanate-1,4-dimethylbenzene, ω, ω'-diisocyanate-1,4-diethylbenzene, 1,4-tetramethylxylylene diisocyanate, 1,3-tetramethylxylylene diisocyanate, etc.

Examples of the polyfunctional isocyanate compound include trimethylolpropane adducts of various polyfunctional isocyanate compounds as described above, biurets obtained by reacting with water, and trimers having an isocyanurate ring. things etc. Moreover, you may use these etc. together.

The equivalent ratio of NCO groups to OH groups in polyols and polyfunctional isocyanate compounds is preferably 5.0 or less, more preferably 0.1 to 3.0, more preferably 0.2 to 2.5, and more preferably in terms of NCO groups/OH groups. Preferably it is 0.3-2.5, More preferably, it is 0.3-2.0, More preferably, it is 0.5-2.0, Most preferably, it is 0.5-1.8. When the equivalent ratio of NCO groups/OH groups is within the above range, it is possible to provide a situation where it is difficult to easily peel off the adherend. A surface protective film that does not easily peel off after the exposed surface of the optical member or the electronic member, and can be easily peeled off when peeling is required. Moreover, when the equivalent ratio of NCO group / OH group exists in the said range, haze can be reduced. In particular, if the haze can be reduced to 3% or less, the inspectability of the surface protection 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 still more preferably 2.0% by weight to 25% by weight relative to the polyol. %, more preferably 2.3% by weight to 23% by weight, more preferably 2.3% by weight to 18% by weight, particularly preferably 2.5% by weight to 18% by weight, and most preferably 2.5% by weight to 16% by weight. If the content ratio of the polyfunctional isocyanate compound is within the above-mentioned range, it is possible to provide a situation where it is difficult to easily peel off the adherend, and typically, in the manufacturing process of an optical member or an electronic member, the optical member is attached to the optical member. A surface protection film that does not easily peel off after the exposed surface of the component or the electronic component, and can be easily peeled off when peeling is required. Moreover, when the content ratio of a polyfunctional isocyanate compound exists in the said range, haze can be reduced. In particular, if the haze can be reduced to 3% or less, the inspectability of the surface protection film according to the embodiment of the present invention will be further improved.

In order to harden the composition containing a polyol and a polyfunctional isocyanate compound, it is preferable to use a catalyst. As such a catalyst, an organometallic compound, a tertiary amine compound, etc. are mentioned, for example. Only one type of catalyst may be used, or two or more types may be used.

Examples of the organometallic compound include iron-based compounds, tin-based compounds, titanium-based compounds, zirconium-based compounds, lead-based compounds, cobalt-based compounds, zinc-based compounds, and the like. Among them, an iron-based compound and a tin-based compound are preferred in terms of the reaction rate and the pot life of the adhesive layer.

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

Examples of tin-based compounds include dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin maleate, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin sulfide, and tributylmethanol. Tin, tributyltin acetate, triethyltin ethoxide, tributyltin ethoxide, dioctyltin oxide, dioctyltin dilaurate, tributyltin chloride, tributyltin trichloroacetate, tin 2-ethylhexanoate Wait.

As a titanium type compound, dibutyl titanium dichloride, tetrabutyl titanate, butoxy titanium trichloride, etc. are mentioned, for example.

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

Examples of lead-based compounds include lead oleate, lead 2-ethylhexanoate, and benzoic acid. Lead, lead naphthenate, etc.

As a cobalt-type compound, cobalt 2-ethylhexanoate, cobalt benzoate, etc. are mentioned, for example.

As a zinc-based compound, zinc naphthenate, zinc 2-ethylhexanoate, etc. are mentioned, for example.

As a tertiary amine compound, triethylamine, triethylenediamine, 1,8-diazabicyclo-(5,4,0)-undecene-7 etc. are mentioned, for example.

The amount of the catalyst is preferably 0.005% by weight to 1.00% by weight, more preferably 0.01% by weight to 0.75% by weight, still more preferably 0.01% by weight to 0.50% by weight, and particularly preferably 0.01% by weight relative to the polyol. %~0.20% by weight. If the amount of the catalyst is within the above-mentioned range, it is possible to provide a situation where it is difficult to easily peel off the adherend. A surface protection film that is not easy to peel off after the exposed surface of the electronic component, and can be peeled off easily when peeling is required.

In the composition containing a polyol and a polyfunctional isocyanate compound, any appropriate other components may be contained in the range which does not impair the effect of this invention. Examples of such other components include antioxidants, ultraviolet absorbers, light stabilizers, resin components, adhesion imparting agents, crosslinking retarders, inorganic fillers, organic fillers, metal powders, pigments, foils, Softeners, anti-aging agents, conductive agents, surface lubricants, leveling agents, preservatives, heat-resistant stabilizers, polymerization inhibitors, lubricants, solvents, etc.

Among these other components, it is a preferred embodiment to contain anti-deterioration agents such as antioxidants, ultraviolet absorbers, and light stabilizers. By including the anti-deterioration agent in the adhesive composition, it is possible to have excellent paste residue resistance, such as being less likely to remain on the adherend even if the formed adhesive layer is attached to the adherend and then stored in a heated state Paste etc. Only one type of anti-deterioration agent may be used, or two or more types may be used. As an anti-deterioration agent, an antioxidant is especially preferable.

As an antioxidant, a radical chain inhibitor, a peroxide decomposer, etc. are mentioned, for example.

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

As a peroxide decomposer, a sulfur-based antioxidant, a phosphorus-based antioxidant, etc. are mentioned, for example.

As a phenolic antioxidant, a monophenolic antioxidant, a bisphenolic antioxidant, a polymer type phenolic antioxidant, etc. are mentioned, for example.

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

Examples of bisphenol-based antioxidants include 2,2'-methylenebis(4-methyl-6-tert-butylene) phenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 4,4'-thiobis(3-methyl-6-tert-butylphenol) , 4,4'-butylene bis(3-methyl-6-tert-butylphenol), 3,9-bis[1,1-dimethyl-2-[β-(3-tert-butyl) -4-Hydroxy-5-methylphenyl)propionyloxy]ethyl]2,4,8,10-tetraoxaspiro[5,5]undecane, etc.

Examples of high molecular weight phenolic antioxidants include 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 1,3,5-trimethyl base-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, tetra-[methylene-3-(3',5'-di-tert-butyl) yl-4'-hydroxyphenyl)propionate]methane, bis[3,3'-bis-(4'-hydroxy-3'-tert-butylphenyl)butyric acid]glycol ester, 1,3 ,5-Tris(3',5'-di-tert-butyl-4'-hydroxybenzyl)-S-triazine-2,4,6-(1H,3H,5H)trione, tocopherol, etc. .

Examples of sulfur-based antioxidants include dilauryl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate, and di-3,3'-thiodipropionate. Stearyl ester, etc.

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

Examples of the ultraviolet absorber include benzophenone-based ultraviolet absorbers, benzotriazole-based ultraviolet absorbers, salicylic acid-based ultraviolet absorbers, oxaniline-based ultraviolet absorbers, and cyanoacrylate-based ultraviolet absorbers agents, triazine-based UV absorbers, etc.

Examples of the benzophenone-based ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, and 2-hydroxy-4-octyloxydiphenyl Methyl ketone, 2-hydroxy-4-dodecane Oxybenzophenone, 2,2'-dihydroxy-4-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2- Hydroxy-4-methoxy-5-sulfobenzophenone, bis(2-methoxy-4-hydroxy-5-benzylphenyl)methane, etc.

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

As a salicylic acid type ultraviolet absorber, phenyl salicylate, p-tert-butylphenyl salicylate, p-octylphenyl salicylate, etc. are mentioned, for example.

Examples of cyanoacrylate-based ultraviolet absorbers include 2-cyano-3,3'-diphenylacrylic acid-2-ethylhexyl, 2-cyano-3,3'-diphenylacrylic acid ethyl ester, etc.

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

Examples of hindered amine-based light stabilizers include bis(2,2,6,6-tetramethyl-4-sebacic acid) piperidinyl) ester, bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, methyl sebacate-1,2,2,6,6-penta Methyl-4-piperidine ester, etc.

Examples of UV stabilizers include bis(octylphenyl)nickel sulfide, [2,2'-thiobis(4-tert-octylphenol)]-n-butylamine nickel salt, nickel complex- 3,5-Di-tert-butyl-4-hydroxybenzyl-phosphate monoethanolate, nickel dibutyldithiocarbamate, benzoate type quencher, dibutyldithiocarbamate Nickel formate etc.

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

Only one type of polyfunctional isocyanate compound may be used, or two or more types may be used.

As the polyfunctional isocyanate compound, any appropriate polyfunctional isocyanate compound that can be used in the urethane reaction can be used. As such a polyfunctional isocyanate compound, the "polyfunctional isocyanate compound" demonstrated in the item A-1-2 is mentioned, for example.

In the composition containing the urethane prepolymer and the polyfunctional isocyanate compound, any appropriate other components may be contained within the range not impairing the effects of the present invention. Examples of such other components include antioxidants, ultraviolet absorbers, light stabilizers, resin components, adhesion imparting agents, crosslinking retarders, inorganic fillers, organic fillers, metal powders, pigments, foils, Softeners, anti-aging agents, conductive agents, surface lubricants, leveling agents, preservatives, heat-resistant stabilizers, polymerization inhibitors, lubricants, solvents, etc.

Among these other components, it is a preferred embodiment to include anti-deterioration agents such as antioxidants, ultraviolet absorbers, and light stabilizers. By including the anti-deterioration agent in the adhesive composition, it is possible to have excellent anti-paste residue properties, for example, even if the formed adhesive layer is attached to the adherend and then stored in a heated state, the adherend is not likely to remain in the adherend. agent, etc. Only one type of anti-deterioration agent may be used, or two or more types may be used. As an anti-deterioration agent, an antioxidant is especially preferable. For details of antioxidants, ultraviolet absorbers, and light stabilizers, the descriptions in item A-1-2-1 can be cited.

The equivalent ratio of NCO groups to OH groups in the urethane prepolymer and the polyfunctional isocyanate compound is preferably 5.0 or less in terms of NCO groups/OH groups, more preferably 0.01 to 3.0, and still more preferably 0.02~2.0, more preferably 0.03~2.0, still more preferably 0.03~1.9, particularly preferably 0.05~1.9, and most preferably 0.05~1.8. If the equivalent ratio of NCO group/OH group is within the above range, it is possible to provide a product that does not easily peel off from the adherend, typically, in the manufacturing process of an optical member or an electronic member, the optical member is attached to the optical member. Or a surface protective film that does not easily peel off after the exposed surface of the electronic component, and can be easily peeled off when peeling is required. Moreover, when the equivalent ratio of NCO group / OH group exists in the said range, haze can be reduced. In particular, if the haze can be reduced to 3% or less, the inspectability of the surface protection film according to the embodiment of the present invention will be further improved.

Regarding the content ratio of the polyfunctional isocyanate compound, the polyfunctional isocyanate compound is preferably 0.01% by weight to 30% by weight, more preferably 0.05% by weight to 25% by weight, and still more preferably 0.1% by weight to 25% by weight, more preferably 0.5% by weight to 25% by weight, more preferably 0.5% by weight to 23% by weight, particularly preferably 1% by weight to 23% by weight, and most preferably 1% by weight to 21% by weight. If the content ratio of the polyfunctional isocyanate compound is Within the above range, it is possible to provide a situation where it is difficult to easily peel off the adherend. Typically, in the manufacturing process of the optical member or the electronic member, it is attached to the exposed surface of the optical member or the electronic member. A surface protection film that does not easily peel off afterward, and can be easily peeled off when peeling is required. Moreover, when the content ratio of a polyfunctional isocyanate compound exists in the said range, haze can be reduced. In particular, if the haze can be reduced to 3% or less, the inspectability of the surface protection film according to the embodiment of the present invention will be further improved.

<A-1-3. Ionic compound>

As the ionic compound, any appropriate ionic compound can be used within a range that does not impair the effects of the present invention. As such an ionic compound, an ionic liquid is preferable, and an ionic liquid containing a fluorine organic anion is more preferable. By making the adhesive composition contain both the ionic compound and the fluorine-based compound described below in addition to the base polymer, it is possible to provide a method of sufficiently suppressing the peeling electrostatic voltage without causing the optical member or the optical member to be peeled off. The surface protective film of the electronic component is damaged, and the surface protective film is typically a surface protective film containing an adhesive layer. In the manufacturing process of the optical component or the electronic component, in order to prevent the surface of the optical component or the electronic component Damaged during processing, assembly, inspection, transportation, etc., and attached to the exposed surface of the optical component or the electronic component.

Only one type of ionic compound may be used, or two or more types may be used.

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

As the ionic liquid, any suitable ionic liquid can be used within the range that does not impair the effect of the present invention. When the ionic liquid. As such an ionic liquid, an ionic liquid containing a fluoroorganic anion is preferable, and an ionic liquid consisting of a fluoroorganic anion and an onium cation is more preferable. By using an ionic liquid composed of a fluorine organic anion and an onium cation, and by using it in combination with the fluorine-based compound described below, it is possible to provide a more sufficient suppression of the peeling electrostatic voltage to make the optical member or the electron during peeling off. The surface protective film of which the component is less likely to be damaged, the surface protective film is typically a surface protective film containing an adhesive layer, which is used in the manufacturing steps of the optical component or electronic component, in order to prevent the surface of the optical component or the electronic component from being damaged. Damaged during processing, assembly, inspection, transportation, etc., and attached to the exposed surface of the optical component or the electronic component.

As the onium cation that can constitute the ionic liquid, any appropriate onium cation can be used within a range that does not impair the effects of the present invention. Such an onium cation is preferably at least one selected from the group consisting of nitrogen-containing onium cations, sulfur-containing onium cations, and phosphorus-containing onium cations. By selecting these onium cations and using them in combination with the fluorine-based compounds described below, a surface protection film that more fully suppresses the peeling electrostatic voltage and makes the optical member or the electronic member less likely to be damaged during peeling can be provided. , the surface protective film is typically a surface protective film comprising an adhesive layer, in the manufacturing steps of the optical member or electronic member, in order to prevent the surface of the optical member or the electronic member from being processed, assembled, inspected, transported Isochronically damaged and attached to the exposed surface of the optical member or the electronic member.

As an onium cation which can comprise an ionic liquid, it is preferable that it is at least 1 sort(s) chosen from the cations which have the structure represented by general formula (1)-(5).

[hua 1]

In the general formula (1), Ra represents a hydrocarbon group having 4 to 20 carbon atoms, and may contain a heteroatom. Rb and Rc are the same or different, and represent hydrogen or a hydrocarbon group having 1 to 16 carbon atoms, 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 with 2 to 20 carbon atoms, which may contain a heteroatom, and Re, Rf and Rg are the same or different, and represent hydrogen or a hydrocarbon group with 1 to 16 carbon atoms, and may contain a heteroatom.

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

In the general formula (4), Z represents a nitrogen atom, a sulfur atom or a phosphorus atom, and R1, Rm, Rn and Ro are the same or different, represent a hydrocarbon group having 1 to 20 carbon atoms, and may contain a hetero atom. 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 pyridinium cations, pyrrolidinium cations, piperidinium cations, cations having a pyrroline skeleton, and cations having a pyrrole skeleton.

Specific examples of the cation represented by the general formula (1) include, for example, the following: 1-ethylpyridinium cation, 1-butylpyridinium cation, 1-hexylpyridinium cation, 1-ethyl-3- Methylpyridinium cation, 1-butyl-3-methylpyridinium cation, 1-hexyl-3-methylpyridinium cation, 1-butyl-4-methylpyridinium cation, 1-octyl-4 -Pyridinium cations such as methylpyridinium cations, 1-butyl-3,4-dimethylpyridinium cations, 1,1-dimethylpyrrolidinium cations; 1-ethyl-1-methylpyrrolidine cations Onium 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-dipropylpyrrolidine Pyrrolidinium cations such as 1-propyl-1-butylpyrrolidinium cation and 1,1-dibutylpyrrolidinium cation; 1-propylpiperidinium cation, 1-pentylpiperidinium cation Cation, 1-methyl-1-ethylpiperidinium cation, 1-methyl-1-propylpiperidinium cation, 1-methyl-1-butylpiperidinium cation, 1-methyl-1 -Amylpiperidinium 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-heptylpiperidium cation pyridinium cation, 1-propyl-1-butylpiperidinium cation, 1,1-dimethylpiperidinium cation, 1,1-dipropylpiperidinium cation, 1,1-dibutylpiperidium cation Piperidinium cations such as pyridinium cations; 2-methyl-1-pyrroline cations; 1-ethyl-2-phenylindole cations; 1,2-dimethylindole cations; 1-ethylcarbazole cation.

Among them, from the viewpoint of exhibiting the effects of the present invention more preferably, the following are exemplified: 1-ethylpyridinium cation, 1-butylpyridinium cation, 1-hexylpyridinium cation, 1-ethyl-3-methylpyridinium cation, 1-butyl-3-methylpyridinium cation, 1-hexyl-3-methylpyridinium cation, 1-butyl-4-methylpyridinium cation , 1-octyl-4-methylpyridinium cation and other pyridinium cations; 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 and other pyrrolidinium cations; 1-methyl-1-ethylpiperidinium cation, 1-methyl-1-propylpiperidine Onium 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, Piperidinium cations such as 1-ethyl-1-hexylpiperidinium cation, 1-ethyl-1-heptylpiperidinium cation, 1-propyl-1-butylpiperidinium cation, etc., more preferably 1 - Hexylpyridinium cation, 1-ethyl-3-methylpyridinium cation, 1-butyl-3-methylpyridinium cation, 1-octyl-4-methylpyridinium cation, 1-methyl- 1-propylpyrrolidinium cation, 1-methyl-1-propylpiperidinium cation.

As a cation represented by general formula (2), an imidazolium cation, an tetrahydropyrimidinium cation, a dihydropyrimidinium cation, etc. are mentioned, for example.

Specific examples of the cation represented by the general formula (2) include, for example, the following: 1,3-dimethylimidazolium cation, 1,3-diethylimidazolium cation, 1-ethyl-3-methyl cation Imidazolium cation, 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, 1-tetradecyl-3-methylimidazolium cation , 1,2-dimethyl-3-propylimidazolium cation, 1-ethyl-2,3-dimethylimidazolium cation, 1-butyl-2,3-dimethylimidazolium cation, 1 - imidazolium cations such as 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 base-1,4,5,6-tetrahydropyrimidinium cations; 1,3-dimethyl-1,4-dihydropyrimidinium cations, 1,3-dimethyl-1, 6-dihydropyrimidinium cation, 1,2,3-trimethyl-1,4-dihydropyrimidinium cation, 1,2,3-trimethyl-1,6-dihydropyrimidinium cation, 1, Dihydropyrimidinium cations such as 2,3,4-tetramethyl-1,4-dihydropyrimidinium cation and 1,2,3,4-tetramethyl-1,6-dihydropyrimidinium cation.

Among them, 1,3-dimethylimidazolium cations, 1,3-diethylimidazolium cations, 1-ethyl-3-methyl cations, and 1-ethyl-3-methyl cations are preferred from the viewpoint of exhibiting the effects of the present invention. Imidazolium cation, 1-butyl-3-methylimidazolium cation, 1-hexyl-3-methylimidazolium cation, 1-octyl-3-methylimidazolium cation, 1-decyl-3-methyl cation imidazolium cations such as base imidazolium cation, 1-dodecyl-3-methylimidazolium cation, 1-tetradecyl-3-methylimidazolium cation, etc., more preferably, 1-ethyl-3- Methylimidazolium cation, 1-hexyl-3-methylimidazolium cation.

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

Specific examples of the cation represented by the general formula (3) include, for example, the following: 1-methylpyrazolium cation, 3-methylpyrazolium cation, 1-ethyl-2-methylpyrazoline Onium cation, 1- Ethyl-2,3,5-trimethylpyrazolium cation, 1-propyl-2,3,5-trimethylpyrazolium cation, 1-butyl-2,3,5-trimethyl cation Pyrazolonium cations such as pyrazolium cation; 1-ethyl-2,3,5-trimethylpyrazolinium cation, 1-propyl-2,3,5-trimethylpyrazolinium cation, Pyrazolinium cations such as 1-butyl-2,3,5-trimethylpyrazolinium cation.

Examples of cations represented by the general formula (4) include tetraalkylammonium cations, trialkyl perionium cations, tetraalkylphosphonium cations, or a part of the above-mentioned alkyl groups consisting of an alkenyl group or an alkoxy group, and then an epoxy group. Substitutes etc.

Specific examples of the cation represented by the general formula (4) include, for example, tetramethylammonium cation, tetraethylammonium cation, tetrabutylammonium cation, tetrapentylammonium cation, tetrahexylammonium cation, tetraheptylammonium cation Ammonium cation, triethylmethylammonium cation, tributylethylammonium cation, trimethylpropylammonium cation, trimethyldecylammonium cation, N,N-diethyl-N-methyl-N- (2-Methoxyethyl)ammonium cation, glycidyl trimethylammonium cation, trimethyl pericium cation, triethyl pericynium cation, tributyl pericynium cation, trihexyl pericynium cation, diethylmethyl pericium cation Cation, Dibutylethyl Phosphonium Cation, Dimethyl Decyl Phosphonium Cation, Tetramethyl Phosphonium Cation, Tetraethyl Phosphonium Cation, Tetrabutyl Phosphonium Cation, Tetrahexyl Phosphonium Cation, Tetraoctyl Phosphonium Cation, Triethyl Phosphonium Cation Methylphosphonium cation, tributylethylphosphonium cation, trimethyldecylphosphonium cation, diallyldimethylammonium cation, etc.

Among them, in terms of the aspect that the effect of the present invention can be more exhibited, the following are preferred: triethylmethylammonium cation, tributylethylammonium cation, trimethyldecylammonium cation, diethyl ammonium cation, and the like. Methyl perionium cation, dibutylethyl perionium cation, dimethyldecyl perionium cation, triethyl perionate Asymmetric tetraalkylammonium cations, trialkyl perionium cations, tetraalkylphosphonium cations, such as methylmethylphosphonium cation, tributylethylphosphonium cation, trimethyldecylphosphonium cation, etc.; or N,N-diethyl cation Alkyl-N-methyl-N-(2-methoxyethyl)ammonium cation, glycidyltrimethylammonium cation, diallyldimethylammonium cation, N,N-dimethyl-N- Ethyl-N-propylammonium cation, N,N-dimethyl-N-ethyl-n-butylammonium cation, N,N-dimethyl-N-ethyl-N-pentylammonium cation, N ,N-dimethyl-N-ethyl-N-hexylammonium cation, N,N-dimethyl-N-ethyl-N-heptylammonium cation, N,N-dimethyl-N-ethyl -N-nonylammonium cation, N,N-dimethyl-N,N-dipropylammonium cation, N,N-diethyl-N-propyl-n-butyl ammonium cation, N,N-dipropylammonium cation Methyl-N-propyl-N-pentylammonium cation, N,N-dimethyl-N-propyl-N-hexylammonium cation, N,N-dimethyl-N-propyl-N-heptyl cation base ammonium cation, N,N-dimethyl-n-butyl ester-N-hexylammonium cation, N,N-diethyl-n-butyl ester-N-heptylammonium cation, N,N-dimethyl-N - Amyl-N-hexylammonium cation, N,N-dimethyl-N,N-dihexylammonium cation, trimethylheptylammonium cation, N,N-diethyl-N-methyl-N- Propylammonium cation, N,N-diethyl-N-methyl-N-pentylammonium cation, N,N-diethyl-N-methyl-N-heptylammonium cation, N,N-diethylammonium cation Ethyl-N-propyl-N-pentylammonium cation, triethylpropylammonium cation, tripentylammonium cation, triethylheptylammonium cation, N,N-dipropyl-N-methyl- N-ethylammonium cation, N,N-dipropyl-N-methyl-N-pentylammonium cation, N,N-dipropyl-n-butyl ester-N-hexylammonium cation, N,N-dipropylammonium cation Propyl-N,N-dihexylammonium cation, N,N-dibutyl-N-methyl-N-pentylammonium cation, N,N-dibutyl-N-methyl-N-hexylammonium cation , trioctylmethylammonium cation, N-methyl-N-ethyl-N-propyl-N-pentylammonium cation, more preferably trimethylpropylammonium cation.

As the fluoroorganic anion that can constitute the ionic liquid, any appropriate fluoroorganic anion can be used within a range that does not impair the effects of the present invention. This fluoroorganic anion can be fully fluorinated (perfluorinated), also partially fluorinated.

Examples of such fluoroorganic anions include fluorinated arylsulfonates, perfluoroalkanesulfonates, bis(fluorosulfonyl)imide, and bis(perfluoroalkanesulfonyl)imide. Amines, cyanoperfluoroalkanesulfonamides, bis(cyano)perfluoroalkanesulfonamides, cyano-bis-(perfluoroalkanesulfonamides), tris(perfluoroalkanesulfonamides) sulfonyl) methide, trifluoroacetate, perfluoroalkylate, tris(perfluoroalkanesulfonyl)methide, (perfluoroalkanesulfonyl)trifluoroacetamide and the like.

Among these fluoroorganic anions, more preferred are perfluoroalkanesulfonates, bis(fluorosulfonyl)imide, bis(perfluoroalkanesulfonyl)imide, and more specifically, tris fluoromethanesulfonate, pentafluoroethanesulfonate, heptafluoropropanesulfonate, nonafluorobutanesulfonate, bis(fluorosulfonyl)imide, bis(trifluoromethanesulfonyl)imide .

As a specific example of an ionic liquid, it can select and use suitably from the combination of the said cation component and the said anionic component. Specific examples of such ionic liquids include, for example, 1-hexylpyridinium bis(fluorosulfonyl)imide, 1-ethyl-3-methylpyridinium trifluoromethanesulfonate, 1- Ethyl-3-methylpyridinium pentafluoroethanesulfonate, 1-ethyl-3-methylpyridinium heptafluoropropanesulfonate, 1-ethyl-3-methylpyridinium nonafluorobutanesulfonic acid salt, 1-butyl-3-methylpyridinium triflate, 1-butyl-3-methylpyridinium bis(trifluoromethanesulfonyl)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(fluorosulfonyl)imide, 1-methyl-1-butylpyrrolidine Onium bis(trifluoromethanesulfonyl)imide, 1-methyl-1-pentylpyrrolidinium bis(trifluoromethanesulfonyl)imide, 1-methyl-1-hexylpyrrolidinium Bis(trifluoromethanesulfonyl)imide, 1-methyl-1-heptylpyrrolidinium bis(trifluoromethanesulfonyl)imide, 1-ethyl-1-propylpyrrolidinium Bis(trifluoromethanesulfonyl)imide, 1-ethyl-1-butylpyrrolidinium bis(trifluoromethanesulfonyl)imide, 1-ethyl-1-pentylpyrrolidinium Bis(trifluoromethanesulfonyl)imide, 1-ethyl-1-hexylpyrrolidinium bis(trifluoromethanesulfonyl)imide, 1-ethyl-1-heptylpyrrolidinium bis (trifluoromethanesulfonyl)imide, 1,1-dipropylpyrrolidinium bis(trifluoromethanesulfonyl)imide, 1-propyl-1-butylpyrrolidinium bis(trifluoromethanesulfonyl)imide fluoromethanesulfonyl)imide, 1,1-dibutylpyrrolidinium bis(trifluoromethanesulfonyl)imide, 1-propylpiperidinium bis(trifluoromethanesulfonyl)imide Imine, 1-pentylpiperidinium bis(trifluoromethanesulfonyl)imide, 1,1-dimethylpiperidinium bis(trifluoromethanesulfonyl)imide, 1-methyl -1-Ethylpiperidinium bis(trifluoromethanesulfonyl)imide, 1-methyl-1-propylpiperidinium bis(trifluoromethanesulfonyl)imide, 1-methyl -1-propylpiperidinium bis(fluorosulfonyl)imide, 1-methyl-1-butylpiperidinium bis(trifluoromethanesulfonyl)imide, 1-methyl-1 - Amylpiperidinium bis(trifluoromethanesulfonyl)imide, 1-methyl-1-hexylpiperidinium bis(trifluoromethanesulfonyl)imide, 1-methyl-1- Heptylpiperidinium bis(trifluoromethanesulfonyl)imide, 1-ethyl-1-propylpiperidinium bis(trifluoromethanesulfonyl)imide, 1-ethyl-1- Butylpiperidinium bis(trifluoromethanesulfonyl)imide, 1-ethyl-1-pentylpiperidinium bis(trifluoromethanesulfonyl)imide, 1-ethyl-1- Hexylpiperidinium bis(trifluoromethanesulfonyl)imide, 1-ethyl-1-heptylpiperidinium bis(trifluoromethanesulfonyl)imide, 1,1-dipropylpiperidine Peridinium bis(trifluoromethanesulfonyl)imide, 1-propyl-1-butylpiperidinium bis(trifluoromethanesulfonyl)imide, 1,1-dibutylpiperidinium Bis(trifluoromethanesulfonyl)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 yl-1-propylpyrrolidinium bis(pentafluoroethanesulfonyl)imide, 1-ethyl-1-butylpyrrolidinium bis(pentafluoroethanesulfonyl)imide, 1-ethyl yl-1-pentylpyrrolidinium bis(pentafluoroethanesulfonyl)imide, 1-ethyl-1-hexylpyrrolidinium bis(pentafluoroethanesulfonyl)imide, 1-ethyl -1-heptylpyrrolidinium bis(pentafluoroethylsulfonyl)imide, 1,1-dipropylpyrrolidinium bis(pentafluoroethylsulfonyl)imide, 1-propyl-1 -Butylpyrrolidinium bis(pentafluoroethylsulfonyl)imide, 1,1-dibutylpyrrolidinium bis(pentafluoroethylsulfonyl)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-heptylpiperidinium bis(pentafluoroethanesulfonyl) Imide, 1-Ethyl-1-propylpiperidinium bis(pentafluoroethanesulfonyl)imide, 1-ethyl-1-butylpiperidinium bis(pentafluoroethanesulfonyl) Imide, 1-ethyl-1-pentylpiperidinium bis(pentafluoroethanesulfonyl)imide, 1-ethyl-1-hexylpiperidinium bis(pentafluoroethanesulfonyl)imide Imine, 1-Ethyl-1-heptylpiperidinium bis(pentafluoroethanesulfonyl)imide, 1,1-dipropylpiperidinium bis(pentafluoroethanesulfonyl)imide , 1-propyl-1-butylpiperidinium bis(pentafluoroethanesulfonyl)imide, 1,1-dibutylpiperidinium bis(pentafluoroethanesulfonyl)imide, 1 -Ethyl-3-methylimidazolium trifluoroacetate, 1-ethyl-3-methylimidazolium heptafluorobutyrate, 1-ethyl-3-methylimidazolium trifluoromethanesulfonate, 1-ethyl-3-methylimidazolium heptafluoropropanesulfonate, 1-ethyl-3-methylimidazolium nonafluorobutanesulfonate, 1-ethyl-3-methylimidazolium bis(tris fluoromethanesulfonyl)imide, 1-ethyl-3-methylimidazolium bis(fluorosulfonyl)imide, 1-ethyl-3-methylimidazolium bis(pentafluoroethanesulfonyl) yl) imide, 1-ethyl-3-methylimidazolium tris(trifluoromethanesulfonyl) methide, 1-butane yl-3-methylimidazolium trifluoroacetate, 1-butyl-3-methylimidazolium heptafluorobutyrate, 1-butyl-3-methylimidazolium trifluoromethanesulfonate, 1- Butyl-3-methylimidazolium perfluorobutanesulfonate, 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, 1-hexyl-3-methylimidazolium Triflate, 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-trimethylpyridine azolium 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-trimethylpyrazolium bis(pentafluoroethanesulfonyl) ) imide, 1-butyl-2,3,5-trimethylpyrazolium bis(pentafluoroethanesulfonyl)imide, 1-ethyl-2,3,5-trimethylpyridine azolium (trifluoromethanesulfonyl) trifluoroacetamide, 1-propyl-2,3,5-trimethylpyrazolium (trifluoromethanesulfonyl) trifluoroacetamide, 1-butane Alkyl-2,3,5-trimethylpyrazolium (trifluoromethanesulfonyl)trifluoroacetamide, trimethylpropylammonium bis(trifluoromethanesulfonyl)imide, N,N - Dimethyl-N-ethyl-N-propylammonium bis(trifluoromethanesulfonyl)imide, N,N-dimethyl-N-ethyl-n-butylammonium bis(trifluoromethyl) Sulfonyl) imide, N,N-dimethyl-N-ethyl-N-pentylammonium bis(trifluoromethanesulfonyl)imide, N,N-dimethyl-N-ethyl Alkyl-N-hexylammonium bis(trifluoromethanesulfonyl)imide, N,N-dimethyl-N-ethyl-N-heptylammonium bis(trifluoromethanesulfonyl)imide, N,N-Dimethyl-N-ethyl-N-nonylammonium bis(trifluoromethanesulfonyl)imide, N,N-dimethyl-N,N-dipropylammonium bis(trifluoromethanesulfonyl)imide fluoromethanesulfonyl)imide, N,N-dimethyl-N-propyl-n-butyl ester ammonium bis(trifluoromethanesulfonyl)imide, N,N-dimethyl-N- Propyl-N-pentylammonium bis(trifluoromethanesulfonyl)imide, N,N-dimethyl-N-propyl-N-hexylammonium bis(trifluoromethanesulfonyl)imide , N,N-dimethyl-N-propyl-N-heptylammonium bis(trifluoromethanesulfonyl)imide, N,N-dimethyl-n-butyl ester-N-hexylammonium bis( trifluoromethanesulfonyl)imide, N,N-dimethyl-n-butyl ester-N-heptylammonium bis(trifluoromethanesulfonyl)imide, N,N-dimethyl-N -Amyl-N-hexylammonium bis(trifluoromethanesulfonyl)imide, N,N-dimethyl -N,N-dihexylammonium bis(trifluoromethanesulfonyl)imide, trimethylheptylammonium bis(trifluoromethanesulfonyl)imide, N,N-diethyl-N- Methyl-N-propylammonium bis(trifluoromethanesulfonyl)imide, N,N-diethyl-N-methyl-N-pentylammonium bis(trifluoromethanesulfonyl)imide Amine, N,N-diethyl-N-methyl-N,N-heptylammonium bis(trifluoromethanesulfonyl)imide, N,N-diethyl-N-propyl-N- Amylammonium bis(trifluoromethanesulfonyl)imide, triethylpropylammonium bis(trifluoromethanesulfonyl)imide, triamylammonium bis(trifluoromethanesulfonyl)imide Amine, triethylheptylammonium bis(trifluoromethanesulfonyl)imide, N,N-dipropyl-N-methyl-N-ethylammonium bis(trifluoromethanesulfonyl)imide Amine, N,N-dipropyl-N-methyl-N-pentylammonium bis(trifluoromethanesulfonyl)imide, N,N-dipropyl-n-butyl ester-N-hexylammonium bis (trifluoromethanesulfonyl)imide, N,N-dipropyl-N,N-dihexylammonium bis(trifluoromethanesulfonyl)imide, N,N-dibutyl-N- Methyl-N-pentylammonium bis(trifluoromethanesulfonyl)imide, N,N-dibutyl-N-methyl-N-hexylammonium bis(trifluoromethanesulfonyl)imide , trioctylmethylammonium bis(trifluoromethanesulfonyl)imide, N-methyl-N-ethyl-N-propyl-N-pentylammonium bis(trifluoromethanesulfonyl)imide Imine, 1-butylpyridinium(trifluoromethanesulfonyl)trifluoroacetamide, 1-butyl-3-methylpyridinium(trifluoromethanesulfonyl)trifluoroacetamide, 1- Ethyl-3-methylimidazolium(trifluoromethanesulfonyl)trifluoroacetamide, tetrahexylammonium bis(trifluoromethanesulfonyl)imide, diallyldimethylammonium trifluoromethane Sulfonate, diallyldimethylammonium bis(trifluoromethanesulfonyl)imide, diallyldimethylammonium bis(pentafluoroethanesulfonyl)imide, N,N- Diethyl-N-methyl-N-(2-methoxyethyl)ammonium triflate, N,N-diethyl-N-methyl-N-(2-methoxyethyl) yl)ammonium bis(trifluoromethanesulfonyl)imide, N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium bis(pentafluoroethanesulfonyl) Imide, Glycidyltrimethylammonium triflate, Glycidyltrimethylammonium bis(trifluoromethanesulfonyl)imide, Glycidyltrimethylammonium bis(pentafluoroethyl) Sulfonyl)imide, Diallyldimethylammonium bis(trifluoromethanesulfonyl)imide, Diallyldimethylbis(pentafluoroethanesulfonyl)imide, Lithium Bis(trifluoromethanesulfonyl)imide, lithium bis(fluorosulfonyl)imide, and the like.

Among the plasma liquids, more preferred are 1-hexylpyridinium bis(fluorosulfonyl)imide, 1-ethyl-3-methylpyridinium trifluoromethanesulfonate, 1-ethyl-3 -Methylpyridinium pentafluoroethanesulfonate, 1-ethyl-3-methylpyridinium heptafluoropropanesulfonate, 1-ethyl-3-methylpyridinium nonafluorobutanesulfonate, 1- Butyl-3-methylpyridinium triflate, 1-butyl-3-methylpyridinium bis(trifluoromethanesulfonyl)imide, 1-octyl-4-methylpyridine Onium 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(fluoro Sulfonyl)imide, 1-ethyl-3-methylimidazolium trifluoromethanesulfonate, 1-ethyl-3-methylimidazolium heptafluoropropanesulfonate, 1-ethyl-3 - Methylimidazolium bis(trifluoromethanesulfonyl)imide, 1-ethyl-3-methylimidazolium bis(fluorosulfonyl)imide, 1-hexyl-3-methylimidazolium Bis(fluorosulfonyl)imide, trimethylpropylammonium bis(trifluoromethanesulfonyl)imide, lithium bis(trifluoromethanesulfonyl)imide, lithium bis(fluorosulfonyl)imide base) imide.

A commercially available ionic liquid can be used, or it can be synthesized as described below. The method for synthesizing the ionic liquid is not particularly limited as long as the target ionic liquid can be obtained. Generally, the method described in the document "Ionic Liquid-Development Frontier and Future-" (issued by CMC Publishing Co., Ltd.) can be used. The halide method, hydroxide method, acid ester method, complex method and neutralization method, etc.

Hereinafter, regarding the halide method, hydroxide method, acid ester method, complexation method and neutralization method, the synthesis method of nitrogen-containing onium salt will be described as an example. Ionic liquids can also be obtained by the same method.

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

The target anion is obtained by reacting the obtained halide with an acid (HA) or a salt (MA, M is a cation that forms a salt with the target anion such as ammonium, lithium, sodium, potassium, etc.) with the anion structure (A ⁻ ) of the target ionic liquid. Ionic liquid (R ₄ NA).

[Chemical 2] (1)R ₃ N+RX→R ₄ NX(X:Cl,Br,I) (2)R ₄ NX+HA→R ₄ NA+HX (3)R ₄ NX+MA→R ₄ NA+MX (M: NH ₄ , Li, Na, K, Ag, etc.)

The hydroxide method is a method carried out by the reactions shown in the reaction formulas (4) to (8). First, the halide (R ₄ NX) is electrolyzed by an ion exchange membrane method (reaction formula (4)), an OH type ion exchange resin method (reaction formula (5)), or a reaction with silver oxide (Ag ₂ O) ( Reaction formula (6)) to obtain hydroxide (R ₄ NOH) (using chlorine, bromine and iodine as halogen).

The target ionic liquid (R ₄ NA) was obtained by using the reaction of the reaction formulas (7) to (8) in the same manner as the above-mentioned halogenation method with respect to the obtained hydroxide.

[Chemical 3] (4) R ₄ NX+H ₂ O→R ₄ NOH+1/2H ₂ +1/2X ₂ (X: Cl, Br, I) (5) R ₄ NX+P-OH→R ₄ NOH+PX (P-OH: OH type ion exchange resin) (6)R ₄ NX+1/2Ag ₂ O+1/2H ₂ O→R ₄ NOH+AgX (7)R ₄ NOH+HA→R ₄ NA +H ₂ O (8) R ₄ NOH+MA→R ₄ NA+MOH (M: NH ₄ , Li, Na, K, Ag, etc.)

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

The target ionic liquid (R ₄ NA) was obtained by using the reaction of the reaction formulae (10) to (11) in the same manner as the above-mentioned halogenation method with respect to the obtained acid ester. Moreover, an ionic liquid can also be obtained directly by using methyl trifluoromethanesulfonate, methyl trifluoroacetate, etc. as an acid ester.

The neutralization method is a method carried out by the reaction shown in the reaction formula (12). Tertiary amines can be reacted 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, etc. and obtained.

[Chemical 5] (12) R ₃ N+HZ→R ₃ HN ⁺ Z ^- [HZ: 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 and other organic acids]

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

<A-1-4. Fluorine Compounds>

As the fluorine-based compound, any appropriate fluorine-based compound can be used within a range that does not impair the effects of the present invention. By making the adhesive composition contain both the fluorine-based compound and the above-mentioned ionic compound in addition to the base polymer, it is possible to provide the optical member or the electronic member that can sufficiently suppress the peeling electrostatic voltage without causing the optical member or the electronic member to be peeled off. Damaged surface protection film, which is typically a surface protection film containing an adhesive layer, in the manufacturing steps of optical members or electronic members, in order to prevent the surface of the optical member or the electronic member from being processed , assembling, inspecting, transporting, etc., and sticking to the exposed surface of the optical component or the electronic component.

Only one type of fluorine-based compound may be used, or two or more types may be used.

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

The fluorine-containing compound includes, for example, 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 fluorine C1 such as fluoromethane, fluoroethane, fluoropropane, fluoroisopropane, fluorobutane, fluoroisobutane, fluorotert-butane, fluoropentane, and fluorohexane. -C10 alkanes, etc.

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"). The effect of the present invention can be remarkably exhibited by including (combining) both the ionic compound and the above-mentioned "specific fluorine-based compound". The reason for this is presumed to be that, as described above, the ionic compound capable of exhibiting an antistatic effect and the fluorine-based compound (preferably, a specific fluorine-based compound) coexist in the adhesive composition, and the fluorine-based compound The synergistic effect of the compound (preferably, a specific fluorine-based compound) makes the ionic compound segregated on the surface side of the adhesive layer (the side attached to the adherend). As a fluorine-containing group, a fluorine-containing alkyl group (for example, _CF3- etc.) and/or a fluorine-containing alkylene group (for example, _-CF2 - _CF2- etc.) are mentioned typically. Hydrophilic group refers to a group with hydrophilicity, and hydrophilicity is translated as "hydrophilic" in English, which means "affinity with water", which is a well-known characteristic of the industry (for example, refer to McGraw-Hill Glossary of Science and Technology Great Dictionary (Revised 3rd Edition, Nikkan Kogyo Shimbun, etc.). A lipophilic group refers to a group with lipophilicity, and lipophilicity is translated as "lipophilic" in English, which means "affinity with oil", which is a well-known characteristic of the industry (for example, refer to McGraw-Hill Glossary of Science and Technology Great Dictionary (Revised 3rd Edition, Nikkan Kogyo Shimbun, etc.).

As the "specific fluorine-based compound", an oligomer containing a fluorine-containing group, a hydrophilic group, and a lipophilic group is more preferable in that the effect 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.

As for the preferred embodiment of the fluorine-containing compound, in terms of the aspect that can better express the effect of the present invention, the surface tension is preferably 26.0 mN/m~ 27.0 mN/m of fluorine-containing compound (the surface tension of toluene is 27.9 mN/m). In this way, if the surface tension of the fluorine-containing compound is in a very narrow specific range of 26.0mN/m~27.0mN/m when it is made into a 0.1% toluene solution, the effect of the present invention can be better exhibited, especially the It exhibited an unexpectedly remarkable effect of sufficiently suppressing the peeling electrostatic voltage of glass and the peeling electrostatic voltage of resin. In particular, when it is assumed that the surface protection film in the preferred embodiment of the present invention is used for a predetermined purpose, that is, the purpose of attaching to the exposed surface of an optical member or an electronic member, it can exhibit a peeling electrostatic voltage regardless of whether it is a glass. , or the effect of sufficiently suppressing the peeling electrostatic voltage of the resin is extremely important.

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 the surface tension is 26.0 mN/m~27.0 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 the surface tension is 26.0mN/m~27.0mN/ when it is made into a 0.1% toluene solution m (the surface tension of toluene is 27.9 mN/m), the effect of the present invention can be better exhibited, especially, the peeling electrostatic voltage of glass and the peeling electrostatic voltage of resin can be extremely sufficiently suppressed. Unexpected and very significant effect. In particular, when it is assumed that the surface protection film in the preferred embodiment of the present invention is used for a predetermined purpose, that is, the purpose of attaching to the exposed surface of an optical member or an electronic member, it can exhibit a peeling electrostatic voltage regardless of whether it is a glass. , it is also extremely important for the effect of extremely sufficient suppression of the peeling electrostatic voltage of the resin.

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

MEGAFAC Series manufactured by DIC (stock):

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

Surflon Series manufactured by AGC Qingmei Chemical Co., Ltd.:

Typically, "S-242", "S-243", "S-386", etc.

FC Series manufactured by Sumitomo 3M Co., Ltd.:

Typically, "FC-4430", "FC-4432", etc.

FTERGENT Series manufactured by NEOS (stock):

Typically, "FTERGENT100", "FTERGENT100C", "FTERGENT110", "FTERGENT150", "FTERGENT150CH", "FTERGENT250", "FTERGENT400SW" and the like.

PF Series manufactured by Kitamura Chemical Industry Co., Ltd.:

Typically, "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 fluorine-based compound, for example, known resins can be used, and examples thereof include International Publication No. 94/06870, Japanese Patent Laid-Open No. 8-12921, Japanese Patent Laid-Open No. 10-72569, Japanese Patent Laid-Open No. 10-72569, The hydroxyl group-containing fluororesin described in Japanese Patent Laid-Open No. 4-275379, International Publication No. 97/11130, International Publication No. 96/26254, and the like. Examples of other hydroxyl-containing fluororesins include: Japanese Patent Laid-Open No. 8-231919, Japanese Patent Laid-Open No. 10-265731, Japanese Patent Laid-Open No. 10-204374, and Japanese Patent Laid-Open No. Hei 8-12922 Fluoroolefin copolymers and the like described in the gazette and the like. In addition, copolymers of hydroxyl-containing compounds and compounds having a fluorinated alkyl group, fluorine-containing organic compounds obtained by copolymerization of hydroxyl-containing compounds and fluorine-containing compounds, fluorine-containing compounds containing hydroxyl-containing organic compounds, etc. . Examples of commercially available products of such a hydroxyl group-containing fluorine-based compound include a product named "Lumiflon" (manufactured by Asahi Glass Co., Ltd.), a product named "CEFRAL COAT" (manufactured by Chuo Glass Co., Ltd.), A product named "ZAFFLON" (manufactured by Toa Gosei Co., Ltd.), a product named "ZEFFLE" (manufactured by Daikin Industries, Ltd.), etc.

Examples of the crosslinkable functional group-containing fluorine-based compound include carboxylic acid compounds having a fluorinated alkyl group such as perfluorooctanoic acid, compounds having a crosslinkable functional group, and compounds having a fluorinated alkyl group. Fluorine-containing organic compounds obtained by copolymerization of cross-linkable functional group-containing compounds and fluorine-containing compounds, fluorine-containing compounds containing cross-linkable functional group-containing compounds, etc. Examples of commercially available products of such a crosslinkable functional group-containing fluorine-based compound include "MEGAFAC F-570", "MEGAFAC RS-55", "MEGAFAC RS-56", and "MEGAFAC RS-72- Products of "K", "MEGAFAC RS-75", "MEGAFAC RS-76-E", "MEGAFAC RS-76-NS", "MEGAFAC RS-78", "MEGAFAC RS-90" (manufactured by DIC Corporation) Wait.

Among the fluorine-containing compounds that can be obtained in the form of commercial products, DIC (stock ) manufactured the following fluorine-containing compound: "MEGAFAC F-477" (oligomer containing fluorine-containing group, hydrophilic group and lipophilic group, surface tension = 26.4mN/m in the case of 0.1% toluene solution) ; "MEGAFAC F-551-A" (oligomer containing fluorine group and lipophilic group, surface tension = 25.6mN/m when made into 0.1% toluene solution); "MEGAFAC F-553" (containing Oligomers containing fluorine group, hydrophilic group and lipophilic group, surface tension = 26.4mN/m when made into 0.1% toluene solution); "MEGAFAC F-554" (containing fluorine group and lipophilic group The oligomer of 0.1% toluene solution, the surface tension = 25.0mN/m); "MEGAFAC F-555-A" (oligomer containing fluorine group, hydrophilic group and lipophilic group, In the case of making 0.1% toluene solution, surface tension=20.4mN/m); "MEGAFAC F-557" (oligomer containing fluorine group, hydrophilic group and lipophilic group, surface tension = 26.3mN/m when prepared as a 0.1% toluene solution); "MEGAFAC F-559" ( Oligomers containing fluorine-containing groups, hydrophilic groups and lipophilic groups, surface tension = 26.1 mN/m in the case of 0.1% toluene solution); "MEGAFAC F-563" (containing fluorine-containing groups and lipophilic oligomer based on 0.1% toluene solution, surface tension = 20.2mN/m); "MEGAFAC F-569" (oligomer containing fluorine-containing and hydrophilic groups, in 0.1% In the case of the toluene solution, the surface tension = 19.7 mN/m) and the like.

Among the fluorine-containing compounds that can be obtained in the form of commercial products, as the above-mentioned "oligomer containing fluorine-containing groups, hydrophilic groups and lipophilic groups, the surface tension is 26.0 when it is made into a 0.1% toluene solution. mN/m~27.0mN/m (the surface tension of toluene is 27.9mN/m), fluorine-containing compounds, typically, the following fluorine-containing compounds manufactured by DIC Corporation: "MEGAFAC F-477" (Surface tension = 26.4mN/m when the oligomer containing fluorine-containing group, hydrophilic group and lipophilic group is made into 0.1% toluene solution); "MEGAFAC F-553" (containing fluorine-containing group, hydrophilic group The oligomer of lipophilic and lipophilic groups, when made into 0.1% toluene solution, the surface tension = 26.4mN/m); "MEGAFAC F-557" (containing a fluorine-containing group, a hydrophilic group and a lipophilic group Oligomer, surface tension = 26.3mN/m in the case of 0.1% toluene solution); "MEGAFAC F-559" (oligomer containing fluorine, hydrophilic and lipophilic groups, prepared in In the case of 0.1% toluene solution, the surface tension = 26.1 mN/m), etc.

<A-1-5. Other ingredients>

The adhesive composition may contain any appropriate other components within the range that does not impair the effects of the present invention. Examples of such other components include resin components, cross-linking accelerators, cross-linking catalysts, silane coupling agents, silicone-based additives such as modified silicone oil, adhesion-imparting resins (rosin derivatives, polyterpene resins) , petroleum resin, oil-soluble phenol, etc.), anti-aging agent, inorganic filler, organic filler, metal powder, colorant (pigment or dye, etc.), foil, ultraviolet absorber, antioxidant, light stabilizer, chain Transfer agent, plasticizer, softener, conductive agent, stabilizer, surface lubricant, preservative, heat-resistant stabilizer, polymerization inhibitor, lubricant, solvent, catalyst, etc.

As other components in the adhesive composition, typically, modified silicone oil can be contained within a range not impairing the effects of the present invention. By including the modified silicone oil in the adhesive composition, the effect of antistatic properties can be exhibited. In particular, by using together with an ionic liquid, the effect of antistatic properties can be more effectively expressed.

When the adhesive composition contains the modified silicone oil, the content ratio of the modified silicone oil is relative to 100 parts by weight of the base polymer, preferably 0.001 parts by weight to 50 parts by weight, more preferably 0.005 parts by weight ~40 parts 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 to the above range, the effect of antistatic properties can be more effectively exhibited.

As the modified silicone oil, any appropriate modified silicone oil can be used within a range that does not impair the effects of the present invention. As such a modified silicone oil, the modified silicone oil available from Shin-Etsu Chemical Industry Co., Ltd. is mentioned, for example.

As the modified silicone oil, polyether-modified silicone oil is preferred. By using polyether modified silicone oil, the effect of antistatic properties can be more effectively exhibited.

As the polyether-modified silicone oil, a side-chain type polyether-modified silicone oil, a double-terminal type polyether-modified silicone oil, and the like can be mentioned. Among them, two-terminal type polyether-modified silicone oil is preferable in that the effect of antistatic properties can be sufficiently and more effectively exhibited.

≪A-2. Substrate layer≫

The base material layer may be only one layer, or may be two or more layers. The substrate layer may be extended.

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 winding body that is easy to unwind on the surface of the base material layer without the adhesive layer, for example, aliphatic amides, polyethyleneimine, long-chain alkyl-based additives, etc. can be added to the base material layer. Perform release treatment, or set up a coating containing any appropriate release agent such as silicone, long-chain alkyl, and fluorine.

As the material of the base material layer, any appropriate material can be adopted according to the application. For example, plastic, paper, metal film, nonwoven fabric, etc. are mentioned. Preferably it is plastic. That is, the base material layer is preferably a plastic film. The base material layer may be composed of one kind of material, or may be composed of two or more kinds of materials. For example, it may consist of two or more types of plastics.

As said plastics, a polyester-type resin, a polyamide-type resin, a polyolefin-type resin, etc. are mentioned, for example. As polyester-based resin, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, etc. are mentioned, for example. As a polyolefin resin, the homopolymer of an olefin monomer, the copolymer of an olefin monomer, etc. are mentioned, for example. Specific examples of polyolefin-based resins include: homopolypropylene; propylene-based copolymers such as block-based, random-based, and graft-based copolymers using ethylene as a copolymerization component; Reactor-TPO (reactor for direct production of thermoplastic polyolefins) ); low density, high density, linear low density, ultra-low density and other ethylene polymers; ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer , ethylene-butyl acrylate copolymer, ethylene-methacrylic acid copolymer, ethylene-methyl methacrylate copolymer and other ethylene-based copolymers, etc.

The base material layer may contain any appropriate additives as needed. As an additive which can be contained in a base material layer, antioxidant, an ultraviolet absorber, a light stabilizer, an antistatic agent, a filler, a pigment, etc. are mentioned, for example. The kind 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, in order to prevent deterioration or the like, it is preferable to contain some of the above-mentioned additives. In order to improve weather resistance etc., as an additive, antioxidant, a ultraviolet absorber, a light stabilizer, and a filler are mentioned especially as an additive.

As the antioxidant, any appropriate antioxidant can be used. Examples of such antioxidants include phenolic antioxidants, phosphorus-based processing heat stabilizers, lactone-based processing heat stabilizers, sulfur-based heat-resistant stabilizers, and phenol/phosphorus-based antioxidants. Regarding the content ratio of the antioxidant, with respect to the base resin of the base material layer (in the case where the base material layer is a blend, the blend is the base resin), It is preferably 1% by weight or less, more preferably 0.5% by weight or less, and still more preferably 0.01% by weight to 0.2% by weight.

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

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

As the filler, any appropriate filler can be used. As such a filler, an inorganic type filler etc. are mentioned, for example. 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 wt % or less, more preferably 10 wt %, with respect to the base resin forming the base layer (when the base layer is a blend, the blend is the base resin). % or less, more preferably 0.01% by weight to 10% by weight.

Furthermore, as an additive, in order to impart antistatic properties, it is also preferable to include: interfacial activity Inorganic, low molecular weight and high molecular weight antistatic agents such as agents, inorganic salts, polyols, metal compounds, carbon, etc. In particular, in order to prevent contamination and maintain adhesiveness, a high molecular weight antistatic agent or carbon is preferable.

≪≪B. Use≫≫

The surface protective film of the embodiment of the present invention can sufficiently suppress the peeling electrostatic voltage without damaging the optical member or the electronic member during peeling. Typically, in the manufacturing process of the optical member or the electronic member, In order to prevent the surface of the optical component or the electronic component from being damaged during processing, assembly, inspection, transportation, etc., it is attached to the exposed surface of the optical component or the electronic component, and includes a surface protection film of an adhesive layer. Therefore, it is suitable for surface protection of optical members or electronic members. The optical member of the present invention is bonded with the surface protection film of the present invention. The electronic component of the present invention is bonded with the surface protection film of the present invention.

[Example]

Hereinafter, the present invention will be specifically described using examples, but the present invention is not limited by these examples at all. In addition, the test and evaluation method in an Example etc. are as follows. In addition, when describing as "parts", unless otherwise specified, it means "weight part", and when describing as "%", unless specified otherwise, means "weight %".

<Measurement of Surface Free Energy of Diiodomethane on the Surface of the Adhesive Layer>

Cut the surface protective film of the peeled separator into a size of 50mm in width and 100mm in length, and fix it on a contact angle meter (manufactured by Kyowa Interface Science Co., Ltd., model "CA-X") with the surface of the adhesive layer as the upper surface. 2.0 μL of water was added dropwise to the surface of the layer, and the contact angle was measured. Second, According to the same procedure, 2.0 μL of diiodomethane was added dropwise, and the contact angle was measured. According to the above contact angle values of the two liquids, the surface free energy of the surface of the adhesive layer to diiodomethane was calculated using the Owens-Wendt method.

<Measurement of peeling force from glass plate (after being left at a temperature of 23°C for 30 minutes)>

The adhesive layer side of the surface protective film (width 25mm×length 140mm) of the peeled separator was pasted to a glass plate (soda lime glass, manufactured by Songnang Glass Industry Co., Ltd.) by using a 2kg hand roller back and forth once, and at 23 ℃ ambient temperature for 30 minutes.

The evaluation samples obtained in the above-described manner were measured with a tensile testing machine. As the tensile testing machine, a product called "Autograph AG-Xplus HS 6000mm/min high-speed model (AG-50NX plus)" manufactured by Shimadzu Corporation was used. The sample for evaluation was set in the tensile testing machine, and the tensile test was started. Specifically, the load at the time of peeling the surface protective film from the glass plate was measured, and the average load at that time was defined as the peeling force of the surface protective film from the glass plate. The conditions of the tensile test were set as the test environment temperature: 23° C., the peeling angle: 180 degrees, and the peeling speed (tensile speed): 300 mm/min.

<Measurement of peeling electrostatic voltage to glass and peeling electrostatic voltage to acrylic resin board>

Cut the surface protective film of the peeled separator into a width of 70mm and a length of 100mm, so that one end of the surface protective film protrudes 30mm from the end of the glass, and is pressed to the glass (soda-lime glass) with a hand roller. , made by Matsunami Glass Co., Ltd.) or acrylic resin board (Acrylite, made by Mitsubishi Chemical Co., Ltd.).

The sample was placed in an environment of 23° C.×50% RH for 1 day, and then set at a predetermined position of a sample fixing table with a height of 20 mm. Fix the end of the surface protection film that protrudes 30mm from the glass In an automatic coiler, peeling was performed so that a peeling angle might be 150 degrees, and peeling speed might be 30 m/min. The potential of the surface of the adherend generated at this time was measured by a potentiometer (manufactured by Shishido Electrostatic Gas Co., Ltd., model "STATIRON DZ-4") fixed at a height of 30 mm from the center of the adherend, and set as The peeling electrostatic voltage to glass or the peeling electrostatic voltage to acrylic resin board. The measurement was carried out in an environment of 23°C and 50% RH.

<Measurement of residual adhesive force on glass>

The surface protective film was adhered to the glass plate (manufactured by Matsunami Glass, 1.35mm×10cm×10cm) over the entire surface with a hand pressing roller, and was stored for 24 hours in an atmosphere of The surface protective film was peeled off at a speed of 1 min, and the No.31B tape (Nitto Denko Co., Ltd.) cut to a length of 150 mm and a width of 19 mm was attached with a 2.0 kg roller back and forth once in an atmosphere of temperature 23 °C and humidity 55% RH. manufacture, substrate thickness: 25 μm). Cured for 30 minutes in an atmosphere with a temperature of 23°C and a humidity of 55% RH, and then used a tensile tester (a product called "Autograph AG-Xplus HS 6000mm/min high-speed model (AG-50NX plus)" manufactured by Shimadzu Corporation ), peeling was performed at a peeling angle of 180 degrees and a tensile speed of 300 mm/min, and the adhesive force was measured.

Moreover, the adhesive force of No. 31B tape of 19 mm width was similarly measured about the glass plate which did not carry out the above-mentioned process, and the residual adhesion rate was calculated by the following formula.

Residual adhesion rate (%)=(No.31B adhesion force to glass plate after peeling off surface protective film/No.31B adhesion force to glass plate)×100

The residual adhesion rate to glass is an indicator of how much the adhesive component of the surface protection film is transferred to the surface of the adherend and whether it causes pollution. The higher the value of the residual adhesion rate to the glass, the lower the possibility of the surface protective film contaminating the adherend. The lower the value of the adhesion rate, the higher the possibility that the surface protective film will contaminate the adherend.

<Measurement of haze>

The adhesive solution obtained in the following examples and comparative examples will be coated on a polyester film with a thickness of 75 μm (commercial product) which has been treated with silicone peeling on one side under the conditions described in the following examples and comparative examples. Name: DIAFOIL MRF75, manufactured by Mitsubishi Chemical Co., Ltd.), the peeling-treated surface was dried to prepare an adhesive layer. Next, a polyester film with a thickness of 75 μm (trade name: DIAFOIL MRE75, manufactured by Mitsubishi Chemical Co., Ltd.) whose one side was peeled off with silicone was coated on the adhesive so that the peeled side of the film became the side of the adhesive layer. The surface of the layer was aged at room temperature for 5 days. Prepare 2 sheets of 50mm×50mm thick paper with a hole of 20mm×20mm in the center, and stick the sample to one of the thick sheets by hand pressing the roller back and forth once, and then stick the other thick paper. The evaluation sample obtained in the above-mentioned manner was measured using "HM-150N" manufactured by Murakami Color Technology Research Institute.

<Description of Fluorine-Containing Compounds Used in Examples and Comparative Examples>

The fluorine-containing compounds used in the examples and comparative examples are as follows.

"MEGAFAC F-477" (manufactured by DIC Corporation, an oligomer containing fluorine, hydrophilic and lipophilic groups, surface tension = 26.4mN/m when prepared as a 0.1% toluene solution); " MEGAFAC F-551-A" (manufactured by DIC Corporation, an oligomer containing fluorine-containing groups and lipophilic groups, surface tension = 25.6mN/m when prepared as a 0.1% toluene solution); "MEGAFAC F- 553" (manufactured by DIC (stock), an oligomer containing fluorine group, hydrophilic group and lipophilic group, surface tension = 26.4mN/m when prepared as a 0.1% toluene solution); "MEGAFAC F-554 ” (manufactured by DIC (stock), an oligomer containing a fluorine-containing group and a lipophilic group material, surface tension = 25.0mN/m in the case of making a 0.1% toluene solution); "MEGAFAC F-555-A" (manufactured by DIC (stock), containing a low level of fluorine-containing group, hydrophilic group and lipophilic group polymer, surface tension = 20.4mN/m in the case of 0.1% toluene solution); "MEGAFAC F-557" (manufactured by DIC (stock), an oligomer containing fluorine-containing, hydrophilic and lipophilic groups material, surface tension = 26.3mN/m in the case of making a 0.1% toluene solution); "MEGAFAC F-559" (manufactured by DIC (stock), an oligomer containing a fluorine-containing group, a hydrophilic group and a lipophilic group , in the case of making 0.1% toluene solution, the surface tension = 26.1mN/m); "MEGAFAC F-563" (manufactured by DIC (stock), an oligomer containing fluorine-containing groups and lipophilic groups, when made into 0.1 In the case of % toluene solution, surface tension=20.2mN/m); "MEGAFAC F-569" (manufactured by DIC Co., Ltd., an oligomer containing fluorine and hydrophilic groups, in the case of 0.1% toluene solution) When the surface tension = 19.7mN/m).

[Example 1]

As a polyol, 85 parts by weight of PREMINOL S3011 (manufactured by Asahi Glass Co., Ltd., Mn=10000), a polyol having three hydroxyl groups, and 13 parts by weight of SANNIX GP3000 (manufactured by Sanyo Chemical Co., Ltd., Mn=3000), a polyol having three hydroxyl groups parts, 2 parts by weight of SANNIX GP1000 (manufactured by Sanyo Chemical Co., Ltd., Mn=1000) of a polyol having 3 hydroxyl groups; 18 parts by weight of an isocyanate compound (Coronate HX: C/HX, manufactured by Nippon Polyurethane Co., Ltd.) as a crosslinking agent; 0.02 parts by weight of iron triacetate (manufactured by Nippon Chemical Industry Co., Ltd.) as a catalyst, 1 part by weight of MEGAFAC F-553 (manufactured by DIC Corporation) as a fluorine-based oligomer; 1-ethyl-3 as an ionic compound - 1 part by weight of methylimidazolium tris(fluoromethanesulfonyl)imide (AS110, manufactured by Daiichi Industrial Pharmaceutical Co., Ltd.), used so that the solid content of the whole is 35% by weight Ethyl acetate was diluted, and the urethane type adhesive solution was obtained. Then, the urethane-based adhesive solution was applied to a base material containing a polyester resin (trade name "T100-75S", thickness 75 μm, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying was 20 μm. , aged and dried at a drying temperature of 130°C and a drying time of 2 minutes. Next, the silicone-treated surface of a release sheet (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Co., Ltd.) containing a polyester resin having a thickness of 25 μm and having been silicone-treated on one side was attached to the obtained sheet. The surface of the adhesive layer is obtained to obtain a surface protection film (1). After 5 days of aging at room temperature, evaluation was performed. The release sheet was released immediately prior to evaluation. The results are shown in Table 1.

[Example 2]

As shown in Table 1, except having changed the fluorine-based oligomer (trade name "F-569", manufactured by DIC) to 0.25 parts by weight in terms of solid content The adhesive layer of the agent composition (2) is formed, thereby obtaining a surface protection film (2). The results are shown in Table 1.

[Example 3]

As shown in Table 1, except having changed the fluorine-based oligomer (trade name "F-554", manufactured by DIC) to 1 part by weight in terms of solid content The adhesive layer of the agent composition (3) is formed, thereby obtaining a surface protection film (3). The results are shown in Table 1.

[Example 4]

As shown in Table 1, except having changed the fluorine-based oligomer (trade name "F-553", manufactured by DIC) to 0.25 parts by weight in terms of solid content The adhesive layer of the agent composition (4) is formed, thereby obtaining a surface protection film (4). The results are shown in Table 1.

[Example 5]

As shown in Table 1, a fluorine-based oligomer (trade name "F-553", manufactured by DIC) was changed to 0.25 parts by weight in terms of solid content, and an ionic compound (trade name "AS110", manufactured by Daiichi Industries A surface protective film (5) was obtained by producing an adhesive layer containing the adhesive composition (5) in the same manner as in Example 1, except that it was changed to 0.5 parts by weight. The results are shown in Table 1.

[Example 6]

As shown in Table 1, a fluorine-based oligomer (trade name "F-553", manufactured by DIC) was changed to 0.25 parts by weight in terms of solid content, and an ionic compound (trade name "AS110", manufactured by Daiichi Industries A surface protective film (6) was obtained by producing an adhesive layer containing an adhesive composition (6) in the same manner as in Example 1, except that it was changed to 0.25 parts by weight. The results are shown in Table 1.

[Example 7]

As shown in Table 1, it was produced in the same manner as in Example 1, 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. An adhesive layer comprising the adhesive composition (7) is obtained, thereby obtaining a surface protection film (7). The results are shown in Table 1.

[Example 8]

As shown in Table 1, except having changed the fluorine-based oligomer (trade name "F-559", manufactured by DIC) to 0.25 parts by weight in terms of solid content The adhesive layer of the agent composition (8) is formed, thereby obtaining a surface protection film (8). The results are shown in Table 1.

[Example 9]

As shown in Table 1, except having changed the fluorine-based oligomer (trade name "F-477", manufactured by DIC) to 1 part by weight in terms of solid content The adhesive layer of the agent composition (9) is formed, thereby obtaining a surface protection film (9). The results are shown in Table 1.

[Example 10]

As shown in Table 1, except having changed the fluorine-based oligomer (trade name "F-554", manufactured by DIC) to 0.25 parts by weight in terms of solid content The adhesive layer of the agent composition (10) is formed, thereby obtaining a surface protection film (10). The results are shown in Table 1.

[Example 11]

As shown in Table 1, except having changed the fluorine-based oligomer (trade name "F-553", manufactured by DIC) to 0.1 part by weight in terms of solid content The adhesive layer of the agent composition (11) is formed, thereby obtaining a surface protection film (11). The results are shown in Table 1.

[Example 12]

As shown in Table 1, except having changed the fluorine-based oligomer (trade name "F-477", manufactured by DIC) to 0.25 parts by weight in terms of solid content The adhesive layer of the agent composition (12) is formed, thereby obtaining a surface protection film (12). The results are shown in Table 1.

[Example 13]

As shown in Table 1, a fluorine-based oligomer (trade name "F-477", manufactured by DIC) was changed to 0.25 parts by weight in terms of solid content, and an ionic compound (trade name "AS110", manufactured by Daiichi Industries A surface protective film (13) was obtained by producing an adhesive layer containing an adhesive composition (13) in the same manner as in Example 1, except that it was changed to 0.5 parts by weight. The results are shown in Table 1.

[Example 14]

As shown in Table 1, a fluorine-based oligomer (trade name "F-477", manufactured by DIC) was changed to 0.25 parts by weight in terms of solid content, and an ionic compound (trade name "AS110", manufactured by Daiichi Industries A surface protective film (14) was obtained by producing an adhesive layer containing an adhesive composition (14) in the same manner as in Example 1, except that it was changed to 0.25 parts by weight. The results are shown in Table 1.

[Example 15]

As shown in Table 1, it was produced in the same manner as in Example 1, 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. An adhesive layer containing the adhesive composition (15) is obtained, thereby obtaining a surface protection film (15). The results are shown in Table 1.

[Example 16]

As shown in Table 1, the fluorine-based oligomer (trade name "F-556", DIC manufacture) was changed to 0.25 weight part, except having produced the adhesive layer containing the adhesive composition (16) similarly to Example 1, and obtained the surface protection film (16). The results are shown in Table 1.

[Example 17]

As shown in Table 1, it was produced in the same manner as in Example 1, 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. An adhesive layer containing the adhesive composition (17) is obtained, thereby obtaining a surface protection film (17). The results are shown in Table 1.

[Example 18]

As shown in Table 1, except having changed the fluorine-based oligomer (trade name "F-554", manufactured by DIC) to 0.1 part by weight in terms of solid content The adhesive layer of the agent composition (18) is formed, thereby obtaining a surface protection film (18). The results are shown in Table 1.

[Example 19]

As shown in Table 1, except having changed the fluorine-based oligomer (trade name "F-563", manufactured by DIC) to 0.25 parts by weight in terms of solid content The adhesive layer of the agent composition (19) is formed, thereby obtaining a surface protection film (19). The results are shown in Table 1.

[Example 20]

As shown in Table 1, the fluorine-based oligomer (trade name "F-477", DIC manufacture) was changed to 0.1 weight part, except having produced the adhesive layer containing the adhesive composition (20) similarly to Example 1, and obtained the surface protection film (20). The results are shown in Table 1.

[Example 21]

As shown in Table 1, a fluorine-based oligomer (trade name "F-553", manufactured by DIC) was changed to 2.0 parts by weight in terms of solid content The adhesive layer of the agent composition (21) is formed, thereby obtaining a surface protection film (21). The results are shown in Table 1.

[Example 22]

As shown in Table 1, a fluorine-based oligomer (trade name "F-553", manufactured by DIC) was changed to 4.0 parts by weight in terms of solid content The adhesive layer of the agent composition (22) is formed, thereby obtaining a surface protection film (22). The results are shown in Table 1.

[Example 23]

As shown in Table 1, except having changed the fluorine-based oligomer (trade name "F-553", manufactured by DIC) to 6.0 parts by weight in terms of solid content The adhesive layer of the agent composition (23) is formed, thereby obtaining a surface protection film (23). The results are shown in Table 1.

[Example 24]

As shown in Table 1, except having changed the fluorine-based oligomer (trade name "F-477", manufactured by DIC) to 2.0 parts by weight in terms of solid content The adhesive layer of the agent composition (24) is formed, thereby obtaining a surface protection film (24). The results are shown in Table 1.

[Example 25]

As shown in Table 1, a fluorine-based oligomer (trade name "F-477", manufactured by DIC) was changed to 4.0 parts by weight in terms of solid content The adhesive layer of the agent composition (25) is formed, thereby obtaining a surface protection film (25). The results are shown in Table 1.

[Example 26]

As shown in Table 1, except having changed the fluorine-based oligomer (trade name "F-477", manufactured by DIC) to 6.0 parts by weight in terms of solid content The adhesive layer of the agent composition (26) is formed, thereby obtaining a surface protection film (26). The results are shown in Table 1.

[Example 27]

As shown in Table 1, except that the isocyanate compound (Coronate HX: C/HX, manufactured by Nippon Polyurethane Co., Ltd.) was changed to 15.9 parts by weight in terms of solid content, a combination containing an adhesive was prepared in the same manner as in Example 4. The adhesive layer of the object (27) is formed, thereby obtaining a surface protection film (27). The results are shown in Table 1.

[Example 28]

As shown in Table 1, except that the isocyanate compound (Coronate HX: C/HX, manufactured by Nippon Polyurethane Co., Ltd.) was changed to 14.1 parts by weight in terms of solid content, a combination containing an adhesive was prepared in the same manner as in Example 4. The adhesive layer of the object (28) is formed, thereby obtaining a surface protection film (28). The results are shown in Table 1.

[Example 29]

As shown in Table 1, except that the isocyanate compound (Coronate HX: C/HX, manufactured by Nippon Polyurethane Co., Ltd.) was changed to 12.4 parts by weight in terms of solid content, a combination containing an adhesive was prepared in the same manner as in Example 4. The adhesive layer of the object (29) is obtained, thereby obtaining a surface protection film (29). The results are shown in Table 1.

[Example 30]

As shown in Table 1, except that the isocyanate compound (Coronate HX: C/HX, manufactured by Nippon Polyurethane Co., Ltd.) was changed to 10.6 parts by weight in terms of solid content, a combination containing an adhesive was prepared in the same manner as in Example 4. The adhesive layer of the object (30) is formed, thereby obtaining a surface protection film (30). The results are shown in Table 1.

[Example 31]

As shown in Table 1, except that the isocyanate compound (Coronate HX: C/HX, manufactured by Nippon Polyurethane Co., Ltd.) was changed to 8.8 parts by weight in terms of solid content, a combination containing an adhesive was prepared in the same manner as in Example 4. The adhesive layer of the object (31) is obtained, thereby obtaining a surface protection film (31). The results are shown in Table 1.

[Example 32]

As shown in Table 1, except that the isocyanate compound (Coronate HX: C/HX, manufactured by Nippon Polyurethane Co., Ltd.) was changed to 15.9 parts by weight in terms of solid content, a combination containing an adhesive was prepared in the same manner as in Example 12. The adhesive layer of the object (32) is formed, thereby obtaining a surface protection film (32). The results are shown in Table 1.

[Example 33]

As shown in Table 1, except that the isocyanate compound (Coronate HX: C/HX, manufactured by Nippon Polyurethane Co., Ltd.) was changed to 14.1 parts by weight in terms of solid content, a combination containing an adhesive was prepared in the same manner as in Example 12. The adhesive layer of the object (33) is formed, thereby obtaining a surface protection film (33). The results are shown in Table 1.

[Example 34]

As shown in Table 1, except that the isocyanate compound (Coronate HX: C/HX, manufactured by Nippon Polyurethane Co., Ltd.) was changed to 12.4 parts by weight in terms of solid content, a combination containing an adhesive was prepared in the same manner as in Example 12. The adhesive layer of the object (34) is formed, thereby obtaining a surface protection film (34). The results are shown in Table 1.

[Example 35]

As shown in Table 1, a combination containing an adhesive was prepared in the same manner as in Example 12, except that the isocyanate compound (Coronate HX: C/HX, manufactured by Nippon Polyurethane) was changed to 10.6 parts by weight in terms of solid content. The adhesive layer of the object (35) is formed, thereby obtaining a surface protection film (35). The results are shown in Table 1.

[Example 36]

As shown in Table 1, except that the isocyanate compound (Coronate HX: C/HX, manufactured by Nippon Polyurethane Co., Ltd.) was changed to 8.8 parts by weight in terms of solid content, a combination containing an adhesive was prepared in the same manner as in Example 12. The adhesive layer of the material (36) is formed, thereby obtaining a surface protection film (36). The results are shown in Table 1.

[Example 37]

As shown in Table 1, except having changed the fluorine-based oligomer (trade name "F-557", manufactured by DIC) to 0.25 parts by weight in terms of solid content The adhesive layer of the agent composition (37) is formed, thereby obtaining a surface protection film (37). The results are shown in Table 1.

[Example 38]

As shown in Table 1, except that the isocyanate compound (Coronate HX: C/HX, manufactured by Nippon Polyurethane Co., Ltd.) was changed to 15.9 parts by weight in terms of solid content, a combination containing an adhesive was prepared in the same manner as in Example 37. The adhesive layer of the object (38) is formed, thereby obtaining a surface protection film (38). The results are shown in Table 1.

[Example 39]

As shown in Table 1, a composition containing an adhesive was prepared in the same manner as in Example 37, except that the isocyanate compound (Coronate HX: C/HX, manufactured by Nippon Polyurethane) was changed to 14.1 parts by weight in terms of solid content. The adhesive layer of the object (39) is formed, thereby obtaining a surface protection film (39). The results are shown in Table 1.

[Example 40]

As shown in Table 1, except that the isocyanate compound (Coronate HX: C/HX, manufactured by Nippon Polyurethane Co., Ltd.) was changed to 12.4 parts by weight in terms of solid content, a combination containing an adhesive was prepared in the same manner as in Example 37. The adhesive layer of the object (40), so as to obtain surface protection protective film (40). The results are shown in Table 1.

[Example 41]

As shown in Table 1, except that the isocyanate compound (Coronate HX: C/HX, manufactured by Nippon Polyurethane Co., Ltd.) was changed to 10.6 parts by weight in terms of solid content, a combination containing an adhesive was prepared in the same manner as in Example 37. The adhesive layer of the object (41) is obtained, thereby obtaining a surface protection film (41). The results are shown in Table 1.

[Example 42]

As shown in Table 1, except that the isocyanate compound (Coronate HX: C/HX, manufactured by Nippon Polyurethane Co., Ltd.) was changed to 8.8 parts by weight in terms of solid content, a combination containing an adhesive was prepared in the same manner as in Example 37. The adhesive layer of the object (42) is formed, thereby obtaining a surface protection film (42). The results are shown in Table 1.

[Example 43]

As shown in Table 1, except that the isocyanate compound (Coronate HX: C/HX, manufactured by Nippon Polyurethane Co., Ltd.) was changed to 15.9 parts by weight in terms of solid content, a combination containing an adhesive was prepared in the same manner as in Example 8. The adhesive layer of the object (43) is formed, thereby obtaining a surface protection film (43). The results are shown in Table 1.

[Example 44]

As shown in Table 1, the isocyanate compound (Coronate HX: C/HX, manufactured by Nippon Polyurethane Co., Ltd.) was changed to 14.1 parts by weight in terms of solid content, and the same In Example 8, an adhesive layer containing the adhesive composition (44) was produced in the same manner to obtain a surface protection film (44). The results are shown in Table 1.

[Example 45]

As shown in Table 1, except that the isocyanate compound (Coronate HX: C/HX, manufactured by Nippon Polyurethane Co., Ltd.) was changed to 12.4 parts by weight in terms of solid content, a combination containing an adhesive was prepared in the same manner as in Example 8. The adhesive layer of the object (45) is formed, thereby obtaining a surface protection film (45). The results are shown in Table 1.

[Example 46]

As shown in Table 1, except that the isocyanate compound (Coronate HX: C/HX, manufactured by Nippon Polyurethane Co., Ltd.) was changed to 10.6 parts by weight in terms of solid content, a combination containing an adhesive was prepared in the same manner as in Example 8. The adhesive layer of the material (46) is formed, thereby obtaining a surface protection film (46). The results are shown in Table 1.

[Example 47]

As shown in Table 1, except that the isocyanate compound (Coronate HX: C/HX, manufactured by Nippon Polyurethane Co., Ltd.) was changed to 8.8 parts by weight in terms of solid content, a combination containing an adhesive was prepared in the same manner as in Example 8. The adhesive layer of the object (47) is formed, thereby obtaining a surface protection film (47). The results are shown in Table 1.

[Example 48]

100 parts by weight of urethane prepolymer A, an isocyanate compound as a crosslinking agent (Coronate HX: C/HX, manufactured by Nippon Polyurethane Co., Ltd.) 3 parts by weight, 0.5 part by weight of Irganox 1010 (manufactured by BASF Corporation) as an antioxidant, 1 part by weight of MEGAFAC F-553 (manufactured by DIC Corporation) as a fluorine-based oligomer, As an ionic compound, 1-ethyl-3-methylimidazolium tris(fluoromethanesulfonyl)imide (AS110, manufactured by Daiichi Industrial Pharmaceutical Co., Ltd.) is 1 part by weight, and the total solid content is 49 weight parts % was diluted with ethyl acetate to obtain a urethane-based adhesive solution. Then, the urethane-based adhesive solution was applied to a substrate containing a polyester resin (trade name "T100-75S", thickness 75 μm, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying was 75 μm. , curing and drying under the conditions of a drying temperature of 120° C. and a drying time of 3 minutes to produce an adhesive layer comprising an adhesive composition (48). Next, the silicone-treated surface of a release sheet (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Co., Ltd.) containing a polyester resin with a thickness of 25 μm treated with silicone was attached to the obtained adhesive The surface of the agent layer is obtained to obtain a surface protection film (48). After 5 days of aging at room temperature, evaluation was performed. The release sheet was released immediately prior to evaluation. The results are shown in Table 1.

[Example 49]

As shown in Table 1, a fluorine-based oligomer (trade name "F-477", manufactured by DIC) was changed to 1.0 parts by weight in terms of solid content The adhesive layer of the agent composition (49) is formed, thereby obtaining a surface protection film (49). The results are shown in Table 1.

[Example 50]

As shown in Table 1, fluorine-based oligomer (trade name "F-557", A surface protective film (50) was obtained by producing an adhesive layer containing an adhesive composition (50) in the same manner as in Example 48, except that it was changed to 1.0 parts by weight, manufactured by DIC. The results are shown in Table 1.

[Example 51]

As shown in Table 1, a fluorine-based oligomer (trade name "F-559", manufactured by DIC) was changed to 1.0 parts by weight in terms of solid content The adhesive layer of the agent composition (51) is formed, thereby obtaining a surface protection 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) was 0.25 parts by weight in terms of solid content, and an ionic compound (trade name "AS110", manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd.) was not used. production), except that it carried out similarly to Example 1, produced the adhesive bond layer containing the adhesive composition (C1), and obtained the surface protection film (C1). 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) was 0.25 parts by weight in terms of solid content, and an ionic compound (trade name "AS110", manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd.) was not used. production), except that it carried out similarly to Example 1, and produced the adhesive bond layer containing the adhesive bond composition (C2), and obtained the surface protection film (C2). 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) was 0.25 parts by weight in terms of solid content, and an ionic compound (trade name "AS110", manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd.) was not used. production), except that it carried out similarly to Example 1, produced the adhesive bond layer containing the adhesive composition (C3), and obtained the surface protection film (C3). The results are shown in Table 1.

[Comparative Example 4]

As shown in Table 1, the fluorine-based oligomer (trade name "F-551-A", manufactured by DIC) was 0.25 parts by weight in terms of solid content, and an ionic compound (trade name "AS110", the first Industrial Pharmaceutical Co., Ltd.), except that it carried out similarly to Example 1, and produced the adhesive agent layer containing an adhesive agent composition (C4), and obtained the surface protection film (C4). The results are shown in Table 1.

[Comparative Example 5]

As shown in Table 1, except having changed the fluorine-based oligomer (trade name "F-571", manufactured by DIC) to 0.25 parts by weight in terms of solid content The adhesive layer of the agent composition (C5) was obtained to obtain a surface protection film (C5). The results are shown in Table 1.

[Comparative Example 6]

As shown in Table 1, except having changed the fluorine-based oligomer (trade name "F-552", manufactured by DIC) to 0.25 parts by weight in terms of solid content The adhesive layer of the agent composition (C6) was obtained to obtain a surface protection film (C6). The results are shown in Table 1.

[Comparative Example 7]

As shown in Table 1, except that the fluorine-based oligomer was not used, an adhesive layer containing the adhesive composition (C7) was produced in the same manner as in Example 1, thereby obtaining a surface protection film (C7). The results are shown in Table 1.

[Comparative Example 8]

As shown in Table 1, a combination containing an adhesive was prepared in the same manner as in Example 1, except that a fluorine-based oligomer and an ionic compound (trade name "AS110", manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd.) were not used. The adhesive layer of the product (C8) is obtained, thereby obtaining a surface protection film (C8). The results are shown in Table 1.

[Comparative Example 9]

As shown in Table 1, except that a fluorine-based oligomer was not used and an ionic compound (trade name "AS110", manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd.) was not used, a combination containing an adhesive was prepared in the same manner as in Example 48. The adhesive layer of the product (C9) was obtained, thereby obtaining a surface protection film (C9). The results are shown in Table 1.

[Comparative Example 10]

As shown in Table 1, a combination containing an adhesive was prepared in the same manner as in Example 49, except that a fluorine-based oligomer and an ionic compound (trade name "AS110", manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd.) were not used. The adhesive layer of the material (C10) was obtained, thereby obtaining a surface protection film (C10). The results are shown in Table 1.

[Comparative Example 11]

As shown in Table 1, except having changed the fluorine-based oligomer (trade name "F-571", manufactured by DIC) to 1 part by weight in terms of solid content The adhesive layer of the agent composition (C11) was obtained to obtain a surface protection film (C11). The results are shown in Table 1.

[Table 1]

[Examples 52 to 103]

For each of the surface protection films (1) to (51) obtained using Examples 1 to 51, the isolation The parts were peeled off, and the adhesive layer side was bonded to a polarizing plate (product named "TEG1465DUHC" manufactured by Nitto Denko Co., Ltd.) as an optical member, thereby obtaining an optical member with a surface protective film bonded thereto.

[Examples 104 to 155]

For each of the surface protection films (1) to (51) obtained in Examples 1 to 51, the separator was peeled off, and the adhesive layer side was attached to a conductive film (Nitto Denko Co., Ltd.) which is an electronic member. The product named "ELECRYSTA V270L-TFMP" was manufactured) to obtain an electronic component with a surface protective film attached.

[Industrial Availability]

The surface protective film of the present invention can be used for any appropriate purpose. Preferably, the surface protection film of the present invention can be preferably used in the field of optical components or electronic components.

1: substrate layer

2: Adhesive layer

10: Surface protection film

Claims (9)

A surface protective film comprising an adhesive layer, and the adhesive constituting the adhesive layer is formed from an adhesive composition, the adhesive composition comprising a polyol and a urethane prepolymer At least one, polyfunctional isocyanate, ionic compound and fluorine-based compound, the equivalent ratio of NCO group and OH group in the polyol and the polyfunctional isocyanate compound is 1.8 or less, the haze is 3% or less, and the surface of the adhesive layer is The surface free energy for diiodomethane is 6mJ/m ² ~30mJ/m ² . The surface protective film of claim 1, wherein the content ratio of the ionic compound to 100 parts by weight of the at least one selected from the group consisting of polyols and urethane prepolymers is 0.2 parts by weight or more. The surface protection film of claim 1, wherein the content ratio of the fluorine-based compound to 100 parts by weight of at least one selected from the group consisting of polyols and urethane prepolymers is 0.05 parts by weight or more. The surface protective film of claim 2, wherein the content ratio of the fluorine-based compound to 100 parts by weight of at least one selected from the group consisting of polyols and urethane prepolymers is 0.05 parts by weight or more. The surface protective film according to any one of claims 1 to 4, wherein the content ratio of the polyfunctional isocyanate compound to the polyol is 16 wt % or less. The surface protective film according to any one of claims 1 to 4, wherein the above-mentioned adhesive layer contained in the above-mentioned surface protective film is attached to a glass plate and left at a temperature of 23°C for 30 minutes, and then at a temperature of 23°C with The peeling angle was 180 degrees, and the peeling speed was 300 mm/min. The surface protection film was peeled off from the glass plate, and the peeling force was 0.005 N/25 mm to 0.1 N/25 mm at this time. The surface protective film of claim 5, wherein the above-mentioned adhesive layer contained in the above-mentioned surface protective film is attached to a glass plate and placed at a temperature of 23° C. for 30 minutes, and then at a temperature of 23° C. at a peeling angle of 180 degrees, peeling off The surface protection film was peeled off from the glass plate at a speed of 300 mm/min, and the peeling force at this time was 0.005 N/25 mm to 0.1 N/25 mm. An optical member to which the surface protection film of any one of claims 1 to 7 is attached. An electronic component with the surface protection film according to any one of claims 1 to 7 attached thereto.

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