Surface protection film

Abstract

Provided is a surface protective film capable of exhibiting a light peeling property and capable of suppressing the generation of black spots. Also provided are an optical member and an electronic member each having the surface protective film attached thereto. The surface protective film of an embodiment of the present application is a surface protective film including an adhesive layer composed of a urethane-based adhesive formed from a urethane-based adhesive composition including a base polymer including a urethane prepolymer and a fluorine-based compound, the proportion of hydroxyl groups included in the urethane-based adhesive composition being less than 30 mmol with respect to 100 g of the base polymer.

Description

TECHNICAL FIELD

[0001] The present application relates to a surface protection film. BACKGROUND

[0002] An optical member, an electronic member to which a surface protection film is attached in order to prevent damage to the surface at the time of processing, assembly, inspection, transportation, and the like. Such a surface protection film is peeled from the optical member, the electronic member when surface protection is not required (Patent Document 1).

[0003] It is important for an optical member, an electronic member to which such a surface protection film is attached to be able to be smoothly peeled only at the interface between the surface protection film and the optical member, the electronic member when the surface protection film is to be peeled as described above.

[0004] As an adhesive layer possessed by a surface protection film, an adhesive layer composed of a urethane-based adhesive is known. Note that, as a production method of a urethane-based adhesive, two kinds of production methods are known: a one-step method of directly reacting a polyol with a polyfunctional isocyanate without using a urethane prepolymer to produce a urethane adhesive; and a prepolymer method of reacting a urethane prepolymer with a polyfunctional isocyanate to produce a urethane adhesive.

[0005] In a surface protection film that possesses an adhesive layer composed of a urethane-based adhesive, in order to exhibit easy peeling and the like, a technique of containing a fluorine-based compound in an adhesive composition that forms the urethane-based adhesive is known (Patent Document 2).

[0006] However, upon observation of a conventional surface protection film that possesses an adhesive layer composed of a urethane-based adhesive formed from an adhesive composition containing a fluorine-based compound, it was seen that black spots presumed to be caused by adhesive sink were generated. When such black spots are generated in large numbers, not only is there a concern that the quality of the surface protection film will decrease, but there is also a concern that the inspectability of the surface protection film attached to, for example, an optical member, an electronic member will decrease.

[0007] PRIOR ART DOCUMENTS

[0008] PATENT DOCUMENTS

[0009] Patent Document 1: Japanese Patent Application Publication No. 2016-17109

[0010] Patent Document 2: Japanese Patent No. 6896927 SUMMARY

[0011] PROBLEMS TO BE SOLVED BY THE INVENTION

[0012] An object of the present application is to provide a surface protective film capable of exhibiting a light peeling property and capable of suppressing generation of black spots. In addition, an optical member and an electronic member each having the surface protective film attached thereto are provided.

[0013] Solution to the problem

[0014] The surface protective film of the embodiment of the present application includes an adhesive layer,

[0015] The adhesive layer is composed of a urethane-based adhesive formed from a urethane-based adhesive composition,

[0016] The urethane-based adhesive composition includes a base polymer and a fluorine-based compound,

[0017] The base polymer includes a urethane prepolymer,

[0018] The proportion of hydroxyl groups included in the urethane-based adhesive composition is less than 30 mmol with respect to 100 g of the base polymer.

[0019] In one embodiment, the above base polymer includes a polyoxyalkylene structure represented by General Formula (1).

[0020]

[0021] (In General Formula (1), R 1 represents one selected from the group consisting of a hydrogen atom, an alkyl group having a carbon number of 1 to 4, and a hydroxyalkyl group having a carbon number of 1 to 6. A plurality of R 1 may be the same as or different from each other. n represents an integer of 1 to 4. m represents an integer of 1 to 200.)

[0022] In one embodiment, the above urethane prepolymer includes a polyoxyalkylene structure represented by General Formula (1).

[0023] In one embodiment, the above base polymer includes a polyol that is not a urethane prepolymer.

[0024] In one embodiment, the above polyol includes a polyoxyalkylene structure represented by General Formula (1).

[0025]

[0026] (In General Formula (1), R 1 represents one selected from the group consisting of a hydrogen atom, an alkyl group having a carbon number of 1 to 4, and a hydroxyalkyl group having a carbon number of 1 to 6. A plurality of R 1 may be the same as or different from each other. n represents an integer of 1 to 4. m represents an integer of 1 to 200.)

[0027] In one embodiment, the content ratio of the urethane prepolymer to the polyol in the urethane-based adhesive composition described above is, in terms of weight ratio, urethane prepolymer : polyol = 70 : 30 to 100 : 0.

[0028] In one embodiment, the haze of the adhesive layer described above is 3.5% or less.

[0029] In one embodiment, the surface tension of the fluorine-based compound described above when made into a 0.1% propylene glycol monomethyl ether solution is 23 mN / m or more.

[0030] In one embodiment, the urethane-based adhesive composition described above contains 0.05 parts by weight or more of an ionic compound per 100 parts by weight of the base polymer.

[0031] The optical member of an embodiment of the present application is attached with the surface protective film of an embodiment of the present application.

[0032] The electronic member of an embodiment of the present application is attached with the surface protective film of an embodiment of the present application.

[0033] Effects of the Invention

[0034] According to the present application, it is possible to provide a surface protective film capable of exhibiting light peeling properties and capable of suppressing the generation of black spots. In addition, it is possible to provide an optical member and an electronic member to which such a surface protective film is attached. BRIEF DESCRIPTION OF DRAWINGS

[0035] Figure 1 Cross-sectional view of the surface protective film which is a preferred embodiment of the present application. DETAILED DESCRIPTION

[0036] 《《《1. Surface protective film》》》

[0037] The surface protective film of an embodiment of the present application contains an adhesive layer. The surface protective film of an embodiment of the present application preferably contains a base material layer and an adhesive layer.

[0038] The base material layer can be only one layer, or two or more layers.

[0039] The adhesive layer can be only one layer, or two or more layers.

[0040] On the adhesive face (sometimes referred to as the gum face) side of the adhesive layer, any appropriate release liner can be attached within a range that does not impair the effects of the present application.

[0041] As the release liner, for example, a release liner in which the surface of a substrate (liner substrate) of paper, plastic film, or the like is subjected to silicone treatment; a release liner in which the surface of a substrate (liner substrate) of paper, plastic film, or the like is laminated with a polyolefin-based resin can be exemplified.

[0042] As the plastic film of the substrate provided as the release liner, any appropriate plastic film can be used within a range not impairing the effects of the present application. As such a plastic film, for example, a polyethylene film, a polypropylene film, a polybutylene film, a polybutadiene film, a polymethylpentene film, a polyvinyl chloride film, a vinyl chloride copolymer film, a polyethylene terephthalate film, a polybutylene terephthalate film, a polyurethane film, an ethylene-vinyl acetate copolymer film can be exemplified.

[0043] 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.

[0044] When the surface protective film of the embodiment of the present application includes a substrate layer and an adhesive layer, for the surface of the substrate layer on the opposite side from the adhesive layer, for the purpose of forming a roll body from which roll-off is easy, or the like, for example, a release treatment can be performed by adding a fatty acid amide, a polyethylene imine, a long-chain alkyl-based additive, or the like in the substrate layer, or a coating layer formed of any appropriate release agent of a silicone-based, a long-chain alkyl-based, a fluorine-based, or the like can be provided.

[0045] The surface protective film of the embodiment of the present application can have any appropriate other layer within a range not impairing the effects of the present application.

[0046] Figure 1 A cross-sectional view of the surface protective film of the preferred embodiment of the present application is shown. As shown in FIG. 1, the surface protective film 10 of the preferred embodiment of the present application includes a substrate layer 1 and an adhesive layer 2, and is formed by directly laminating the substrate layer 1 and the adhesive layer 2. Figure 1

[0047] The thickness of the surface protective film of the embodiment of the present application can be set to any appropriate thickness according to the use. Typically, the thickness is preferably 10 μm to 300 μm, more preferably 15 μm to 250 μm, further preferably 20 μm to 200 μm, particularly preferably 25 μm to 170 μm.

[0048] ​The surface protective film of the embodiment of the present application preferably can exhibit light peeling property. The surface protective film of the present application preferably has a peeling force of 0.5 gf / 25 mm to 5.0 gf / 25 mm, more preferably 0.5 gf / 25 mm to 4.0 gf / 25 mm, further preferably 0.5 gf / 25 mm to 3.0 gf / 25 mm, particularly preferably 0.5 gf / 25 mm to 2.5 gf / 25 mm, most preferably 0.5 gf / 25 mm to 2.0 gf / 25 mm, when the adhesive layer contained therein is adhered to a glass plate and peeled therefrom at a peeling angle of 180 degrees and a peeling speed of 300 mm / min after 30 minutes at 23°C. When the peeling force is within the above range, the surface protective film of the embodiment of the present application can exhibit excellent light peeling property. Note that the details of the method for measuring the peeling force are described later.

[0049] The surface protective film of the embodiment of the present application preferably can achieve low haze. The adhesive layer contained in the surface protective film of the present application preferably has a haze of 4.0% or less, more preferably 3.0% or less, further preferably 2.0% or less, particularly preferably 1.5% or less, most preferably 1.0% or less. When the haze is within the above range, the surface protective film of the embodiment of the present application can achieve excellent low haze, for example, can exhibit excellent checkability. Note that the details of the method for measuring the haze are described later.

[0050] The surface protective film of the embodiment of the present application preferably has a peeling static voltage of 15 kV or less, more preferably 10 kV or less, further preferably 5 kV or less, particularly preferably 2 kV or less, most preferably 1 kV or less, when the adhesive layer contained therein is adhered to a glass plate and peeled therefrom at a peeling angle of 150 degrees and a peeling speed of 30 m / min after 1 day at 23°C and 50% RH. When the peeling static voltage is within the above range, the surface protective film of the embodiment of the present application can effectively prevent static electricity at the time of peeling. Note that the details of the method for measuring the peeling static voltage are described later.

[0051] 《《1-1. Adhesive Layer》

[0052] The adhesive layer is composed of a urethane-based adhesive. The urethane-based adhesive is formed from a urethane-based adhesive composition. That is, the urethane-based adhesive formed from the urethane-based adhesive composition is formed into the adhesive layer by the layer shape.

[0053] The thickness of the adhesive layer can be set to any appropriate thickness depending on the use. Typically, it is preferably from 1 μm to 150 μm, more preferably from 5 μm to 130 μm, further preferably from 10 μm to 110 μm, particularly preferably from 20 μm to 100 μm.

[0054] The urethane-based adhesive composition contains a base polymer and a fluorine-based compound. The base polymer can be only one or two or more. The fluorine-based compound can be only one or two or more.

[0055] The base polymer contains a urethane prepolymer. Details of the urethane prepolymer are described later.

[0056] The base polymer optionally contains a polyol. Details of the polyol are described later. Note that, as described later, the polyol of the present application is not a urethane prepolymer.

[0057] The embodiment of the base polymer of the present application is preferably:

[0058] (A) an embodiment containing a urethane prepolymer and not containing a polyol, or

[0059] (B) an embodiment containing both a urethane prepolymer and a polyol.

[0060] The embodiment of the base polymer of the present application is more preferably:

[0061] (a) an embodiment formed of a urethane prepolymer, or

[0062] (b) an embodiment formed of a urethane prepolymer and a polyol.

[0063] The content ratio of the base polymer in the urethane-based adhesive composition is preferably from 50% by weight to 99.99% by weight, more preferably from 70% by weight to 99.99% by weight, further preferably from 90% by weight to 99.99% by weight, particularly preferably from 95% by weight to 99.99% by weight, from the viewpoint of further exhibiting the effects of the present application. By adjusting the content ratio of the base polymer in the urethane-based adhesive composition to the above range, the surface protective film of the present application can further exhibit the effects of the present application.

[0064] The proportion of the hydroxyl group contained in the urethane-based adhesive composition is less than 30 mmol, preferably 5 mmol to 28 mmol, more preferably 5 mmol to 25 mmol, further preferably 5 mmol to 22 mmol, particularly preferably 5 mmol to 20 mmol, per 100 g of the base polymer. By setting the proportion of the hydroxyl group contained in the urethane-based adhesive composition to the above range per 100 g of the base polymer, the effect of the present application can be exhibited.

[0065] In completing the present application, the present inventors and others have conducted various studies on the suppression of black spot generation as a problem. As a result, it was considered that, as a cause of black spot generation, around a bubble generated in the process of forming an adhesive, a stable micelle is formed by a fluorine-based compound functioning as a surfactant, and, at the time of finally forming an adhesive layer, a gel sag caused by the bubble is generated. Therefore, the present inventors and others have conceived that if the formation of the above micelle can be suppressed, the generation of black spots can be suppressed, and further conducted studies, as a result of which attention was paid to the compatibility of the base polymer (representatively, a urethane prepolymer and a polyol as an optional component) in the urethane-based adhesive composition with the fluorine-based compound. Moreover, from the viewpoint of adjusting the compatibility of the base polymer with the fluorine-based compound, repeated studies were conducted, as a result of which it was found that, by setting the proportion of the hydroxyl group contained in the urethane-based adhesive composition to the above range per 100 g of the base polymer, the generation of black spots can be effectively suppressed.

[0066] The urethane-based adhesive can be defined as a substance formed from the urethane-based adhesive composition. This is because the urethane-based adhesive is a substance in which the urethane-based adhesive composition has undergone a cross-linking reaction or the like by heating, ultraviolet irradiation, or the like to become a urethane-based adhesive, and therefore the urethane-based adhesive cannot be directly defined by its structure, and there is a case where it is almost impossible to define the urethane-based adhesive ("impossible / impractical case"), and therefore the urethane-based adhesive is appropriately defined as a "substance" by the definition of "a substance formed from the urethane-based adhesive composition".

[0067] As a method of forming the urethane-based adhesive from the urethane-based adhesive composition, any appropriate formation method can be employed without impairing the effects of the present application. As such a formation method, for example, a method in which the urethane-based adhesive composition is directly applied to an arbitrary appropriate base film (for example, the base layer in the surface protective film of the embodiments of the present application) and dried or cured (direct method) ; a method in which the urethane-based adhesive composition is applied to the surface (release surface) of a release liner and dried or cured to form a urethane-based adhesive layer on the surface, and the urethane-based adhesive layer is laminated to a base film (for example, the base layer in the surface protective film of the embodiments of the present application) to transfer the urethane-based adhesive layer (transfer method) can be exemplified.

[0068] As a method of applying the urethane-based adhesive composition, any appropriate application method can be employed without impairing the effects of the present application. As such an application method, for example, roll coating, gravure coating, reverse coating, kiss coating, dip roll coating, bar coating, roll brushing, spray coating, blade coating, air knife coating, comma coating, direct coating, die coating, and roll brushing can be exemplified.

[0069] Drying of the urethane-based adhesive composition can be performed under heating (for example, heating to about 60°C to 150°C) as needed.

[0070] As a means of curing the urethane-based adhesive composition, any appropriate curing means can be employed without impairing the effects of the present application. As such a curing means, for example, ultraviolet irradiation, laser light irradiation, α-ray irradiation, β-ray irradiation, γ-ray irradiation, X-ray irradiation, and electron beam irradiation can be exemplified.

[0071] The base polymer (typically, at least one selected from the urethane prepolymer and the polyol described later) preferably contains a polyoxyalkylene structure represented by General Formula (1). By causing the base polymer to contain a polyoxyalkylene structure represented by General Formula (1), light peeling properties can be further exhibited. Note that the fact that the base polymer contains a polyoxyalkylene structure represented by General Formula (1) can be confirmed by any appropriate method. As such a method, for example, NMR measurement, IR measurement, and the like can be exemplified.

[0072]

[0073] In General Formula (1), R 1 represents one selected from the group consisting of a hydrogen atom, an alkyl group having a carbon number of 1 to 4, and a hydroxyalkyl group having a carbon number of 1 to 6. Note that a plurality of R 1 may be the same as or different from each other.

[0074] In General Formula (1), R 1 When R

[0075] In General Formula (1), R 1 When R

[0076] When R 1 is selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 4 carbons, more preferably one selected from the group consisting of a hydrogen atom and a methyl group, and further preferably a hydrogen atom.

[0077] In General Formula (1), n is the number of repetitions of the structural unit, and represents an integer of 1 to 4. From the viewpoint of further exhibiting the effects of the present application, n is preferably an integer of 1 to 3, more preferably 1 or 2, and further preferably 2.

[0078] In General Formula (1), m is the number of repetitions of the structural unit, and represents an integer of 1 to 200. From the viewpoint of further exhibiting the effects of the present application, m is preferably 10 to 100, more preferably 15 to 75, and further preferably 20 to 50.

[0079] The base polymer (representatively at least one selected from the urethane prepolymer and the polyol described later) preferably contains a polyoxyalkylene structure represented by General Formula (2). By causing the base polymer to contain a polyoxyalkylene structure represented by General Formula (2), the easy release property can be further exhibited. Note that the fact that the base polymer contains a polyoxyalkylene structure represented by General Formula (2) can be confirmed by any appropriate method. As such a method, for example, NMR measurement, IR measurement, and the like can be cited.

[0080]

[0081] In General Formula (2), R 2 represents one selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 4 carbons. Note that a plurality of R 2 may be the same as or different from each other.

[0082] In General Formula (2), R 2 When R

[0083] When R 2, preferably one selected from the group consisting of a hydrogen atom and a methyl group, more preferably a hydrogen atom.

[0084] In General Formula (2), p is the number of repeating units of the structure, and represents an integer of 1 to 300. From the viewpoint of further exhibiting the effects of the present application, p is preferably an integer of 10 to 250, more preferably an integer of 20 to 200, further preferably an integer of 30 to 150.

[0085] "1-1-1. Carbamate prepolymer"

[0086] The base polymer contains a carbamate prepolymer.

[0087] The carbamate prepolymer can be only one kind, or two or more kinds.

[0088] The number average molecular weight Mn of the carbamate prepolymer is preferably 1000 to 100000 from the viewpoint of further exhibiting the effects of the present application.

[0089] The base polymer optionally contains a polyol as described later. Among them, the polyol of the present application is not a carbamate prepolymer. That is, the carbamate-based adhesive composition optionally contains a polyol which is not a carbamate prepolymer. As such, the reason why the polyol in the present specification is defined as not a carbamate prepolymer is described below. That is, because the carbamate prepolymer in the present specification is different from a "polyol" (polyol used in one-step method) from the "carbamate prepolymer" (carbamate prepolymer used in prepolymer method) commonly called by those skilled in the art in the production of a carbamate resin, but the carbamate prepolymer also has a plurality of hydroxyl groups, the carbamate prepolymer is clearly distinguished from the polyol in the present specification.

[0090] The contained ratio of the carbamate prepolymer and the polyol in the base polymer is preferably carbamate prepolymer : polyol = 50 : 50 to 100 : 0 in terms of weight ratio from the viewpoint of further exhibiting the effects of the present application, more preferably carbamate prepolymer : polyol = 55 : 45 to 100 : 0, further preferably carbamate prepolymer : polyol = 60 : 40 to 100 : 0, particularly preferably carbamate prepolymer : polyol = 70 : 30 to 100 : 0, most preferably carbamate prepolymer : polyol = 80 : 20 to 100 : 0.

[0091] The content ratio of the urethane prepolymer in the urethane-based adhesive composition is preferably 80 to 99.99% by weight, more preferably 85 to 99.99% by weight, further preferably 90 to 99.99% by weight, particularly preferably 95 to 99.99% by weight, in the case where the base polymer does not contain a polyol. By adjusting the content ratio of the urethane prepolymer in the urethane-based adhesive composition to the above range in the case where the base polymer does not contain a polyol, the surface protection film of the present application can further exhibit the effects of the present application.

[0092] The content ratio of the urethane prepolymer in the urethane-based adhesive composition is preferably 40 to 99.98% by weight, more preferably 42 to 99.98% by weight, further preferably 44 to 99.98% by weight, particularly preferably 46 to 99.98% by weight, in the case where the base polymer contains a polyol. By adjusting the content ratio of the urethane prepolymer in the urethane-based adhesive composition to the above range in the case where the base polymer contains a polyol, the surface protection film of the present application can further exhibit the effects of the present application.

[0093] The urethane prepolymer preferably contains a polyoxyalkylene structure represented by the above general formula (1). By causing the urethane prepolymer to contain a polyoxyalkylene structure represented by the above general formula (1), light peeling properties can be further exhibited.

[0094] The urethane prepolymer preferably contains a polyoxyalkylene structure represented by the above general formula (2). By causing the urethane prepolymer to contain a polyoxyalkylene structure represented by the above general formula (2), light peeling properties can be further exhibited.

[0095] As specific preferred embodiments of the urethane prepolymer, the following can be cited:

[0096] <Embodiment a> a urethane prepolymer (Ul) containing a polyoxyalkylene structure represented by the above general formula (1) and not containing a polyoxyalkylene structure represented by the above general formula (2),

[0097] <Embodiment b> a urethane prepolymer (U2) containing both a polyoxyalkylene structure represented by the above general formula (1) and a polyoxyalkylene structure represented by the above general formula (2),

[0098] <Embodiment c> a urethane prepolymer (U3) containing a polyoxyalkylene structure represented by the above general formula (2) and not containing a polyoxyalkylene structure represented by the above general formula (2).

[0099] The content ratio of the polyoxyalkylene structure represented by the above general formula (1) and the polyoxyalkylene structure represented by the above general formula (2) in the urethane prepolymer (U2) can be any appropriate content ratio within a range not impairing the effects of the present application. As such a content ratio, the content ratio of the polyoxyalkylene structure represented by the above general formula (1) is preferably 50% by weight or more and 99.9% by weight or less, more preferably 60% by weight or more and 99% by weight or less, further preferably 65% by weight or more and 98% by weight or less, particularly preferably 70% by weight or more and 95% by weight or less, based on the total amount of the polyoxyalkylene structure represented by the above general formula (1) and the polyoxyalkylene structure represented by the above general formula (2). By adjusting the content ratio of the polyoxyalkylene structure represented by the above general formula (1) to the above range based on the total amount of the polyoxyalkylene structure represented by the above general formula (1) and the polyoxyalkylene structure represented by the above general formula (2), the surface protective film of the present application can further exhibit the effects of the present application.

[0100] The urethane prepolymer is typically a polyurethane polyol, which is preferably obtained by reacting at least one selected from a polyether polyol and a polyester polyol with a polyfunctional isocyanate compound (A) in the presence of a catalyst or without a catalyst.

[0101] The polyether polyol can be only one or two or more.

[0102] The polyester polyol can be only one or two or more.

[0103] As the urethane prepolymer, a urethane prepolymer available as a commercial product can be used.

[0104] As the polyether polyol, any appropriate polyether polyol can be used within a range not impairing the effects of the present application. As such a polyether polyol, for example, a polyether polyol obtained by polymerizing an epoxy compound such as ethylene oxide, propylene oxide, butylene oxide, or tetrahydrofuran using a low-molecular-weight polyol such as water, propylene glycol, ethylene glycol, glycerol, or trimethylolpropane as an initiator can be exemplified. As such a polyether polyol, for example, a polypropylene glycol (also referred to as a polyoxypropylene glycol), a polyethylene glycol (also referred to as a polyoxyethylene glycol), a polytetramethylene glycol (also referred to as a polyoxytetramethylene glycol), a polyoxypropylene triol, or the like having a functional group number of two or more, and a modified product thereof can be exemplified.

[0105] The polyether polyol can be used in combination with a part of it being replaced with, for example, a diol such as ethylene glycol, 1,4-butanediol, neopentyl glycol, butyl ethyl pentanediol, glycerol, trimethylolpropane, or pentaerythritol, a polyamine such as ethylenediamine, N-aminoethyl ethanolamine, isophorone diamine, or xylylenediamine, as needed.

[0106] The number average molecular weight Mn of the polyether polyol is preferably 500 to 5000, more preferably 1000 to 4500, further preferably 1000 to 4000. When the number average molecular weight is less than 500, there is a concern that the reactivity becomes high and gelling easily occurs. When the number average molecular weight exceeds 5000, there is a concern that the reactivity becomes low and further the cohesive force of the urethane prepolymer itself becomes small.

[0107] As the polyether polyol, only a 2-functional polyether polyol can be used, or a part or all of a polyether polyol having a number average molecular weight of 500 to 5000 and having at least 3 or more hydroxyl groups in one molecule can be used. When a part or all of a polyether polyol having an average molecular weight of 500 to 5000 and having at least 3 or more hydroxyl groups in one molecule is used as the polyether polyol, the balance between the adhesion and the re-peelability can become good. In such a polyether polyol, when the number average molecular weight is less than 500, there is a concern that the reactivity becomes high and gelling easily occurs. In addition, in such a polyether polyol, when the number average molecular weight exceeds 5000, there is a concern that the reactivity becomes low and further the cohesive force of the urethane prepolymer itself becomes small.

[0108] As the polyester polyol, any appropriate polyester polyol can be used within a range not impairing the effects of the present application. As such a polyester polyol, for example, a polyester polyol obtained by reacting an acid component with a diol component can be cited. As the acid component, for example, terephthalic acid, adipic acid, azelaic acid, sebacic acid, phthalic anhydride, isophthalic acid, trimellitic acid can be cited. As the diol component, for example, ethylene glycol, propylene glycol, diethylene glycol, butylene glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 3,3'-dihydroxymethylheptane, polyoxyethylene glycol, polyoxypropylene glycol, 1,4-butanediol, neopentyl glycol, butyl ethyl pentanediol, glycerol, trimethylolpropane, pentaerythritol as the polyol component can be cited. As the polyester polyol, in addition to these, for example, a polyester polyol obtained by ring-opening polymerization of a lactone such as polycaprolactone, poly(β-methyl-γ-valerolactone), polyvalerolactone, etc. can be cited.

[0109] The number average molecular weight Mn of the polyester polyol is preferably 500 to 5000. When the number average molecular weight is less than 500, there is a concern that the reactivity becomes high and gelling easily occurs. When the number average molecular weight exceeds 5000, there is a concern that the reactivity becomes low and further the cohesive force of the urethane prepolymer itself becomes small. Note that the use amount of the polyester polyol is preferably 1 to 90 mol%, more preferably 3 to 70 mol%, further preferably 5 to 50 mol%, particularly preferably 7 to 30 mol% in the total amount of the polyether polyol and the polyester polyol as the raw material of the urethane prepolymer from the viewpoint that the effects of the present application can be further exhibited.

[0110] When the urethane prepolymer (U1) is used as the urethane prepolymer, the polyol (at least one selected from the group consisting of a polyether polyol and a polyester polyol) as a raw material of the urethane prepolymer preferably contains the polyether polyol (PO1) containing the polyoxyalkylene structure represented by the above general formula (1) and does not contain the polyether polyol (PO2) containing the polyoxyalkylene structure represented by the above general formula (2). In this case, the contained ratio of the polyether polyol (PO1) in the total amount of the polyol (at least one selected from the group consisting of a polyether polyol and a polyester polyol) as a raw material of the urethane prepolymer is preferably 50% by weight or more to 100% by weight or less, more preferably 70% by weight or more to 100% by weight or less, further preferably 90% by weight or more to 100% by weight or less, and most preferably 95% by weight or more to 100% by weight or less, from the viewpoint that the effects of the present application can be further exhibited.

[0111] When the urethane prepolymer (U2) is used as the urethane prepolymer, the polyol (at least one selected from the group consisting of a polyether polyol and a polyester polyol) as a raw material of the urethane prepolymer preferably contains both the polyether polyol (PO1) containing the polyoxyalkylene structure represented by the above general formula (1) and the polyether polyol (PO2) containing the polyoxyalkylene structure represented by the above general formula (2). In this case, the use ratio of the polyether polyol (PO1) and the polyether polyol (PO2) is preferably 50% by weight or more to 99% by weight or less, more preferably 60% by weight or more to 95% by weight or less, further preferably 70% by weight or more to 90% by weight or less, and particularly preferably 75% by weight or more to 85% by weight or less, with respect to the amount of the polyether polyol (PO1) to the total amount of the polyether polyol (PO1) and the polyether polyol (PO2), from the viewpoint that the effects of the present application can be further exhibited.

[0112] When the urethane prepolymer (U3) is used as the urethane prepolymer, the polyol (at least one selected from the group consisting of a polyether polyol and a polyester polyol) as a raw material of the urethane prepolymer preferably contains the polyether polyol (PO2) containing the polyoxyalkylene structure represented by the above general formula (2) and does not contain the polyether polyol (PO1) containing the polyoxyalkylene structure represented by the above general formula (1). In this case, the contained ratio of the polyether polyol (PO2) in the total amount of the polyol (at least one selected from the group consisting of a polyether polyol and a polyester polyol) as a raw material of the urethane prepolymer is preferably 50% by weight or more to 100% by weight or less, more preferably 60% by weight or more to 100% by weight or less, further preferably 70% by weight or more to 100% by weight or less, and most preferably 80% by weight or more to 100% by weight or less, from the viewpoint that the effects of the present application can be further exhibited.

[0113] As the polyether polyol (PO1), for example, polytetramethylene glycol (also referred to as polyoxytetramethylene glycol), a modified product thereof can be exemplified.

[0114] The number average molecular weight Mn of the polyether polyol (PO1) is preferably from 1000 to 5000, more preferably from 1500 to 4500, further preferably from 2000 to 4000, particularly preferably from 2200 to 3800, most preferably from 2500 to 3500, from the viewpoint that the effects of the present application can be further exhibited.

[0115] As the polyether polyol (PO2), for example, polypropylene glycol (also referred to as polyoxypropylene glycol), polyethylene glycol (also referred to as polyoxyethylene glycol), polyoxypropylene triol, and modified products thereof can be exemplified.

[0116] The number average molecular weight Mn of the polyether polyol (PO2) is preferably from 500 to 4500, more preferably from 600 to 4000, further preferably from 700 to 3500, particularly preferably from 800 to 3000, most preferably from 900 to 2500, from the viewpoint that the effects of the present application can be further exhibited.

[0117] When the polyether polyol (PO2) is used as a raw material of the urethane prepolymer (U3), from the viewpoint that the effects of the present application can be further exhibited, it is preferable to use in combination a polyether polyol (PO2) having a number average molecular weight Mn of 1500 or more and a polyether polyol (PO2) having a number average molecular weight Mn of less than 1500. In this case, the content ratio of the polyether polyol (PO2) having a number average molecular weight Mn of 1500 or more in the total amount of the polyether polyol (PO2) used as a raw material of the urethane prepolymer (U3) is preferably from 10% by mass to 90% by mass, more preferably from 20% by mass to 80% by mass, further preferably from 30% by mass to 70% by mass, most preferably from 40% by mass to 60% by mass.

[0118] As the polyfunctional isocyanate compound (A), any appropriate polyfunctional isocyanate compound can be used without impairing the effects of the present application. As such a polyfunctional isocyanate compound (A), for example, aromatic polyisocyanate, aliphatic polyisocyanate, aromatic aliphatic polyisocyanate, alicyclic polyisocyanate can be exemplified.

[0119] As the aromatic polyisocyanate, for example, 1,3-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,4-phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 2,2'-diphenylmethane diisocyanate, 4,4'-toluene diisocyanate, 2,4,6-triisocyanatetoluene, 1,3,5-triisocyanatobenzene, o-xylylene diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4',4"-triphenylmethane triisocyanate, 1,5-naphthalene diisocyanate, xylene diisocyanate can be exemplified.

[0120] As the aliphatic polyisocyanate, for example, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, 1,2- propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate can be exemplified.

[0121] As the aromatic aliphatic polyisocyanate, 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 can be exemplified.

[0122] As the alicyclic polyisocyanate, for example, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate, 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4'-methylenebis(cyclohexyl isocyanate), 1,4-bis(isocyanatomethyl)cyclohexane, 1,4-bis(isocyanatomethyl)cyclohexane, isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylene diisocyanate, hydrogenated toluene diisocyanate, hydrogenated tetramethylxylylene diisocyanate can be exemplified.

[0123] As the polyfunctional isocyanate compound (A), trimethylolpropane adducts of various polyfunctional isocyanate compounds described above, biuret bodies obtained by reacting with water, and trimers having isocyanurate rings can also be exemplified. In addition, they can be used in combination.

[0124] As the catalyst which can be used at the time of producing the urethane prepolymer, any appropriate catalyst can be used within a range not impairing the effects of the present application. As such a catalyst, for example, tertiary amine-based compounds, organometal-based compounds can be cited. The catalyst can be only one kind, or two or more kinds.

[0125] As the tertiary amine-based compounds, for example, triethylamine, triethylene diamine, 1,8-diazabicyclo(5,4,0)-undec-7-ene (DBU) can be cited.

[0126] As the organometal-based compounds, for example, tin-based compounds, non-tin-based compounds can be cited.

[0127] As the tin-based compounds, for example, 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 can be cited.

[0128] As the non-tin-based compounds, for example, dibutyltitanium dichloride, tetrabutyl titanate, titanium-based compounds such as butoxytitanium trichloride; lead-based compounds such as lead oleate, lead 2-ethylhexanoate, lead benzoate, lead naphthenate; iron-based compounds such as iron 2-ethylhexanoate, iron acetylacetonate; cobalt-based compounds such as cobalt benzoate, cobalt 2-ethylhexanoate; zinc-based compounds such as zinc naphthenate, zinc 2-ethylhexanoate; zirconium-based compounds such as zirconium naphthenate can be cited.

[0129] As the catalyst, from the viewpoint of further exhibiting the effects of the present application, it is preferable to use tin-based compounds, on the other hand, from the viewpoint of environmental measures, it is preferable to use non-tin-based compounds.

[0130] In the case where a catalyst is used at the time of producing the urethane prepolymer, the amount of use of the catalyst is preferably 0.01 to 1.0% by weight relative to the total amount of the polyol (at least one kind selected from the group consisting of polyether polyol and polyester polyol) and the polyfunctional isocyanate compound (A) as raw materials of the urethane prepolymer.

[0131] In the case where a catalyst is used at the time of producing the urethane prepolymer, the reaction temperature is preferably less than 100°C, more preferably 85 to 95°C. In the case of 100°C or more, there is a concern that the reaction rate, the control of crosslinking structure become difficult, and there is a concern that it is difficult to obtain a urethane prepolymer having a prescribed molecular weight.

[0132] In the production of the urethane prepolymer, a catalyst can not be used. In this case, the reaction temperature is preferably 100°C or higher, more preferably 110°C or higher. In addition, in the production of the urethane prepolymer without a catalyst, the reaction is preferably performed for 3 hours or longer.

[0133] As the method for producing the urethane prepolymer, for example, 1) a method in which the polyol (at least one selected from the group consisting of a polyether polyol and a polyester polyol), the catalyst, and the polyfunctional isocyanate compound (A) as raw materials are all added to a reactor, and 2) a method in which the polyol (at least one selected from the group consisting of a polyether polyol and a polyester polyol), the catalyst are added to a reactor, and then the polyfunctional isocyanate compound (A) is added dropwise. From the viewpoint of controlling the reaction, the method of 2) is preferable.

[0134] In the production of the urethane prepolymer, any appropriate solvent can be used within a range not impairing the effects of the present application. As such a solvent, for example, methyl ethyl ketone, ethyl acetate, toluene, xylene, and acetone can be exemplified. Among these solvents, ethyl acetate and toluene are preferable.

[0135] "1-1-2. Polyol"

[0136] The base polymer optionally contains a polyol. Among them, as described above, the polyol in the present application is not the urethane prepolymer.

[0137] When the base polymer contains a polyol, the content ratio of the polyol in the urethane adhesive composition is preferably 0.02% by weight or more and 80% by weight or less, more preferably 0.02% by weight or more and 70% by weight or less, further preferably 0.02% by weight or more and 60% by weight or less, particularly preferably 0.02% by weight or more and 55% by weight or less. When the base polymer contains a polyol, by adjusting the content ratio of the polyol in the urethane adhesive composition to the above range, the surface protection film of the present application can further exhibit the effects of the present application.

[0138] As the polyol, for example, a polyester polyol, a polyether polyol, a polycaprolactone polyol, a polycarbonate polyol, and a castor oil-based polyol can be exemplified. As the polyol, a polyester polyol and a polyether polyol are more preferable.

[0139] As the polyester polyol, for example, it can be obtained by an esterification reaction of a polyol component and an acid component.

[0140] As the polyol component, for example, ethylene glycol, diethylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2-butyl-2-ethyl-1,3-propanediol, 2,4-diethyl-1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, 1,8-decanediol, octadecanediol, glycerol, trimethylolpropane, pentaerythritol, hexanetriol, polypropylene glycol can be exemplified.

[0141] As the acid component, for example, succinic acid, methylsuccinic acid, adipic acid, pimelic acid, azelaic acid, sebacic acid, 1,12-dodecanedioic acid, 1,14-tetradecanedioic acid, dimer acid, 2-methyl-1,4-cyclohexanedicarboxylic acid, 2-ethyl-1,4-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, isophthalic acid, terephthalic acid, 1,4-naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, anhydrides thereof can be exemplified.

[0142] As the polyether polyol, for example, polyether polyols obtained by addition polymerization of alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, etc. with water, low molecular polyols (propylene glycol, ethylene glycol, glycerol, trimethylolpropane, pentaerythritol, etc.), bisphenols (bisphenol A, etc.), dihydroxybenzene (catechol, resorcinol, hydroquinone, etc.), etc. as initiators can be exemplified. Specifically, for example, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, etc. can be exemplified.

[0143] As the polycaprolactone polyol, for example, caprolactone-based polyester diols obtained by ring-opening polymerization of cyclic ester monomers such as ε-caprolactone, σ-valerolactone, etc. can be exemplified.

[0144] As the polycarbonate polyol, for example, polycarbonate polyols obtained by subjecting the above polyol component to a polycondensation reaction with phosgene; polycarbonate polyols obtained by subjecting the above polyol component to a transesterification condensation with carbonic acid diesters such as dimethyl carbonate, diethyl carbonate, dipropyl carbonate, diisopropyl carbonate, dibutyl carbonate, ethyl butyl carbonate, ethylene carbonate, propylene carbonate, diphenyl carbonate, dibenzyl carbonate, and the like; copolymer polycarbonate polyols obtained by using two or more kinds of the above polyol components in combination; polycarbonate polyols obtained by subjecting the above various polycarbonate polyols to an esterification reaction with a carboxyl-containing compound; polycarbonate polyols obtained by subjecting the above various polycarbonate polyols to an etherification reaction with a hydroxyl-containing compound; polycarbonate polyols obtained by subjecting the above various polycarbonate polyols to a transesterification reaction with an ester compound; polycarbonate polyols obtained by subjecting the above various polycarbonate polyols to a transesterification reaction with a hydroxyl-containing compound; polyester-based polycarbonate polyols obtained by subjecting the above various polycarbonate polyols to a polycondensation reaction with a dicarboxylic acid compound; and copolymer polyether-based polycarbonate polyols obtained by subjecting the above various polycarbonate polyols to copolymerization with an alkylene oxide can be exemplified.

[0145] As the castor oil-based polyol, for example, castor oil-based polyols obtained by subjecting castor oil fatty acid to a reaction with the above polyol component can be exemplified. Specifically, for example, castor oil-based polyols obtained by subjecting castor oil fatty acid to a reaction with polypropylene glycol can be exemplified.

[0146] As the polyol, a polyether polyol (PO1) containing a polyoxyalkylene structure represented by the above general formula (1) can be used.

[0147] As the polyether polyol (PO1), the same as the aforementioned, for example, polytetramethylene glycol (also referred to as polyoxytetramethylene glycol), a modified product thereof can be exemplified.

[0148] The polyol is preferably composed of a first polyol having a number average molecular weight Mn of 5000 to 20000 and a second polyol having a number average molecular weight Mn of 300 to 4999 from the viewpoint that the effects of the present application can be further exhibited.

[0149] The first polyol A1 can be only one kind, or two or more kinds.

[0150] The second polyol A2 can be only one kind, or two or more kinds.

[0151] The content ratio of the total amount of the first polyol and the second polyol in the polyol is preferably 80% by weight or more to 100% by weight or less, more preferably 90% by weight or more to 100% by weight or less, further preferably 95% by weight or more to 100% by weight or less, particularly preferably 98% by weight or more to 100% by weight or less, and most preferably substantially 100% by weight, from the viewpoint that the effects of the present application can be further exhibited.

[0152] The number average molecular weight Mn of the first polyol is preferably 5,000 to 20,000, more preferably 6,000 to 18,000, further preferably 7,000 to 16,000, particularly preferably 8,000 to 15,000, and most preferably 9,000 to 14,000. When the number average molecular weight Mn of the first polyol is within the above range, the effects of the present application can be further exhibited.

[0153] The number average molecular weight Mn of the second polyol is preferably 300 to 4,999, more preferably 500 to 4,500, further preferably 1,000 to 4,000, particularly preferably 1,500 to 3,800, and most preferably 2,000 to 3,500. When the number average molecular weight Mn of the second polyol is within the above range, the effects of the present application can be further exhibited.

[0154] The weight ratio of the first polyol to the second polyol is preferably 0.7 or more to 3.5 or less, more preferably 1.0 or more to 3.0 or less, further preferably 1.1 or more to 2.5 or less, and particularly preferably 1.2 or more to 2.0 or less. When the weight ratio of the first polyol to the second polyol is within the above range, the surface protective film of the embodiment of the present application can achieve excellent low haze, for example, and can exhibit excellent inspectability.

[0155] The first polyol preferably has 3 to 6 OH groups, more preferably 3 to 5 OH groups, further preferably 3 to 4 OH groups, and particularly preferably 3 OH groups, from the viewpoint that the effects of the present application can be further exhibited.

[0156] The first polyol preferably contains 50% by weight or more to 100% by weight or less of a triol having 3 OH groups, more preferably 70% by weight or more to 100% by weight or less, further preferably 90% by weight or more to 100% by weight or less, particularly preferably 95% by weight or more to 100% by weight or less, and most preferably substantially 100% by weight, from the viewpoint that the effects of the present application can be further exhibited.

[0157] The second polyol preferably has 3 to 6 OH groups, more preferably 3 to 5 OH groups, further preferably 3 to 4 OH groups, and particularly preferably 3 OH groups, from the viewpoint that the effects of the present application can be further exhibited.

[0158] The second polyol is preferably one that contains 50 to 100% by weight of a triol having 3 OH groups from the viewpoint of further exhibiting the effects of the present application, more preferably one that contains 70 to 100% by weight, further preferably one that contains 90 to 100% by weight, particularly preferably one that contains 95 to 100% by weight, most preferably one that contains substantially 100% by weight.

[0159] 1-1-3. Polyfunctional isocyanate compound (B)

[0160] The urethane-based adhesive composition preferably contains a polyfunctional isocyanate compound (B). The urethane-based adhesive composition, by containing the polyfunctional isocyanate compound (B), undergoes cross-linking reaction with the urethane prepolymer contained in the urethane-based adhesive composition, and the polyol that can be contained as an optional component, to form the urethane-based adhesive.

[0161] The polyfunctional isocyanate compound (B) can be only one or two or more.

[0162] As the polyfunctional isocyanate compound (B), any appropriate polyfunctional isocyanate compound that can be used in urethane-forming reaction can be used. As such a polyfunctional isocyanate compound (B), for example, aromatic polyisocyanates, aliphatic polyisocyanates, aromatic-aliphatic polyisocyanates, alicyclic polyisocyanates can be exemplified.

[0163] As the aromatic polyisocyanate, for example, 1,3-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,4-phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 2,2'-diphenylmethane diisocyanate, 4,4'-toluidine diisocyanate, 2,4,6-triisocyanatotoluene, 1,3,5-triisocyanatobenzene, o-xylylene diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4',4"-triphenylmethane triisocyanate, 1,5-naphthalene diisocyanate, xylylene diisocyanate can be exemplified.

[0164] As the aliphatic polyisocyanate, for example, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, 1,2- propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate can be exemplified.

[0165] As the aromatic aliphatic polyisocyanate, for example, there can be mentioned ω,ω'-diisocyanate-1,3-dimethylbenzene, ω,ω'-diisocyanate-1,4-dimethylbenzene, ω,ω'-diisocyanate-1,4-diethylbenzene, 1,4-tetramethylbenzenedimethylene diisocyanate, 1,3-tetramethylbenzenedimethylene diisocyanate.

[0166] As the alicyclic polyisocyanate, for example, there can be mentioned 3-isocyanatemethyl-3,5,5-trimethylcyclohexyl isocyanate, 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4'-methylenebis(cyclohexyl isocyanate), 1,4-bis(isocyanatemethyl)cyclohexane, 1,4-bis(isocyanatemethyl)cyclohexane, isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated toluene diisocyanate, hydrogenated tetramethylxylylene diisocyanate.

[0167] As the polyfunctional isocyanate compound (B), there can also be mentioned trimethylolpropane adducts of various polyfunctional isocyanate compounds as described above, biuret bodies obtained by reacting with water, and trimers having isocyanurate rings. In addition, they can be used in combination.

[0168] The content ratio of the polyfunctional isocyanate compound (B) in the urethane-based adhesive composition is preferably 2.0 parts by weight to 40 parts by weight, more preferably 2.3 parts by weight to 30 parts by weight, further preferably 2.5 parts by weight to 20 parts by weight, and particularly preferably 3.0 parts by weight to 15 parts by weight, relative to 100 parts by weight of the base polymer, from the viewpoint that the effects of the present application can be further exhibited.

[0169] The equivalent ratio of the NCO group and the OH group in the urethane-based adhesive composition is preferably 1.0 to 2.0, more preferably 1.1 to 1.9, further preferably 1.2 to 1.8, and particularly preferably 1.2 to 1.7, in terms of NCO group / OH group, from the viewpoint that the effects of the present application can be further exhibited.

[0170] 1-1-4. Fluorine-based compound

[0171] The urethane-based adhesive composition contains a fluorine-based compound. By containing the fluorine-based compound in the urethane-based adhesive composition, the effects of the present application can be further exhibited.

[0172] The fluorine-based compound can be only one kind, or two or more kinds.

[0173] The content ratio of the fluorine-based compound in the urethane-based adhesive composition is preferably 0.01 parts by weight or more, more preferably 0.03 parts by weight to 30 parts by weight, further preferably 0.05 parts by weight to 10 parts by weight, and particularly preferably 0.05 parts by weight to 1 part by weight, relative to 100 parts by weight of the base polymer, from the viewpoint of further exhibiting the effects of the present application.

[0174] The surface tension of the fluorine-based compound when made into a 0.1% propylene glycol monomethyl ether solution is preferably 23 mN / m or more, and more preferably 23 mN / m to 26 mN / m (the surface tension of propylene glycol monomethyl ether is 27.1 mN / m). When the surface tension of the fluorine-based compound when made into a 0.1% propylene glycol monomethyl ether solution is set within the above range, the effects of the present application can be further exhibited. In particular, when the surface tension of the fluorine-based compound when made into a 0.1% propylene glycol monomethyl ether solution is set within the above range, the generation of black spots can be more effectively suppressed.

[0175] As the fluorine-based compound, for example, at least one selected from the group consisting of a fluorine-containing compound, a hydroxyl group-containing fluorine-based compound, and a crosslinkable functional group-containing fluorine-based compound can be exemplified.

[0176] As the fluorine-containing compound, 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 can be exemplified. As the fluoroaliphatic hydrocarbon skeleton, for example, fluoro-C1-C10 alkane such as fluoromethane, fluoroethane, fluoropropane, fluoroisopropane, fluorobutane, fluoroisobutane, fluorotert-butane, fluoropentane, and fluorohexane can be exemplified. Here, the expression "C1-C10" means that the number of carbons is 1 to 10.

[0177] A preferable embodiment of the fluorine-containing compound is an oligomer having a fluorine-containing group and having a hydrophilic group and / or a lipophilic group ("specific fluorine-based compound").

[0178] As the fluorine-containing group, a fluorine-containing alkyl group (for example, CF3- and the like) and / or a fluorine-containing alkylene group (for example, -CF2-CF2- and the like) can be exemplified as representative.

[0179] The hydrophilic group refers to a group having hydrophilicity, which is a property generally known to those skilled in the art as the meaning of "hydrophilic" and "having affinity with water" (for example, see McGraw-Hill Dictionary of Scientific & Technical Terms (Revised 3rd Edition, NIKKAN KOGYO SHIMBUN, LTD.), etc.). The lipophilic group refers to a group having lipophilicity, which is a property generally known to those skilled in the art as the meaning of "lipophilic" and "having affinity with oil" (for example, see McGraw-Hill Dictionary of Scientific & Technical Terms (Revised 3rd Edition, NIKKAN KOGYO SHIMBUN, LTD.), etc.).

[0180] By using such a "specific fluorine-based compound" as the fluorine-based compound, the effect of the present application can be further exhibited. In particular, by using the "specific fluorine-based compound" as the fluorine-based compound, the surface protective film of the embodiment of the present application can exhibit excellent light peeling properties.

[0181] When such a "specific fluorine-based compound" is used in combination with the ionic compound described later, the antistatic properties of the surface protective film of the embodiment of the present application can be further improved. It is presumed that this is because, due to the specific fluorine-based compound, the ionic compound is present more on the surface side (the side to be adhered to the adherend) of the urethane-based adhesive layer.

[0182] As the fluorine-containing compound, as a commercially available product, for example, the following substances can be listed.

[0183] Megafac series manufactured by DIC Corporation:

[0184] Megafac F-114, Megafac F-253, Megafac F-281, Megafac F-410, Megafac F-430, Megafac F-444, Megafac F-477, Megafac F-510, Megafac F-551, Megafac F-553, Megafac F-554, Megafac F-556, Megafac F-557, Megafac F-559, Megafac F-561, Megafac F-562, Megafac F-565, Megafac F-568, Megafac F-570, Megafac F-571, 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, and the like.

[0185] Surflon series manufactured by AGC Seimi Chemical Co., Ltd.:

[0186] Representative examples include "S-242", "S-243", "S-386", and the like.

[0187] FC series manufactured by Sumitomo 3M Co., Ltd.:

[0188] Representative examples include "FC-4430", "FC-4432", and the like.

[0189] Ftergent series manufactured by NEOS Corporation:

[0190] Representative examples include "Ftergent 100", "Ftergent 100C", "Ftergent 110", "Ftergent 150", "Ftergent 150CH", "Ftergent 250", "Ftergent 400SW", and the like.

[0191] PF series manufactured by Kitagawa Chemical Industry Co., Ltd.:

[0192] Representative examples include "PF-136A", "PF-156A", "PF-151N", "PF-636", "PF-6320", "PF-656", "PF-6520", "PF-651", "PF-652", "PF-3320", and the like.

[0193] As the hydroxyl group-containing fluorine-based compound, for example, a resin known in the past can be used, and for example, a hydroxyl group-containing fluororesin described in International Publication No. 94 / 06870, Japanese Patent Application Laid-Open No. 8-12921, Japanese Patent Application Laid-Open No. 10-72569, Japanese Patent Application Laid-Open No. 4-275379, International Publication No. 97 / 11130, International Publication No. 96 / 26254, and the like can be exemplified. As other hydroxyl group-containing fluororesin, for example, a fluorinated olefin copolymer described in Japanese Patent Application Laid-Open No. 8-231919, Japanese Patent Application Laid-Open No. 10-265731, Japanese Patent Application Laid-Open No. 10-204374, Japanese Patent Application Laid-Open No. 8-12922, and the like can be exemplified. Further, a copolymer of a compound having a fluorinated alkyl group among the hydroxyl group-containing compounds, a fluorine-containing organic compound obtained by copolymerizing a hydroxyl group-containing compound with a fluorine-containing compound, a fluorine-containing compound containing a hydroxyl group-containing organic compound, and the like can be exemplified. As such a hydroxyl group-containing fluorine-based compound, as a commercial product, for example, a product with a trade name of "Lumiflon" (manufactured by Asahi Glass Co., Ltd.), a product with a trade name of "Cefral Coat" (manufactured by Central Glass Co., Ltd.), a product with a trade name of "Zaflon" (manufactured by Toagosei Co., Ltd.), a product with a trade name of "Zeffle" (manufactured by Daikin Industries, Ltd.) can be exemplified.

[0194] As the fluorine-based compound containing a crosslinkable functional group, for example, a carboxylic acid compound having a fluorinated alkyl group such as perfluorooctanoic acid, a copolymer of a compound having a fluorinated alkyl group among the compounds containing a crosslinkable functional group, a fluorine-containing organic compound obtained by copolymerizing a compound containing a crosslinkable functional group with a fluorine-containing compound, a fluorine-containing compound containing a compound containing a crosslinkable functional group can be exemplified. As such a fluorine-based compound containing a crosslinkable functional group, as a commercial product, for example, a product with a trade name of "Megafac F-570", "Megafac RS-55", "Megafac RS-56", "Megafac RS-72-K", "Megafac RS-75", "Megafac RS-76-E", "Megafac RS-76-NS", "Megafac RS-78", "Megafac RS-90" (manufactured by DIC Corporation) can be exemplified.

[0195] Among the fluorine-containing compounds available as commercial products, as the fluorine-containing compound belonging to the aforementioned "oligomer having a fluorine-containing group and having a hydrophilic group and / or a lipophilic group", representative are DIC Corporation's "Megafac F- 251" (oligomer having a fluorine-containing group, a hydrophilic group, and a lipophilic group, surface tension = 22.7 mN / m when made into a 0.1% propylene glycol monomethyl ether solution),

[0196] "Megafac F-477" (oligomer having a fluorine-containing group, a hydrophilic group, and a lipophilic group, surface tension = 25.4 mN / m when made into a 0.1% propylene glycol monomethyl ether solution),

[0197] "Megafac F-477" (oligomer having a fluorine-containing group, a hydrophilic group, and a lipophilic group, surface tension = 25.4 mN / m when made into a 0.1% propylene glycol monomethyl ether solution),

[0198] "Megafac F-477" (oligomer having a fluorine-containing group, a hydrophilic group, and a lipophilic group, surface tension = 25.4 mN / m when made into a 0.1% propylene glycol monomethyl ether solution),

[0199] "Megafac F-477" (oligomer having a fluorine-containing group, a hydrophilic group, and a lipophilic group, surface tension = 25.4 mN / m when made into a 0.1% propylene glycol monomethyl ether solution),

[0200] "Megafac F-477" (oligomer having a fluorine-containing group, a hydrophilic group, and a lipophilic group, surface tension = 25.4 mN / m when made into a 0.1% propylene glycol monomethyl ether solution),

[0201] "Megafac F-477" (oligomer having a fluorine-containing group, a hydrophilic group, and a lipophilic group, surface tension = 25.4 mN / m when made into a 0.1% propylene glycol monomethyl ether solution),

[0202] "Megafac F-477" (oligomer having a fluorine-containing group, a hydrophilic group, and a lipophilic group, surface tension = 25.4 mN / m when made into a 0.1% propylene glycol monomethyl ether solution),

[0203] "Megafac F-477" (oligomer having a fluorine-containing group, a hydrophilic group, and a lipophilic group, surface tension = 25.4 mN / m when made into a 0.1% propylene glycol monomethyl ether solution),

[0204] "Megafac F-477" (oligomer having a fluorine-containing group, a hydrophilic group, and a lipophilic group, surface tension = 25.4 mN / m when made into a 0.1% propylene glycol monomethyl ether solution),

[0205] "Megafac F-569" (oligomer containing a fluorine-containing group and a hydrophilic group, surface tension = 19.7 mN / m when made into a 0.1% propylene glycol monomethyl ether solution),

[0206] "Megafac F-571" (oligomer containing a fluorine-containing group and a hydrophilic group, surface tension = 24.2 mN / m when made into a 0.1% propylene glycol monomethyl ether solution), and the like.

[0207] "1-1-5. Ionic Compound"

[0208] The urethane-based adhesive composition optionally contains an ionic compound. When the urethane-based adhesive composition contains an ionic compound, the antistatic properties of the surface protective film of the embodiments of the present application can be further improved.

[0209] The content ratio of the ionic compound can be any appropriate content ratio within a range that does not impair the effects of the present application. From the viewpoint of further improving the antistatic properties of the surface protective film of the present application, the content ratio of the ionic compound in the urethane-based adhesive composition is preferably 0.05 parts by weight or more, more preferably 0.10 parts by weight to 50 parts by weight, further preferably 0.20 parts by weight to 30 parts by weight, particularly preferably 0.30 parts by weight to 10 parts by weight, and most preferably 0.40 parts by weight to 1 part by weight, relative to 100 parts by weight of the base polymer. When the content ratio of the ionic compound in the urethane-based adhesive composition is too small, deviating from the above range, there is a concern that sufficient antistatic properties cannot be imparted to the surface protective film of the present application. When the content ratio of the ionic compound in the urethane-based adhesive composition is too large, deviating from the above range, there is a concern that the contamination of the adherend increases.

[0210] As the ionic compound, any appropriate ionic compound can be used within a range that does not impair the effects of the present application.

[0211] The ionic compound can be only one kind or two or more kinds.

[0212] As the ionic compound, from the viewpoint of further exhibiting the effects of the present application, an ionic compound containing at least one selected from the group consisting of onium cations and metal cations and a fluorine organic anion, and an organic silicon oligomer containing an ionic group are preferred, and from the viewpoint of making the appearance of the adhesive layer more excellent, an ionic compound containing at least one selected from the group consisting of onium cations and metal cations and a fluorine organic anion is more preferred.

[0213] The ionic compound can also be an ionic liquid. The ionic liquid refers to a molten salt (ionic compound) that is in a liquid state at 25°C.

[0214] As the organosilicon oligomer containing an ionic group, any appropriate organosilicon oligomer containing an ionic group can be used within a range not impairing the effects of the present application. As the organosilicon oligomer containing an ionic group, for example, "X-40-2450" manufactured by Shokubai Co., Ltd. can be cited.

[0215] As the onium cation, any appropriate onium cation can be used within a range not impairing the effects of the present application. From the viewpoint that the effects of the present application can be further exhibited, as such onium cation, at least one selected from the group consisting of an ammonium cation (a nitrogen-containing onium cation), a sulfonium cation (a sulfur-containing onium cation), and a phosphorus-containing onium cation (a phosphonium cation) is preferred, and an ammonium cation is more preferred.

[0216] As the metal cation, any appropriate metal cation can be used within a range not impairing the effects of the present application. From the viewpoint that the effects of the present application can be further exhibited, as such metal cation, an alkali metal cation such as a Li cation, a Na cation, and a K cation is preferred.

[0217] As the fluoroorganic anion, any appropriate fluoroorganic anion can be used within a range not impairing the effects of the present application. The fluoroorganic anion can be completely fluorinated (perfluorinated) or partially fluorinated.

[0218] As such fluoroorganic anion, for example, a fluorinated aryl sulfonate, a perfluoroalkanesulfonate, a bis(fluorosulfonyl)imide, a bis(perfluoroalkanesulfonyl)imide, a cyano perfluoroalkanesulfonamide, a bis(cyano)perfluoroalkanesulfonylmethide, a cyano-bis-(perfluoroalkanesulfonyl)methide, a tris(perfluoroalkanesulfonyl)methide, a trifluoroacetate, a perfluoroalkylate, a tris(perfluoroalkanesulfonyl)methide, a (perfluoroalkanesulfonyl)trifluoroacetamide, and the like can be cited.

[0219] Among these fluoroorganic anions, from the viewpoint that the effects of the present application can be further exhibited, a perfluoroalkylsulfonate, a bis(fluorosulfonyl)imide, and a bis(perfluoroalkanesulfonyl)imide are preferred, and more specifically, for example, a trifluoromethanesulfonate, a pentafluoroethanesulfonate, a heptafluoropropylsulfonate, a nonafluorobutylsulfonate, a bis(fluorosulfonyl)imide, a bis(trifluoromethylsulfonyl)imide are preferred, and a bis(fluorosulfonyl)imide and a bis(trifluoromethylsulfonyl)imide are preferred.

[0220] As the ionic compound, from the viewpoint that the effects of the present application can be further exhibited, a ionic compound composed of an onium cation and a fluoroorganic anion is more preferred.

[0221] As the onium cation, at least one selected from the group consisting of structures represented by General Formulae (3) to (6) is preferred.

[0222]

[0223] In General Formula (3), Ra represents a hydrocarbon group having a carbon number of 4 to 20, optionally containing a hetero atom, Rb and Rc are the same or different, and represent hydrogen or a hydrocarbon group having a carbon number of 1 to 16, optionally containing a hetero atom. When a nitrogen atom contains a double bond, Rc is not present.

[0224] In General Formula (4), Rd represents a hydrocarbon group having a carbon number of 2 to 20, optionally containing a hetero atom, Re, Rf, and Rg are the same or different, and represent hydrogen or a hydrocarbon group having a carbon number of 1 to 16, optionally containing a hetero atom.

[0225] In General Formula (5), Rh represents a hydrocarbon group having a carbon number of 2 to 20, optionally containing a hetero atom, Ri, Rj, and Rk are the same or different, and represent hydrogen or a hydrocarbon group having a carbon number of 1 to 16, optionally containing a hetero atom.

[0226] In General Formula (6), Z represents a nitrogen atom, a sulfur atom, or a phosphorus atom, and Rl, Rm, Rn, and Ro are the same or different, and represent a hydrocarbon group having a carbon number of 1 to 20, optionally containing a hetero atom. When Z is a sulfur atom, Ro is not present.

[0227] Examples of the cation structure represented by General Formula (3) include a pyridinium cation structure, a pyrrolidinium cation structure, a piperidinium cation structure, a cation structure having a pyrroline skeleton, and a cation structure having a pyrrole skeleton.

[0228] As specific examples of the cation represented by General Formula (3), for example, there can be mentioned pyridinium cations such as 1-ethylpyridinium cation, 1-butylpyridinium cation, 1-hexylpyridinium cation, 1-ethyl-3-methylpyridinium cation, 1-butyl-3-methylpyridinium cation, 1-hexyl-3-methylpyridinium cation, 1-butyl-4-methylpyridinium cation, 1-octyl-4-methylpyridinium cation, 1-butyl-3,4-dimethylpyridinium cation, 1,1-dimethylpyrrolidinium cation, and the like; pyrrolidinium cations such as 1-ethyl-1-methylpyrrolidinium cation, 1-methyl-1-propylpyrrolidinium cation, 1-methyl-1-butylpyrrolidinium cation, 1-methyl-1-pentylpyrrolidinium cation, 1-methyl-1-hexylpyrrolidinium cation, 1-methyl-1-heptylpyrrolidinium cation, 1-ethyl-1-propylpyrrolidinium cation, 1-ethyl-1-butylpyrrolidinium cation, 1-ethyl-1-pentylpyrrolidinium cation, 1-ethyl-1-hexylpyrrolidinium cation, 1-ethyl-1-heptylpyrrolidinium cation, 1,1-dipropylpyrrolidinium cation, 1-propyl-1-butylpyrrolidinium cation, 1,1-dibutylpyrrolidinium cation, and the like; piperidinium cations such as 1-propylpiperidinium cation, 1-pentylpiperidinium cation, 1-methyl-1-ethylpiperidinium cation, 1-methyl-1-propylpiperidinium cation, 1-methyl-1-butylpiperidinium cation, 1-methyl-1-pentylpiperidinium cation, 1-methyl-1-hexylpiperidinium cation, 1-methyl-1-heptylpiperidinium cation, 1-ethyl-1-propylpiperidinium cation, 1-ethyl-1-butylpiperidinium cation, 1-ethyl-1-pentylpiperidinium cation, 1-ethyl-1-hexylpiperidinium cation, 1-ethyl-1-heptylpiperidinium cation, 1-propyl-1-butylpiperidinium cation, 1,1-dimethylpiperidinium cation, 1,1-dipropylpiperidinium cation, 1,1-dibutylpiperidinium cation, and the like; 2-methyl-1-pyrrolinium cation; 1-ethyl-2-phenylindolium cation; 1,2-dimethylindolium cation; 1-ethylcarbazolium cation; and the like. These cations further have at least one selected from the group consisting of a vinyl group (CH2=CH- group) and an allyl group (CH2=CH-CH2- group).

[0229] Among these, from the viewpoint of further exhibiting the effects of the present application, pyridinium cations such as 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 the like; pyrrolidinium cations such as 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 the like; piperidinium cations such as 1-methyl-1-ethylpiperidinium cation, 1-methyl-1-propylpiperidinium cation, 1-methyl-1-butylpiperidinium cation, 1-methyl-1-pentylpiperidinium cation, 1-methyl-1-hexylpiperidinium cation, 1-methyl-1-heptylpiperidinium cation, 1-ethyl-1-propylpiperidinium cation, 1-ethyl-1-butylpiperidinium cation, 1-ethyl-1-pentylpiperidinium cation, 1-ethyl-1-hexylpiperidinium cation, 1-ethyl-1-heptylpiperidinium cation, 1-propyl-1-butylpiperidinium cation, and the like; and cations further having at least one selected from the group consisting of a vinyl group (CH2=CH- group) and an allyl group (CH2=CH-CH2- group) are preferable.

[0230] As the cation structure represented by General Formula (4), for example, imidazolium cation structures, tetrahydropyrimidinium cation structures, dihydropyrimidinium cation structures can be cited.

[0231] As specific examples of the cation represented by General Formula (4), for example, there can be mentioned imidazolium cations such as 1,3-dimethylimidazolium cation, 1,3-diethylimidazolium cation, 1-ethyl-3-methylimidazolium cation, 1-butyl-3-methylimidazolium cation, 1-hexyl-3-methylimidazolium cation, 1-octyl-3-methylimidazolium cation, 1-decyl-3-methylimidazolium cation, 1-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-hexyl-2,3-dimethylimidazolium cation, and the like; tetrahydropyrimidinium cations such as 1,3-dimethyl-1,4,5,6-tetrahydropyrimidinium cation, 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-1,4,5,6-tetrahydropyrimidinium cation, and the like; dihydropyrimidinium cations such as 1,3-dimethyl-1,4-dihydropyrimidinium cation, 1,3-dimethyl-1,6-dihydropyrimidinium cation, 1,2,3-trimethyl-1,4-dihydropyrimidinium cation, 1,2,3-trimethyl-1,6-dihydropyrimidinium cation, 1,2,3,4-tetramethyl-1,4-dihydropyrimidinium cation, 1,2,3,4-tetramethyl-1,6-dihydropyrimidinium cation, and the like; and cations further having at least one selected from the group consisting of a vinyl group (CH2=CH- group) and an allyl group (CH2=CH-CH2- group).

[0232] Among these, from the viewpoint of further exhibiting the effects of the present application, imidazolium cations such as 1,3-dimethylimidazolium cation, 1,3-diethylimidazolium cation, 1-ethyl-3-methylimidazolium cation, 1-butyl-3-methylimidazolium cation, 1-hexyl-3-methylimidazolium cation, 1-octyl-3-methylimidazolium cation, 1-decyl-3-methylimidazolium cation, 1-dodecyl-3-methylimidazolium cation, 1-tetradecyl-3-methylimidazolium cation, and cations further having at least one selected from the group consisting of a vinyl group (CH2=CH- group) and an allyl group (CH2=CH-CH2- group) are preferable, and 1-ethyl-3-methylimidazolium cation, 1-hexyl-3-methylimidazolium cation, and cations further having at least one selected from the group consisting of a vinyl group (CH2=CH- group) and an allyl group (CH2=CH-CH2- group) are more preferable.

[0233] As the cation structure represented by General Formula (5), for example, there can be mentioned pyrazolium cation structures, pyrazolinium cation structures.

[0234] As specific examples of the cation represented by General Formula (5), for example, there can be mentioned 1-methylpyrazolium cation, 3-methylpyrazolium cation, 1-ethyl-2-methylpyrazolinium cation, 1-ethyl-2,3,5-trimethylpyrazolium cation, 1-propyl-2,3,5-trimethylpyrazolium cation, 1-butyl-2,3,5-trimethylpyrazolium cation, and the like pyrazolium cation; 1-ethyl-2,3,5-trimethylpyrazolinium cation, 1-propyl-2,3,5-trimethylpyrazolinium cation, 1-butyl-2,3,5-trimethylpyrazolinium cation, and the like pyrazolinium cation; and these cations further having at least one selected from the group consisting of a vinyl group (CH2=CH- group) and an allyl group (CH2=CH-CH2- group).

[0235] As the cation structure represented by General Formula (6), for example, there can be mentioned a tetraalkylammonium cation structure, a trialkylsulfonium cation structure, a tetraalkylphosphonium cation structure, and a cation structure in which a part of the alkyl group is replaced with an alkenyl group, an alkoxy group, or an epoxy group.

[0236] As specific examples of the cation represented by General Formula (6), for example, there can be mentioned tetramethylammonium cation, tetraethylammonium cation, tetrabutylammonium cation, tetrapentylammonium cation, tetrahexylammonium cation, tetraheptylammonium cation, triethylmethylammonium cation, tributylethylammonium cation, trimethylpropylammonium cation, trimethyldecylammonium cation, N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium cation, glycidyltrimethylammonium cation, diallyldimethylammonium cation, N,N-dimethyl-N-ethyl-N-propylammonium cation, N,N-dimethyl-N-ethyl-N-butylammonium cation, N,N-dimethyl-N-ethyl-N-pentylammonium cation, N,N-dimethyl-N-ethyl-N-hexylammonium cation, N,N-dimethyl-N-ethyl-N-heptylammonium cation, N,N-dimethyl-N-ethyl-N-nonylammonium cation, N,N-dimethyl-N,N-dipropylammonium cation, N,N-diethyl-N-propyl-N-butylammonium cation, N,N-dimethyl-N-propyl-N-pentylammonium cation, N,N-dimethyl-N-propyl-N-hexylammonium cation, N,N-dimethyl-N-propyl-N-heptylammonium cation, N,N-dimethyl-N-butyl-N-hexylammonium cation, N,N-diethyl-N-butyl-N-heptylammonium cation, N,N-dimethyl-N-pentyl-N-hexylammonium cation, N,N-dimethyl-N,N-dihexylammonium cation, trimethylheptylammonium cation, N,N-diethyl-N-methyl-N-propylammonium cation, N,N-diethyl-N-methyl-N-pentylammonium cation, N,N-diethyl-N-methyl-N-heptylammonium cation, N,N-diethyl-N-propyl-N-pentylammonium cation, triethylpropylammonium cation, triethylpentylammonium cation, triethylheptylammonium cation, N,N-dipropyl-N-methyl-N-ethylammonium cation, N,N-dipropyl-N-methyl-N-pentylammonium cation, N,N-dipropyl-N-butyl-N-hexylammonium cation, N,N-dipropyl-N,N-dihexylammonium cation, N,N-dibutyl-N-methyl-N-pentylammonium cation, N,N-dibutyl-N-methyl-N-hexylammonium cation, trioctylmethylammonium cation, N-methyl-N-ethyl-N-propyl-N-pentylammonium cation, and the like tetraalkylammonium cations; trimethylsulfonium cation, triethylsulfonium cation, tributylsulfonium cation, trihexylsulfonium cation, diethylmethylsulfonium cation, dibutylethylsulfonium cation, dimethyldecylsulfonium cation, and the like trialkylsulfonium cations; tetramethylphosphonium cation, tetraethylphosphonium cation, tetrabutylphosphonium cation, tetrahexylphosphonium cation, tetraoctylphosphonium cation, triethylmethylphosphonium cation, tributylethylphosphonium cation, trimethyldecylphosphonium cation, and the like tetraalkylphosphonium cations; these cations further having at least one selected from a vinyl group (CH2=CH- group) and an allyl group (CH2=CH-CH2- group) to form a cation.

[0237] As the ionic compound, preferably, it is an ionic compound comprising at least one selected from the above-mentioned onium cation and the above-mentioned metal cation and the above-mentioned fluoroorganic anion, a silicone oligomer containing an ionic group, more preferably, it is an ionic compound comprising at least one selected from the above-mentioned onium cation and the above-mentioned metal cation and the above-mentioned fluoroorganic anion, further preferably, it is an ionic compound comprising the above-mentioned onium cation and the above-mentioned fluoroorganic anion.

[0238] As the ionic compound, specifically, preferably, it is 1-hexylpyridinium bis(fluorosulfonyl)imide, 1-ethyl-3-methylpyridinium triflate, 1-ethyl-3-methylpyridinium pentaf luorothioethanesulfonate, 1-ethyl-3-methylpyridinium heptafluoropropylsulfonate, 1-ethyl-3-methylpyridinium nonafluorobutanesulfonate, 1-butyl-3-methylpyridinium triflate, 1-butyl-3-methylpyridinium bis(trifluoromethylsulfonyl)imide, 1-octyl-4-methylpyridinium bis(fluorosulfonyl)imide, 1-methyl-1-propylpyrrolidinium bis(trifluoromethylsulfonyl)imide, 1-methyl-1-propylpyrrolidinium bis(fluorosulfonyl)imide, 1-methyl-1-propylpiperidinium bis(trifluoromethylsulfonyl)imide, 1-methyl-1-propylpiperidinium bis(fluorosulfonyl)imide, 1-ethyl-3-methylimidazolium triflate, 1-ethyl-3-methylimidazolium heptafluoropropylsulfonate, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, 1-ethyl-3-methylimidazolium bis(fluorosulfonyl)imide, 1-hexyl-3-methylimidazolium bis(fluorosulfonyl)imide, 1-allyl-3-methyl-imidazolium triflate, 1-allyl-3-methyl-imidazolium heptafluoropropylsulfonate, 1-allyl-3-methyl-imidazolium bis(trifluoromethylsulfonyl)imide, 1-allyl-3-methyl-imidazolium bis(fluorosulfonyl)imide, methyltrioctylammonium bis(trifluoromethylsulfonyl)imide, trimethylpropylammonium bis(trifluoromethylsulfonyl)imide, lithium bis(trifluoromethylsulfonyl)imide, lithium bis(fluorosulfonyl)imide, further preferably, 1-butyl-3-methylpyridinium bis(trifluoromethylsulfonyl)imide, 1-ethyl-3-methylimidazolium bis(fluorosulfonyl)imide, 1-allyl-3-methyl-imidazolium bis(trifluoromethylsulfonyl)imide, methyltrioctylammonium bis(trifluoromethylsulfonyl)imide, trimethylpropylammonium bis(trifluoromethylsulfonyl)imide, lithium bis(trifluoromethylsulfonyl)imide, particularly preferably, 1-butyl-3-methylpyridinium bis(trifluoromethylsulfonyl)imide, 1-ethyl-3-methylimidazolium bis(fluorosulfonyl)imide, 1-allyl-3-methyl-imidazolium bis(trifluoromethylsulfonyl)imide, methyltrioctylammonium bis(trifluoromethylsulfonyl)imide, trimethylpropylammonium bis(trifluoromethylsulfonyl)imide.

[0239] The ionic compound can be used as a commercially available substance or a substance synthesized by any appropriate method. For example, the ionic liquid can be synthesized by the halide method, the hydroxide method, the acid ester method, the complex formation method, and the neutralization method described in "Ionic Liquids - Frontiers and Perspectives" (CMC Publishing) or the like.

[0240] 1-1-6. Other Components

[0241] The urethane-based adhesive composition can contain any appropriate other component within a range not impairing the effects of the present application. As such other components, for example, there can be mentioned a resin component other than the base polymer, a crosslinking agent other than the polyfunctional isocyanate compound (B), a crosslinking retarder, a silicone-based additive, a fatty acid ester, an adhesion promoter, an inorganic filler, an organic filler, a metal powder, a pigment, a foil, a softening agent, an age resistor, a conductive agent, a UV absorber, an antioxidant, a light stabilizer, a surface lubricant, a leveling agent, a preservative, a heat-resistant stabilizer, a polymerization inhibitor, a lubricant, a catalyst, a solvent. Representative other components are described below.

[0242] [Silicone-based additive]

[0243] It is one of preferable embodiments that the urethane-based adhesive composition contains a silicone-based additive. When a silicone-based additive is contained as the other component, the surface-protective film of the embodiment of the present application can be further improved in the easy-peeling property.

[0244] From the viewpoint of further exhibiting the effects of the present application, the content ratio of the silicone-based additive in the urethane-based adhesive composition is preferably 0.01 parts by weight or more, more preferably 0.03 parts by weight to 30 parts by weight, further preferably 0.05 parts by weight to 10 parts by weight, particularly preferably 0.05 parts by weight to 1 part by weight, relative to 100 parts by weight of the base polymer.

[0245] As the silicone-based additive, any appropriate silicone-based additive can be used within a range not impairing the effects of the present application.

[0246] The silicone-based additive can be only one kind or two or more kinds.

[0247] From the viewpoint of further exhibiting the effects of the present application, the content ratio of the total amount of the silicone-based additive and the aforementioned fluorine-based additive is preferably 0.01 parts by weight or more, more preferably 0.03 parts by weight to 30 parts by weight, further preferably 0.05 parts by weight to 10 parts by weight, particularly preferably 0.05 parts by weight to 1 part by weight, relative to 100 parts by weight of the base polymer.

[0248] The silicone-based additive can employ any appropriate silicone-based additive within a range not impairing the effects of the present application. As such a silicone-based additive, for example, reactive silicone oil, non-reactive silicone oil can be cited.

[0249] As the reactive silicone oil, for example, side chain type reactive silicone oil having an organic group bonded as a side chain to the Si atom for a siloxane bond, both end type reactive silicone oil having an organic group bonded to the Si atoms at both ends of the structure, mono-end type reactive silicone oil having an organic group bonded to only one of the Si atoms at both ends of the structure, side chain both end type reactive silicone oil having an organic group bonded as a side chain to the Si atom for a siloxane bond and having an organic group bonded to the Si atoms at both ends of the structure can be cited.

[0250] 〔Antioxidant〕

[0251] The urethane-based adhesive composition, from the viewpoint of deterioration inhibition of the urethane-based adhesive layer and the like, optionally contains an antioxidant as the other component. The antioxidant can be only one kind, or two or more kinds.

[0252] The content ratio of the antioxidant in the urethane-based adhesive composition can employ any appropriate content ratio within a range not impairing the effects of the present application. The content ratio of the antioxidant in the urethane-based adhesive composition is preferably 0.01 parts by weight to 10 parts by weight, more preferably 0.05 parts by weight to 5 parts by weight, further preferably 0.1 parts by weight to 3 parts by weight, particularly preferably 0.2 parts by weight to 1 part by weight, relative to 100 parts by weight of the base polymer.

[0253] As the antioxidant, for example, radical chain inhibitor, peroxide decomposer and the like can be cited.

[0254] As the radical chain inhibitor, for example, phenol-based antioxidant, amine-based antioxidant and the like can be cited.

[0255] As the peroxide decomposer, for example, sulfur-based antioxidant, phosphorus-based antioxidant can be cited.

[0256] As the phenol-based antioxidant, for example, monophenol-based antioxidant, biphenol-based antioxidant, high molecular weight phenol-based antioxidant can be cited.

[0257] As the monophenol-based antioxidant, for example, 2,6-di-tert-butyl-p-cresol, butylated hydroxyl anisole, 2,6-di-tert-butyl-4-ethylphenol, β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid stearyl ester can be cited.

[0258] As the bisphenol-based antioxidant, for example, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 4,4'-thiobis(3-methyl-6-tert-butylphenol), 4,4'-butylidenebis(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 can be exemplified.

[0259] As the high molecular weight phenol-based antioxidant, for example, 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, tetra-[methylene-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate]methane, bis[3,3'-bis-(4'-hydroxy-3'-tert-butylphenyl)butanoic acid]diol ester, 1,3,5-tris(3',5'-di-tert-butyl-4'-hydroxybenzyl)-s-triazine-2,4,6-(1H,3H,5H)trione, tocopherol can be exemplified.

[0260] As the sulfur-based antioxidant, for example, dilauryl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate, distearyl 3,3'-thiodipropionate can be exemplified.

[0261] As the phosphorus-based antioxidant, for example, triphenyl phosphite, diphenyl isodecyl phosphite, phenyl diisodecyl phosphite can be exemplified.

[0262] 〔Ultraviolet absorber〕

[0263] The urethane-based adhesive composition, from the viewpoint of deterioration inhibition of the urethane-based adhesive layer and the like, optionally contains an ultraviolet absorber as the other component. The ultraviolet absorber can be only one kind, or two or more kinds.

[0264] The content ratio of the ultraviolet absorber in the urethane-based adhesive composition can adopt any appropriate content ratio within a range not impairing the effects of the present application. The content ratio of the ultraviolet absorber in the urethane-based adhesive composition is preferably 0.01 parts by weight or more to 10 parts by weight or less, more preferably 0.05 parts by weight or more to 5 parts by weight or less, further preferably 0.1 parts by weight or more to 3 parts by weight or less, particularly preferably 0.2 parts by weight or more to 1 part by weight or less, relative to 100 parts by weight of the base polymer.

[0265] As the ultraviolet absorber, for example, benzophenone-based ultraviolet absorbers, benzotriazole-based ultraviolet absorbers, salicylic acid-based ultraviolet absorbers, oxanilide-based ultraviolet absorbers, cyano acrylate-based ultraviolet absorbers, and triazine-based ultraviolet absorbers can be exemplified.

[0266] As the benzophenone-based ultraviolet absorber, for example, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octyloxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2,2'-dihydroxy-4-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone, bis(2-methoxy-4-hydroxy-5-benzoylphenyl)methane can be exemplified.

[0267] As the benzotriazole-based ultraviolet absorber, for example, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-5'-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-amylphenyl)benzotriazole, 2-(2'-hydroxy-4'-octyloxyphenyl)benzotriazole, 2-[2'-hydroxy-3'-(3",4",5",6"-tetrahydrophthalimidomethyl)-5'-methylphenyl]benzotriazole, 2,2'methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazol-2-yl)phenol], 2-(2'-hydroxy-5'-methacryloyloxyphenyl)-2H-benzotriazole can be exemplified.

[0268] As the salicylic acid-based ultraviolet absorber, for example, phenyl salicylate, p-tert-butylphenyl salicylate, p-octylphenyl salicylate can be exemplified.

[0269] As the cyano acrylate-based ultraviolet absorber, for example, 2-ethylhexyl-2-cyano-3,3'-diphenyl acrylate, ethyl-2-cyano-3,3'-diphenyl acrylate can be exemplified.

[0270] 〔Light stabilizer〕

[0271] The urethane-based adhesive composition, from the viewpoint of inhibition of deterioration of the urethane-based adhesive layer and the like, optionally contains, as the other component, a light stabilizer. The light stabilizer can be only one kind, or two or more kinds.

[0272] The content ratio of the light stabilizer in the urethane-based adhesive composition can be any appropriate content ratio within a range that does not impair the effects of the present application. The content ratio of the light stabilizer in the urethane-based adhesive composition is preferably 0.01 parts by weight or more to 10 parts by weight or less, more preferably 0.05 parts by weight or more to 5 parts by weight or less, further preferably 0.1 parts by weight or more to 3 parts by weight or less, and particularly preferably 0.2 parts by weight or more to 1 part by weight or less, relative to 100 parts by weight of the base polymer.

[0273] As the light stabilizer, for example, a hindered amine-based light stabilizer, an ultraviolet stabilizer can be cited.

[0274] As the hindered amine-based light stabilizer, for example, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(l,2,2,6,6-pentamethyl-4-piperidyl) sebacate, methyl-l,2,2,6,6-pentamethyl-4-piperidyl sebacate can be cited.

[0275] As the ultraviolet stabilizer, for example, bis(octylphenyl) nickel sulfide, [2,2'-thiobis(4-tert-octylphenol)]-n-butylamine nickel, nickel complex-3,5-di-tert-butyl-4-hydroxybenzyl-phosphonic acid monoethyl ester, nickel dibutyldithiocarbamate, a quencher of the benzoate type, nickel dibutyldithiocarbamate can be cited.

[0276] [Aliphatic acid ester]

[0277] The urethane-based adhesive composition optionally contains an aliphatic acid ester as another component, from the viewpoint of improving the wettability of the urethane-based adhesive layer or the like. The aliphatic acid ester can be only one kind, or two or more kinds.

[0278] The content ratio of the aliphatic acid ester in the urethane-based adhesive composition can be any appropriate content ratio within a range that does not impair the effects of the present application. The content ratio of the aliphatic acid ester in the urethane-based adhesive composition is preferably 0.01 parts by weight or more to 50 parts by weight or less, more preferably 0.05 parts by weight or more to 45 parts by weight or less, further preferably 0.1 parts by weight or more to 40 parts by weight or less, and particularly preferably 0.5 parts by weight or more to 25 parts by weight or less, relative to 100 parts by weight of the base polymer.

[0279] The number average molecular weight Mn of the fatty acid ester is preferably 200 to 400, more preferably 210 to 395, further preferably 230 to 380, particularly preferably 240 to 360, most preferably 250 to 350. By adjusting the number average molecular weight Mn of the fatty acid ester to the above range, the wetting speed can be further improved. If the number average molecular weight Mn of the fatty acid ester is too small, there is a concern that the wetting speed will not improve even if the number of parts added is increased. If the number average molecular weight Mn of the fatty acid ester is too large, there is a concern that the curing properties of the adhesive at the time of drying will deteriorate, adversely affecting not only the wetting properties but also other adhesive properties.

[0280] As the fatty acid ester, any appropriate fatty acid ester can be used within a range that does not impair the effects of the present application. As such a fatty acid ester, for example, polyoxyethylene bisphenyl A laurate, butyl stearate, 2-ethylhexyl palmitate, 2-ethylhexyl stearate, glycerin monobehenate, cetyl 2-ethylhexanoate, isopropyl myristate, isopropyl palmitate, cholesteryl isostearate, lauryl methacrylate, coconut oil fatty acid methyl ester, methyl laurate, methyl oleate, methyl stearate, myristyl myristate, octyldodecyl myristate, pentaerythritol monooleate, pentaerythritol monostearate, pentaerythritol tetrapalmitate, stearyl stearate, isotridecyl stearate, glycerin tri-2-ethylhexanoate, butyl laurate, octyl oleate can be listed.

[0281] 〔Catalyst〕

[0282] As the catalyst that can be contained in the urethane-based adhesive composition, any appropriate catalyst can be used within a range that does not impair the effects of the present application. As such a catalyst, for example, tertiary amine-based compounds, organometal-based compounds can be listed. The catalyst can be only one kind, or two or more kinds.

[0283] As the tertiary amine-based compound, for example, triethylamine, triethylene diamine, 1,8-diazabicyclo(5,4,0)-undec-7-ene (DBU) can be listed.

[0284] As the organometal-based compound, for example, tin-based compounds, non-tin-based compounds can be listed.

[0285] As the tin-based compound, for example, dibutyl tin dichloride, dibutyl tin oxide, dibutyl tin dibromide, dibutyl tin dimaleate, dibutyl tin dilaurate (DBTDL), dibutyl tin diacetate, dibutyl tin sulfide, tributyl tin sulfide, tributyl tin oxide, tributyl tin acetate, triethyl tin ethoxide, tributyl tin ethoxide, dioctyl tin oxide, tributyl tin chloride, tributyl tin trichloroacetate, tin 2-ethylhexanoate can be listed.

[0286] As the non-tin compound, for example, titanium compounds such as dibutyltitanium dichloride, tetrabutyl titanate, and titanium tributoxide; lead compounds such as lead oleate, lead 2-ethylhexanoate, lead benzoate, and lead naphthenate; iron compounds such as iron 2-ethylhexanoate and iron acetylacetonate; cobalt compounds such as cobalt benzoate and cobalt 2-ethylhexanoate; zinc compounds such as zinc naphthenate and zinc 2-ethylhexanoate; and zirconium compounds such as zirconium naphthenate can be exemplified.

[0287] From the viewpoint that the effects of the present application can be further exhibited, as the catalyst that can be contained in the urethane-based adhesive composition, a non-tin compound is preferred, and an iron compound such as iron 2-ethylhexanoate and iron acetylacetonate is more preferred.

[0288] The amount of use of the catalyst that can be contained in the urethane-based adhesive composition is preferably 0.001 to 1.0% by weight relative to the total amount of the base polymer.

[0289] [Solvent]

[0290] As the solvent that can be contained in the urethane-based adhesive composition, any appropriate solvent can be used within a range that does not impair the effects of the present application. As such a solvent, for example, methyl ethyl ketone, ethyl acetate, toluene, xylene, and acetone can be exemplified. Of these solvents, ethyl acetate and toluene are preferred.

[0291] 1-2. Substrate Layer

[0292] As the thickness of the substrate layer, any appropriate thickness can be used depending on the use. The thickness of the substrate layer is preferably 5 to 300 μm, more preferably 10 to 250 μm, further preferably 15 to 200 μm, and particularly preferably 20 to 150 μm.

[0293] The substrate layer can be a single layer or a laminate of two or more layers. The substrate layer can also be stretched.

[0294] As the material of the substrate layer, any appropriate material can be used depending on the use. For example, plastics, paper, metal films, nonwoven fabrics, and the like can be exemplified. Plastics are preferred. The substrate layer can be composed of one material or two or more materials. For example, it can be composed of two or more plastics.

[0295] As the above-mentioned plastics, for example, polyester-based resins, polyamide-based resins, and polyolefin-based resins can be exemplified. Polyester-based resins are preferred, and for example, polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate can be exemplified.

[0296] The base material layer can contain any appropriate additive as needed. As the additive that can be contained in the base material layer, for example, an antioxidant, an ultraviolet absorber, a light stabilizer, an antistatic agent, a filler, a pigment can be listed. The kind, number, content of the additive that can be contained in the base material layer can be appropriately set according to the purpose. Particularly in the case where the material of the base material layer is plastic, it is preferable to contain several of the above-described additives for the purpose of preventing deterioration and the like. From the viewpoint of improving weather resistance and the like, as the additive, an antioxidant, an ultraviolet absorber, a light stabilizer, a filler are particularly preferable.

[0297] 《《《2. Method for manufacturing surface protection film》

[0298] The surface protection film of the embodiment of the present application can be manufactured by any appropriate method. As such a manufacturing method, for example, it can be manufactured according to any appropriate manufacturing method such as the following method or the like:

[0299] (1) a method of coating a solution, a hot melt liquid of a base material of an adhesive layer on a base material layer,

[0300] (2) a method of transferring an adhesive layer formed on a release liner based on the coating to a base material layer,

[0301] (3) a method of extruding and forming a base material layer on which an adhesive layer is coated,

[0302] (4) a method of extruding a base material layer and an adhesive layer in two or more layers,

[0303] (5) a method of laminating an adhesive layer on a base material layer in a single layer or a method of laminating an adhesive layer together with a laminated layer in two layers,

[0304] (6) a method of laminating an adhesive layer and a base material layer such as a film, a laminated layer in two or more layers.

[0305] As the coating method, for example, roll coating, gravure coating, reverse coating, kiss coating, dip roll coating, bar coating, roll brushing, spray coating, blade coating, air knife coating, comma coating, direct coating, die coating, roll brushing coating can be listed.

[0306] 《《《3. Use of surface protection film》

[0307] The surface protection film of the embodiment of the present application can be used for any appropriate use. It is preferable that the surface protection film of the present application is very little contaminated to an adherend, preferably excellent in wettability, reworkability, and thus, it is preferable to be used for surface protection of, for example, an optical member, an electronic member. As the optical member, for example, a touch panel using an LCD, an LCD, a color filter used in an LCD, a polarizing plate, and the like can be listed.

[0308] The member, such as an optical member, an electronic member, to which the surface protective film of the embodiment of the present application is attached can be repeatedly attached and peeled by manual operation.

[0309] That is, the optical member of the embodiment of the present application is attached with the surface protective film of the present application. In addition, the electronic member of the embodiment of the present application is attached with the surface protective film of the present application.

[0310] Example

[0311] Hereinafter, the present application will be specifically described by examples, but the present application is not limited by any of these examples. Note that the test and evaluation methods in the examples and the like are as follows. Note that when described as "parts", it means "parts by weight" unless otherwise specified, and when described as "%", it means "% by weight" unless otherwise specified.

[0312] <Adhesion to glass>

[0313] The surface protective film (25 mm wide x 140 mm long) from which the release liner was peeled was attached to a glass (soda-lime glass, manufactured by Matsushita Seiren Co., Ltd.) by reciprocating a 2 kg hand roller once. Thereafter, it was left for 30 minutes at an ambient temperature of 23°C. The obtained evaluation test piece was measured using a tensile testing machine. As the tensile testing machine, a product name "Autograph AG-Xplus HS 6000 mm / min high speed model (AG-50NX plus)" manufactured by Shimadzu Corporation was used. After the evaluation test piece was set on the tensile testing machine, the tensile test was started. The conditions of the tensile test were set to a peeling angle = 180 degrees, a peeling speed (tensile speed) = 300 mm / minute. The load at the time of peeling the surface protective film from the glass was measured, and the average load at that time was taken as the adhesion to glass (peeling force) of the surface protective film.

[0314] <Static peeling voltage to glass>

[0315] The surface protective film peeled from the release liner was cut into a size of 70 mm in width and 100 mm in length, and was pressure-bonded to the surface of a glass (soda-lime glass, manufactured by Matsunami Glass Ind. Ltd.) by a hand pressure roller so that one end of the surface protective film would project 30 mm from the end of the adherend. After the sample was left to stand for 1 day in an environment of 23°C x 50% RH, the end of the surface protective film projecting 30 mm from the adherend was fixed to an automatic take-up machine (not shown) and peeled at a peeling angle of 150° and a peeling speed of 30 m / min. The "peeling electrostatic voltage" was measured for the potential of the surface of the adherend at this time using a potential measuring device (manufactured by SHISHIDO ELECTROSTATIC, LTD., model "STATIRON DZ-4") fixed at a position 30 mm above the center of the adherend. The measurement was performed in an environment of 23°C, 50% RH.

[0316] "Haze"

[0317] The urethane-based adhesive composition was applied to the release-treated surface of a polyester film (trade name: Diafol MRF75, manufactured by Mitsubishi Chemical Corporation) having a thickness of 75 μm and dried to form a urethane-based adhesive layer. Subsequently, a polyester film (trade name: Diafol MRE75, manufactured by Mitsubishi Chemical Corporation) having a thickness of 75 μm and having a release-treated surface with one side treated with silicone was laminated to the surface of the urethane-based adhesive layer with the release-treated surface of the polyester film on the urethane-based adhesive layer side, and left to stand for 5 days at room temperature.

[0318] Two pieces of paper having a hole of 20 mm x 20 mm in the center of a 50 mm x 50 mm thick paper were prepared, and the sample was adhered to one piece of paper by reciprocating the hand pressure roller once, and then the other piece of paper was adhered.

[0319] The haze of the evaluation sample obtained by the above operation was measured using "HM-150N" manufactured by Murakami Color Research Laboratory Co., Ltd.

[0320] "Residue Evaluation"

[0321] The center of the adhesive surface of the surface protective film (25 mm in width x 140 mm in length) peeled from the release liner was cut 1 cm with the blade of a cutter at an angle of 30 degrees.

[0322] The case where the residue could be visually confirmed was set as X, and the case where the residue could not be confirmed was set as O.

[0323] "Black Spot Evaluation"

[0324] The number of black spots (dimple) per 10 cm square of the surface protective film of the release liner was visually confirmed.

[0325] <Proportion of hydroxyl group contained in urethane-based adhesive composition>

[0326] The OHV (mgKOH / g) and the molecular weight of KOH (56.1) based on 100 g of the total of the base polymers contained in the urethane-based adhesive composition were calculated from the following formula.

[0327] OHV [mgKOH / g] / 56.1 [mg / mmol] = OH [mmol / g]

[0328] 〔Production Example 1〕: Production of solution of urethane prepolymer A

[0329] In a polymerization experimental apparatus equipped with a 1 L round bottom detachable flask, a detachable cap, a separatory funnel, a thermometer, a nitrogen inlet tube, a Liebig condenser, a vacuum seal, a stirring rod, and a stirring blade, polytetramethylene glycol (product name "PTMG3000", manufactured by Mitsubishi Chemical Corporation) 333 g, polypropylene glycol (product name "Sannix GP-1500", manufactured by Soya Kako Co., Ltd.) 83 g, and ethyl acetate (manufactured by Tokyo Chemical Industry Co., Ltd.) 110 g as a solvent were charged, and dibutyltin dilaurate (IV) (manufactured by Wako Pure Chemical Industries, Ltd.) 0.041 g as a catalyst was added while stirring, and nitrogen replacement was performed for 1 hour at normal temperature. Thereafter, hexamethylene diisocyanate (product name "HDI", manufactured by Tokyo Chemical Industry Co., Ltd.) 13.0 g was added while stirring under nitrogen flow, and the solution temperature in the experimental apparatus was controlled to 90 ± 2°C using a water bath, and maintained for 4 hours, to obtain a solution of urethane prepolymer A. Note that, during the polymerization, ethyl acetate was appropriately added dropwise in order to control the temperature during the polymerization and prevent a decrease in stirring performance due to an increase in viscosity. The total amount of the added ethyl acetate was 320 g. The solid content concentration of the solution of urethane prepolymer A was 50% by weight.

[0330] 〔Production Example 2〕: Production of solution of urethane prepolymer B

[0331] In a polymerization apparatus equipped with a 1 L round bottom detachable flask, a detachable cap, a separatory funnel, a thermometer, a nitrogen inlet tube, a Liebig condenser, a vacuum seal, a stirring rod, and stirring blades, 197 g of polypropylene glycol (product name "Sannix PP-2000", manufactured by Sanyo Chemical Industries, Co., Ltd.), 197 g of polyester polyol (product name "kuraray polyol P-2010", manufactured by Kuraray Co., Ltd.), 110 g of toluene (manufactured by Tokyo Chemical Industry Co., Ltd.) as a solvent, and 0.041 g of dibutyltin dilaurate (manufactured by Wako Pure Chemical Industries, Ltd.) as a catalyst were charged, and nitrogen substitution was performed for 1 hour at ordinary temperature while stirring. Thereafter, 33.5 g of hexamethylene diisocyanate (product name "HDI", manufactured by Tokyo Chemical Industry Co., Ltd.) was charged under nitrogen flow while stirring, and the solution temperature in the apparatus was controlled to 90 ± 2°C using a water bath, and maintained for 4 hours. Then, 44 g of polypropylene glycol (product name "GP1000", manufactured by Sanyo Chemical Industries, Co., Ltd.) was charged, and the solution temperature in the apparatus was controlled to 90 ± 2°C using a water bath, and maintained for 2 hours. Then, 25.4 g of hexamethylene diisocyanate (product name "HDI", manufactured by Tokyo Chemical Industry Co., Ltd.) was charged, and the solution temperature in the apparatus was controlled to 90 ± 2°C using a water bath, and maintained for 2 hours, to obtain a solution of urethane prepolymer B. Note that, during the polymerization, toluene was appropriately added dropwise in order to control the temperature during polymerization and to prevent a decrease in stirring properties due to an increase in viscosity. The total amount of the toluene added dropwise was 380 g. The solid content concentration of the solution of urethane prepolymer B was 50% by weight.

[0332] [Example 1]

[0333] The urethane prepolymer A100 parts by weight, isocyanate compound (Coronate HX: C / HX, manufactured by Japan Polyurethane Corporation) 3.2 parts by weight as a crosslinking agent, fluorine-based oligomer Megafac F-571 (manufactured by DIC Corporation) 0.5 parts by weight, Irganox 1010 (manufactured by BASF Corporation) 0.5 parts by weight as an antioxidant, iron acetylacetone (manufactured by Japan Chemical Industry Co., Ltd.) 0.03 parts by weight as a catalyst were diluted with ethyl acetate so that the solid content of the whole was 50% by weight, to obtain a urethane adhesive solution. Then, the urethane adhesive solution was applied to a substrate (trade name "T100-75S", thickness 75 μm, manufactured by Mitsubishi Chemical Corporation) formed of a polyester resin so that the thickness after drying was 75 μm, and cured and dried under conditions of a drying temperature of 130°C and a drying time of 3 minutes, to produce an adhesive layer formed of an adhesive composition. Next, a release liner (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Corporation) formed of a polyester resin, the silicone-treated surface of which had been treated, was attached to the surface of the obtained adhesive layer, to obtain a surface protection film (1). Evaluation was performed after aging for 5 days at ordinary temperature.

[0334] [Example 2]

[0335] The urethane prepolymer B100 parts by weight, isocyanate compound (Coronate HX: C / HX, manufactured by Japan Polyurethane Corporation) 2.9 parts by weight as a crosslinking agent, fluorine-based oligomer Megafac F-571 (manufactured by DIC Corporation) 0.5 parts by weight, Irganox 1010 (manufactured by BASF Corporation) 0.5 parts by weight as an antioxidant, iron acetylacetone (manufactured by Japan Chemical Industry Co., Ltd.) 0.03 parts by weight as a catalyst were diluted with ethyl acetate so that the solid content of the whole was 50% by weight, to obtain a urethane adhesive solution. Then, the urethane adhesive solution was applied to a substrate (trade name "T100-75S", thickness 75 μm, manufactured by Mitsubishi Chemical Corporation) formed of a polyester resin so that the thickness after drying was 75 μm, and cured and dried under conditions of a drying temperature of 130°C and a drying time of 3 minutes, to produce an adhesive layer formed of an adhesive composition. Next, a release liner (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Corporation) formed of a polyester resin, the silicone-treated surface of which had been treated, was attached to the surface of the obtained adhesive layer, to obtain a surface protection film (2). Evaluation was performed after aging for 5 days at ordinary temperature.

[0336] [Example 3]

[0337] A urethane prepolymer B95 95 parts by weight, Preminol S3011 (manufactured by Asahi Glass Co., Ltd., Mn = 10000) 3 parts by weight as a polyol having 3 hydroxyl groups, PTGL3000 (manufactured by Hokuetsu- Chemical Industry Co., Ltd., Mn = 3000) 2 parts by weight as a polyol having 3 hydroxyl groups, an isocyanate compound (Coronate HX: C / HX, manufactured by Japan Polyurethane Co., Ltd.) 3.7 parts by weight as a crosslinking agent, a fluorine-based oligomer Megafac F-571 (manufactured by DIC Corporation) 0.5 parts by weight, Irganox 1010 (manufactured by BASF Corporation) 0.5 parts by weight as an antioxidant, iron acetylacetone (manufactured by Nitto Chemical Industry Co., Ltd.) 0.03 parts by weight as a catalyst were diluted with ethyl acetate so that the total solid content would be 50% by weight, to obtain a urethane adhesive solution. Then, the urethane adhesive solution was applied to a substrate (trade name "T100-75S", thickness 75 μm, manufactured by Mitsubishi Chemical Corporation) formed of a polyester resin so that the thickness after drying would be 75 μm, and cured and dried under conditions of a drying temperature of 130°C and a drying time of 3 minutes, to produce an adhesive layer formed of an adhesive composition. Subsequently, a release liner (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Corporation) formed of a polyester resin having a silicone-treated surface and having a thickness of 25 μm was attached to the surface of the obtained adhesive layer with the silicone-treated surface, to obtain a surface protection film (3). Aging was performed at ordinary temperature for 5 days, and evaluation was performed.

[0338] [Example 4]

[0339] A urethane prepolymer A95 95 parts by weight, Preminol S3011 (manufactured by Asahi Glass Co., Ltd., Mn = 10000) 3.5 parts by weight as a polyol having 3 hydroxyl groups, Sannix GP3000 (manufactured by Sanyo Chemical Industries, Ltd., Mn = 3000) 1.5 parts by weight as a polyol having 3 hydroxyl groups, an isocyanate compound (Coronate HX: C / HX, manufactured by Japan Polyurethane Co., Ltd.) 3.8 parts by weight as a crosslinking agent, a fluorine-based oligomer Megafac F-571 (manufactured by DIC Corporation) 0.5 parts by weight, Irganox 1010 (manufactured by BASF Corporation) 0.5 parts by weight as an antioxidant, iron acetylacetone (manufactured by Japan Chemical Industries Co., Ltd.) 0.03 parts by weight as a catalyst were diluted with ethyl acetate so that the solid content of the whole would be 50% by weight, to obtain a urethane-based adhesive solution. Then, the urethane-based adhesive solution was applied to a substrate (trade name "T100-75S", thickness 75 μm, manufactured by Mitsubishi Chemical Corporation) formed of a polyester resin so that the thickness after drying would be 75 μm, and cured and dried under conditions of a drying temperature of 130°C and a drying time of 3 minutes, to produce an adhesive layer formed of an adhesive composition. Subsequently, a release liner (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Corporation) formed of a polyester resin having a silicone-treated surface and having a thickness of 25 μm was attached to the surface of the obtained adhesive layer with the silicone-treated surface, to obtain a surface-protective film (4). Aging was performed at ordinary temperature for 5 days, and evaluation was performed.

[0340] [Example 5]

[0341] A urethane prepolymer A95 95 parts by weight, Preminol S3011 (manufactured by Asahi Glass Company, Ltd., Mn = 10000) 3 parts by weight as a polyol having 3 hydroxyl groups, Sannix GP3000 (manufactured by Sanyo Chemical Industries, Ltd., Mn = 3000) 2 parts by weight as a polyol having 3 hydroxyl groups, an isocyanate compound (Coronate HX: C / HX, manufactured by Japan Polyurethane Corporation) 3.9 parts by weight as a crosslinking agent, a fluorine-based oligomer Megafac F-571 (manufactured by DIC Corporation) 0.5 parts by weight, Irganox 1010 (manufactured by BASF Corporation) 0.5 parts by weight as an antioxidant, iron acetylacetone (manufactured by Nitto Chemical Industry Co., Ltd.) 0.03 parts by weight as a catalyst were diluted with ethyl acetate so that the total solid content would be 50% by weight, to obtain a urethane adhesive solution. Then, the urethane adhesive solution was applied to a substrate (trade name "T100-75S", thickness 75 μm, manufactured by Mitsubishi Chemical Corporation) formed of a polyester resin so that the thickness after drying would be 75 μm, and cured and dried under conditions of a drying temperature of 130°C and a drying time of 3 minutes, to produce an adhesive layer formed of an adhesive composition. Subsequently, a release liner (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Corporation) formed of a polyester resin having a silicone-treated surface and having a thickness of 25 μm was attached to the surface of the obtained adhesive layer with the silicone-treated surface facing outward, to obtain a surface-protective film (5). Aging was performed at ordinary temperature for 5 days, and evaluation was performed.

[0342] [Example 6]

[0343] A urethane prepolymer A80 80 parts by weight, Preminol S3011 (Asahi Glass Co., Ltd. manufactured, Mn = 10000) as a polyol having 3 hydroxyl groups 12 parts by weight, Sannix GP3000 (Sanyo Chemical Industries, Ltd. manufactured, Mn = 3000) as a polyol having 3 hydroxyl groups 8 parts by weight, an isocyanate compound (Coronate HX: C / HX, Japan Polyurethane Co., Ltd. manufactured) as a crosslinking agent 6.0 parts by weight, a fluorine-based oligomer Megafac F-571 (DIC Corporation manufactured) 0.5 parts by weight, Irganox 1010 (BASF Corporation manufactured) as an antioxidant 0.5 parts by weight, acetylacetone iron (Japan Chemical Industries Co., Ltd. manufactured) as a catalyst 0.03 parts by weight were diluted with ethyl acetate so that the solid content of the whole was 50% by weight, to obtain a urethane adhesive solution. Then, the urethane adhesive solution was applied to a substrate (trade name "T100-75S", thickness 75 μm, Mitsubishi Chemical Corporation manufactured) formed of a polyester resin so that the thickness after drying was 75 μm, and cured and dried under conditions of a drying temperature of 130°C and a drying time of 3 minutes, to produce an adhesive layer formed of an adhesive composition. Next, a release liner (trade name "MRF25", thickness 25 μm, Mitsubishi Chemical Corporation manufactured) formed of a polyester resin having a silicone-treated surface of 25 μm in thickness was attached to the surface of the obtained adhesive layer with the silicone-treated surface, to obtain a surface protection film (6). Aging was performed at normal temperature for 5 days, and evaluation was performed.

[0344] [Example 7]

[0345] A urethane prepolymer A60 60 parts by weight, Preminol S3011 (manufactured by Asahi Glass Co., Ltd., Mn = 10000) as a polyol having 3 hydroxyl groups, 28 parts by weight, Sannix GP3000 (manufactured by Sanyo Chemical Industries, Ltd., Mn = 3000) as a polyol having 3 hydroxyl groups, 12 parts by weight, an isocyanate compound (Coronate HX: C / HX, manufactured by Japan Polyurethane Co., Ltd.) as a crosslinking agent, 8.0 parts by weight, a fluorine-based oligomer Megafac F-571 (manufactured by DIC Corporation) 0.5 parts by weight, Irganox 1010 (manufactured by BASF Corporation) as an antioxidant, 0.5 parts by weight, iron acetylacetone (manufactured by Japan Chemical Industries Co., Ltd.) as a catalyst, 0.03 parts by weight were diluted with ethyl acetate so that the total solid content would be 50% by weight, to obtain a urethane adhesive solution. Then, the urethane adhesive solution was applied to a substrate (trade name "T100-75S", thickness 75 μm, manufactured by Mitsubishi Chemical Corporation) formed of a polyester resin so that the thickness after drying would be 75 μm, and cured and dried under conditions of a drying temperature of 130°C and a drying time of 3 minutes, to produce an adhesive layer formed of an adhesive composition. Subsequently, a release liner (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Corporation) formed of a polyester resin having a silicone-treated surface and having a thickness of 25 μm was attached to the surface of the obtained adhesive layer with the silicone-treated surface, to obtain a surface protection film (7). Aging was performed at ordinary temperature for 5 days, and evaluation was performed.

[0346] [Example 8]

[0347] A urethane prepolymer A60 60 parts by weight, Preminol S3011 (manufactured by Asahi Glass Co., Ltd., Mn = 10000) as a polyol having 3 hydroxyl groups, 25 parts by weight, Sannix GP3000 (manufactured by Sanyo Chemical Industries, Ltd., Mn = 3000) as a polyol having 3 hydroxyl groups, 15 parts by weight, an isocyanate compound (Coronate HX: C / HX, manufactured by Japan Polyurethane Co., Ltd.) as a crosslinking agent, 8.6 parts by weight, Megafac F-571 (manufactured by DIC Corporation) as a fluorine-based oligomer, 0.5 parts by weight, Irganox 1010 (manufactured by BASF Corporation) as an antioxidant, 0.5 parts by weight, iron acetylacetone (manufactured by Japan Chemical Industries Co., Ltd.) as a catalyst, 0.03 parts by weight were diluted with ethyl acetate so that the total solid content would be 50% by weight, to obtain a urethane adhesive solution. Then, the urethane adhesive solution was applied to a substrate (trade name "T100-75S", thickness 75 μm, manufactured by Mitsubishi Chemical Corporation) formed of a polyester resin so that the thickness after drying would be 75 μm, and cured and dried under conditions of a drying temperature of 130°C and a drying time of 3 minutes, to produce an adhesive layer formed of an adhesive composition. Subsequently, a release liner (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Corporation) formed of a polyester resin having a silicone-treated surface and having a thickness of 25 μm was attached to the surface of the obtained adhesive layer with the silicone-treated surface, to obtain a surface protection film (8). Aging was performed at ordinary temperature for 5 days, and evaluation was performed.

[0348] [Example 9]

[0349] A urethane prepolymer A50 50 parts by weight, Preminol S3011 (manufactured by Asahi Glass Co., Ltd., Mn = 10000) as a polyol having 3 hydroxyl groups 30 parts by weight, Sannix GP4000 (manufactured by Sanyo Chemical Industries, Ltd., Mn = 4000) as a polyol having 3 hydroxyl groups 20 parts by weight, an isocyanate compound (Coronate HX: C / HX, manufactured by Japan Polyurethane Co., Ltd.) as a crosslinking agent 8.7 parts by weight, a fluorine-based oligomer Megafac F-571 (manufactured by DIC Corporation) 0.5 parts by weight, Irganox 1010 (manufactured by BASF Corporation) as an antioxidant 0.5 parts by weight, iron acetylacetone (manufactured by Japan Chemical Industries Co., Ltd.) as a catalyst 0.03 parts by weight were diluted with ethyl acetate so that the solid content of the whole would be 50% by weight, to obtain a urethane adhesive solution. Then, the urethane adhesive solution was applied to a substrate (trade name "T100-75S", thickness 75 μm, manufactured by Mitsubishi Chemical Corporation) formed of a polyester resin so that the thickness after drying would be 75 μm, and cured and dried under conditions of a drying temperature of 130°C and a drying time of 3 minutes, to produce an adhesive layer formed of an adhesive composition. Subsequently, a release liner (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Corporation) formed of a polyester resin having a silicone-treated surface of 25 μm in thickness was attached to the surface of the obtained adhesive layer with the silicone-treated surface, to obtain a surface-protective film (9). Aging was performed at ordinary temperature for 5 days, and evaluation was performed.

[0350] [Example 10]

[0351] The urethane prepolymer A100 parts by weight, isocyanate compound (Coronate HX: C / HX, manufactured by Japan Polyurethane Corporation) 3.2 parts by weight as a crosslinking agent, fluorine-based oligomer Megafac F-563 (manufactured by DIC Corporation) 0.5 parts by weight, Irganox 1010 (manufactured by BASF Corporation) 0.5 parts by weight as an antioxidant, iron acetylacetone (manufactured by Japan Chemical Industry Co., Ltd.) 0.03 parts by weight as a catalyst were diluted with ethyl acetate so that the solid content of the whole was 50% by weight, to obtain a urethane adhesive solution. Then, the urethane adhesive solution was applied to a substrate (trade name "T100-75S", thickness 75 μm, manufactured by Mitsubishi Chemical Corporation) formed of a polyester resin so that the dried thickness was 75 μm, and cured and dried under conditions of a drying temperature of 130°C and a drying time of 3 minutes, to produce an adhesive layer formed of an adhesive composition. Next, a release liner (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Corporation) formed of a polyester resin, the silicone-treated surface of which had been treated, was attached to the surface of the obtained adhesive layer, to obtain a surface protection film (10). Aging was performed at ordinary temperature for 5 days, and evaluation was performed.

[0352] [Example 11]

[0353] The urethane prepolymer B100 parts by weight, isocyanate compound (Coronate HX: C / HX, manufactured by Japan Polyurethane Corporation) 2.9 parts by weight as a crosslinking agent, fluorine-based oligomer Megafac F-563 (manufactured by DIC Corporation) 0.5 parts by weight, Irganox 1010 (manufactured by BASF Corporation) 0.5 parts by weight as an antioxidant, iron acetylacetone (manufactured by Japan Chemical Industry Co., Ltd.) 0.03 parts by weight as a catalyst were diluted with ethyl acetate so that the solid content of the whole was 50% by weight, to obtain a urethane adhesive solution. Then, the urethane adhesive solution was applied to a substrate (trade name "T100-75S", thickness 75 μm, manufactured by Mitsubishi Chemical Corporation) formed of a polyester resin so that the dried thickness was 75 μm, and cured and dried under conditions of a drying temperature of 130°C and a drying time of 3 minutes, to produce an adhesive layer formed of an adhesive composition. Next, a release liner (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Corporation) formed of a polyester resin, the silicone-treated surface of which had been treated, was attached to the surface of the obtained adhesive layer, to obtain a surface protection film (11). Aging was performed at ordinary temperature for 5 days, and evaluation was performed.

[0354] [Example 12]

[0355] A urethane prepolymer B95 95 parts by weight, Preminol S3011 (manufactured by Asahi Glass Co., Ltd., Mn = 10000) 3 parts by weight as a polyol having 3 hydroxyl groups, PTGL3000 (manufactured by Hokuetsu- Chemical Industry Co., Ltd., Mn = 3000) 2 parts by weight as a polyol having 3 hydroxyl groups, an isocyanate compound (Coronate HX: C / HX, manufactured by Japan Polyurethane Co., Ltd.) 3.7 parts by weight as a crosslinking agent, a fluorine-based oligomer Megafac F-563 (manufactured by DIC Corporation) 0.5 parts by weight, Irganox 1010 (manufactured by BASF Corporation) 0.5 parts by weight as an antioxidant, iron acetylacetone (manufactured by Nitto Chemical Industry Co., Ltd.) 0.03 parts by weight as a catalyst were diluted with ethyl acetate so that the total solid content would be 50% by weight, to obtain a urethane adhesive solution. Then, the urethane adhesive solution was applied to a substrate (trade name "T100-75S", thickness 75 μm, manufactured by Mitsubishi Chemical Corporation) formed of a polyester resin so that the thickness after drying would be 75 μm, and cured and dried under conditions of a drying temperature of 130°C and a drying time of 3 minutes, to produce an adhesive layer formed of an adhesive composition. Subsequently, a release liner (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Corporation) formed of a polyester resin having a silicone-treated surface and having a thickness of 25 μm was attached to the surface of the obtained adhesive layer with the silicone-treated surface, to obtain a surface protection film (12). Aging was performed at ordinary temperature for 5 days, and evaluation was performed.

[0356] [Example 13]

[0357] A urethane prepolymer A95 95 parts by weight, Preminol S3011 (manufactured by Asahi Glass Co., Ltd., Mn = 10000) 3.5 parts by weight as a polyol having 3 hydroxyl groups, Sannix GP3000 (manufactured by Sanyo Chemical Industries, Ltd., Mn = 3000) 1.5 parts by weight as a polyol having 3 hydroxyl groups, an isocyanate compound (Coronate HX: C / HX, manufactured by Japan Polyurethane Co., Ltd.) 3.8 parts by weight as a crosslinking agent, a fluorine-based oligomer Megafac F-563 (manufactured by DIC Corporation) 0.5 parts by weight, Irganox 1010 (manufactured by BASF Corporation) 0.5 parts by weight as an antioxidant, iron acetylacetone (manufactured by Japan Chemical Industries Co., Ltd.) 0.03 parts by weight as a catalyst were diluted with ethyl acetate so that the total solid content would be 50% by weight, to obtain a urethane adhesive solution. Then, the urethane adhesive solution was applied to a substrate (trade name "T100-75S", thickness 75 μm, manufactured by Mitsubishi Chemical Corporation) formed of a polyester resin so that the thickness after drying would be 75 μm, and cured and dried under conditions of a drying temperature of 130°C and a drying time of 3 minutes, to produce an adhesive layer formed of an adhesive composition. Subsequently, a release liner (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Corporation) formed of a polyester resin having a silicone-treated surface and having a thickness of 25 μm was attached to the surface of the obtained adhesive layer with the silicone-treated surface facing outward, to obtain a surface protection film (13). Aging was performed at ordinary temperature for 5 days, and evaluation was performed.

[0358] [Example 14]

[0359] A urethane prepolymer A95 95 parts by weight, Preminol S3011 (manufactured by Asahi Glass Co., Ltd., Mn = 10000) 3 parts by weight as a polyol having 3 hydroxyl groups, Sannix GP3000 (manufactured by Sanyo Chemical Industries, Ltd., Mn = 3000) 2 parts by weight as a polyol having 3 hydroxyl groups, an isocyanate compound (Coronate HX: C / HX, manufactured by Japan Polyurethane Co., Ltd.) 3.9 parts by weight as a crosslinking agent, a fluorine-based oligomer Megafac F-563 (manufactured by DIC Corporation) 0.5 parts by weight, Irganox 1010 (manufactured by BASF Corporation) 0.5 parts by weight as an antioxidant, iron acetylacetone (manufactured by Japan Chemical Industries Co., Ltd.) 0.03 parts by weight as a catalyst were diluted with ethyl acetate so that the total solid content would be 50% by weight, to obtain a urethane adhesive solution. Then, the urethane adhesive solution was applied to a substrate (trade name "T100-75S", thickness 75 μm, manufactured by Mitsubishi Chemical Corporation) formed of a polyester resin so that the thickness after drying would be 75 μm, and cured and dried under conditions of a drying temperature of 130°C and a drying time of 3 minutes, to produce an adhesive layer formed of an adhesive composition. Subsequently, a release liner (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Corporation) formed of a polyester resin having a silicone-treated surface and having a thickness of 25 μm was attached to the surface of the obtained adhesive layer with the silicone-treated surface facing outward, to obtain a surface protection film (14). Aging was performed at ordinary temperature for 5 days, and evaluation was performed.

[0360] [Example 15]

[0361] A urethane prepolymer A80 80 parts by weight, Preminol S3011 (Asahi Glass Co., Ltd. manufactured, Mn = 10000) as a polyol having 3 hydroxyl groups 12 parts by weight, Sannix GP3000 (Sanyo Chemical Industries, Ltd. manufactured, Mn = 3000) as a polyol having 3 hydroxyl groups 8 parts by weight, an isocyanate compound (Coronate HX: C / HX, Japan Polyurethane Co., Ltd. manufactured) as a crosslinking agent 6.0 parts by weight, a fluorine-based oligomer Megafac F-563 (DIC Corporation manufactured) 0.5 parts by weight, Irganox 1010 (BASF Corporation manufactured) as an antioxidant 0.5 parts by weight, acetylacetone iron (Japan Chemical Industries Co., Ltd. manufactured) as a catalyst 0.03 parts by weight were diluted with ethyl acetate so that the total solid content was 50% by weight, to obtain a urethane adhesive solution. Then, the urethane adhesive solution was applied to a substrate (trade name "T100-75S", thickness 75 μm, Mitsubishi Chemical Corporation manufactured) formed of a polyester resin so that the thickness after drying was 75 μm, and cured and dried under conditions of a drying temperature of 130°C and a drying time of 3 minutes, to produce an adhesive layer formed of an adhesive composition. Next, a release liner (trade name "MRF25", thickness 25 μm, Mitsubishi Chemical Corporation manufactured) formed of a polyester resin having a silicone-treated surface of 25 μm in thickness was attached to the surface of the obtained adhesive layer with the silicone-treated surface, to obtain a surface protection film (15). Aging was performed at normal temperature for 5 days, and evaluation was performed.

[0362] [Example 16]

[0363] A urethane prepolymer A60 60 parts by weight, Preminol S3011 (manufactured by Asahi Glass Company, Ltd., Mn = 10000) as a polyol having 3 hydroxyl groups, 28 parts by weight, Sannix GP3000 (manufactured by Sanyo Chemical Industries, Ltd., Mn = 3000) as a polyol having 3 hydroxyl groups, 12 parts by weight, an isocyanate compound (Coronate HX: C / HX, manufactured by Japan Polyurethane Co., Ltd.) as a crosslinking agent, 8.0 parts by weight, a fluorine-based oligomer Megafac F-563 (manufactured by DIC Corporation) 0.5 parts by weight, Irganox 1010 (manufactured by BASF Corporation) as an antioxidant, 0.5 parts by weight, iron acetylacetone (manufactured by Nitto Chemical Industry Co., Ltd.) as a catalyst, 0.03 parts by weight were diluted with ethyl acetate so that the solid content of the whole would be 50% by weight, to obtain a urethane adhesive solution. Then, the urethane adhesive solution was applied to a substrate (trade name "T100-75S", thickness 75 μm, manufactured by Mitsubishi Chemical Corporation) formed of a polyester resin so that the thickness after drying would be 75 μm, and cured and dried under conditions of a drying temperature of 130°C and a drying time of 3 minutes, to produce an adhesive layer formed of an adhesive composition. Subsequently, a release liner (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Corporation) formed of a polyester resin having a silicone-treated surface of 25 μm in thickness was attached to the surface of the obtained adhesive layer with the silicone-treated surface, to obtain a surface protection film (16). Aging was performed at ordinary temperature for 5 days, and evaluation was performed.

[0364] [Example 17]

[0365] A urethane prepolymer A60 60 parts by weight, Preminol S3011 (manufactured by Asahi Glass Company, Ltd., Mn = 10000) as a polyol having 3 hydroxyl groups, 25 parts by weight, Sannix GP3000 (manufactured by Sanyo Chemical Industries, Ltd., Mn = 3000) as a polyol having 3 hydroxyl groups, 15 parts by weight, an isocyanate compound (Coronate HX: C / HX, manufactured by Japan Polyurethane Co., Ltd.) as a crosslinking agent, 8.6 parts by weight, Megafac F-563 (manufactured by DIC Corporation) as a fluorine-based oligomer, 0.5 parts by weight, Irganox 1010 (manufactured by BASF Corporation) as an antioxidant, 0.5 parts by weight, iron acetylacetone (manufactured by Japan Chemical Industries, Ltd.) as a catalyst, 0.03 parts by weight were diluted with ethyl acetate so that the total solid content would be 50% by weight, to obtain a urethane adhesive solution. Then, the urethane adhesive solution was applied to a substrate (trade name "T100-75S", thickness 75 μm, manufactured by Mitsubishi Chemical Corporation) formed of a polyester resin so that the thickness after drying would be 75 μm, and cured and dried under conditions of a drying temperature of 130°C and a drying time of 3 minutes, to produce an adhesive layer formed of an adhesive composition. Subsequently, a release liner (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Corporation) formed of a polyester resin, whose one face had been subjected to silicone treatment, was attached to the surface of the obtained adhesive layer with the silicone-treated face facing outward, to obtain a surface protection film (17). Aging was performed at ordinary temperature for 5 days, and evaluation was performed.

[0366] [Example 18]

[0367] A urethane prepolymer A50 50 parts by weight, Preminol S3011 (manufactured by Asahi Glass Company, Ltd., Mn = 10000) as a polyol having 3 hydroxyl groups 30 parts by weight, Sannix GP4000 (manufactured by Sanyo Chemical Industries, Ltd., Mn = 4000) as a polyol having 3 hydroxyl groups 20 parts by weight, an isocyanate compound (Coronate HX: C / HX, manufactured by Japan Polyurethane Co., Ltd.) as a crosslinking agent 8.7 parts by weight, a fluorine-based oligomer Megafac F-563 (manufactured by DIC Corporation) 0.5 parts by weight, Irganox 1010 (manufactured by BASF Corporation) as an antioxidant 0.5 parts by weight, iron acetylacetone (manufactured by Japan Chemical Industries, Ltd.) as a catalyst 0.03 parts by weight were diluted with ethyl acetate so that the solid content of the whole would be 50% by weight, to obtain a urethane adhesive solution. Then, the urethane adhesive solution was applied to a substrate (trade name "T100-75S", thickness 75 μm, manufactured by Mitsubishi Chemical Corporation) formed of a polyester resin so that the thickness after drying would be 75 μm, and cured and dried under conditions of a drying temperature of 130°C and a drying time of 3 minutes, to produce an adhesive layer formed of an adhesive composition. Subsequently, a release liner (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Corporation) formed of a polyester resin having a silicone-treated surface of 25 μm in thickness was attached to the surface of the obtained adhesive layer with the silicone-treated surface, to obtain a surface-protective film (18). Aging was performed at ordinary temperature for 5 days, and evaluation was performed.

[0368] [Example 19]

[0369] The urethane prepolymer A100 parts by weight, isocyanate compound (Coronate HX: C / HX, manufactured by Japan Polyurethane Co., Ltd.) 3.2 parts by weight as a crosslinking agent, fluorine-based oligomer Megafac F-477 (manufactured by DIC Corporation) 0.5 parts by weight, Irganox 1010 (manufactured by BASF Corporation) 0.5 parts by weight as an antioxidant, iron acetylacetone (manufactured by Japan Chemical Industry Co., Ltd.) 0.03 parts by weight as a catalyst were diluted with ethyl acetate so that the solid content of the whole was 50% by weight, to obtain a urethane adhesive solution. Then, the urethane adhesive solution was applied to a substrate (trade name "T100-75S", thickness 75 μm, manufactured by Mitsubishi Chemical Corporation) formed of a polyester resin so that the dried thickness was 75 μm, and cured and dried under conditions of a drying temperature of 130°C and a drying time of 3 minutes, to produce an adhesive layer formed of an adhesive composition. Subsequently, a release liner (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Corporation) formed of a polyester resin, the silicone-treated surface of which was treated, was attached to the surface of the obtained adhesive layer, to obtain a surface protection film (19). Evaluation was performed after aging for 5 days at ordinary temperature.

[0370] [Example 20]

[0371] The urethane prepolymer B100 parts by weight, isocyanate compound (Coronate HX: C / HX, manufactured by Japan Polyurethane Co., Ltd.) 2.9 parts by weight as a crosslinking agent, fluorine-based oligomer Megafac F-477 (manufactured by DIC Corporation) 0.5 parts by weight, Irganox 1010 (manufactured by BASF Corporation) 0.5 parts by weight as an antioxidant, iron acetylacetone (manufactured by Japan Chemical Industry Co., Ltd.) 0.03 parts by weight as a catalyst were diluted with ethyl acetate so that the solid content of the whole was 50% by weight, to obtain a urethane adhesive solution. Then, the urethane adhesive solution was applied to a substrate (trade name "T100-75S", thickness 75 μm, manufactured by Mitsubishi Chemical Corporation) formed of a polyester resin so that the dried thickness was 75 μm, and cured and dried under conditions of a drying temperature of 130°C and a drying time of 3 minutes, to produce an adhesive layer formed of an adhesive composition. Subsequently, a release liner (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Corporation) formed of a polyester resin, the silicone-treated surface of which was treated, was attached to the surface of the obtained adhesive layer, to obtain a surface protection film (20). Evaluation was performed after aging for 5 days at ordinary temperature.

[0372] [Example 21]

[0373] The urethane prepolymer A100 parts by weight, an isocyanate compound (Coronate HX: C / HX, manufactured by Japan Polyurethane Co., Ltd.) 3.2 parts by weight as a crosslinking agent, a fluorine-based oligomer Megafac F-556 (manufactured by DIC Corporation) 0.5 parts by weight, Irganox 1010 (manufactured by BASF Corporation) 0.5 parts by weight as an antioxidant, iron acetylacetone (manufactured by Japan Chemical Industry Co., Ltd.) 0.03 parts by weight as a catalyst were diluted with ethyl acetate so that the solid content of the whole was 50% by weight, to obtain a urethane adhesive solution. Then, the urethane adhesive solution was applied to a substrate (trade name "T100-75S", thickness 75 μm, manufactured by Mitsubishi Chemical Corporation) formed of a polyester resin so that the dried thickness was 75 μm, and cured and dried under conditions of a drying temperature of 130°C and a drying time of 3 minutes, to produce an adhesive layer formed of an adhesive composition. Subsequently, a release liner (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Corporation) formed of a polyester resin, which had been subjected to silicone treatment on one face, was attached to the surface of the obtained adhesive layer with the silicone-treated face, to obtain a surface protection film (21). Aging was performed at normal temperature for 5 days, and evaluation was performed.

[0374] [Example 22]

[0375] The urethane prepolymer B100 parts by weight, an isocyanate compound (Coronate HX: C / HX, manufactured by Japan Polyurethane Co., Ltd.) 2.9 parts by weight as a crosslinking agent, a fluorine-based oligomer Megafac F-556 (manufactured by DIC Corporation) 0.5 parts by weight, Irganox 1010 (manufactured by BASF Corporation) 0.5 parts by weight as an antioxidant, iron acetylacetone (manufactured by Japan Chemical Industry Co., Ltd.) 0.03 parts by weight as a catalyst were diluted with ethyl acetate so that the solid content of the whole was 50% by weight, to obtain a urethane adhesive solution. Then, the urethane adhesive solution was applied to a substrate (trade name "T100-75S", thickness 75 μm, manufactured by Mitsubishi Chemical Corporation) formed of a polyester resin so that the dried thickness was 75 μm, and cured and dried under conditions of a drying temperature of 130°C and a drying time of 3 minutes, to produce an adhesive layer formed of an adhesive composition. Subsequently, a release liner (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Corporation) formed of a polyester resin, which had been subjected to silicone treatment on one face, was attached to the surface of the obtained adhesive layer with the silicone-treated face, to obtain a surface protection film (22). Aging was performed at normal temperature for 5 days, and evaluation was performed.

[0376] [Example 23]

[0377] A urethane prepolymer A100 100 parts by weight, an isocyanate compound (Coronate HX: C / HX, manufactured by Japan Polyurethane Co., Ltd.) 3.2 parts by weight as a crosslinking agent, a fluorine-based oligomer Megafac F-571 (manufactured by DIC Corporation) 0.5 parts by weight, 1-ethyl-3-methylimidazolium tris(fluoromethylsulfonyl) imide (AS110, manufactured by the First Industrial Co., Ltd.) 0.05 parts by weight as an ionic compound, Irganox 1010 (manufactured by BASF Corporation) 0.5 parts by weight as an antioxidant, acetylacetone iron (manufactured by Japan Chemical Industry Co., Ltd.) 0.03 parts by weight as a catalyst were diluted with ethyl acetate so that the total solid content was 50% by weight, to obtain a urethane-based adhesive solution. Then, the urethane-based adhesive solution was applied to a substrate (trade name "T100-75S", thickness 75 μm, manufactured by Mitsubishi Chemical Corporation) formed of a polyester resin so that the thickness after drying was 75 μm, and cured and dried under conditions of a drying temperature of 130°C and a drying time of 3 minutes, to produce an adhesive layer formed of an adhesive composition. Next, a release liner (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Corporation) formed of a polyester resin having a silicone-treated surface of 25 μm in thickness was attached to the surface of the obtained adhesive layer with the silicone-treated surface, to obtain a surface protection film (23). Aging was performed at normal temperature for 5 days, and evaluation was performed.

[0378] [Example 24]

[0379] The urethane prepolymer A100 100 parts by weight, an isocyanate compound (Coronate HX: C / HX, manufactured by Japan Polyurethane Co., Ltd.) 3.2 parts by weight as a crosslinking agent, a fluorine-based oligomer Megafac F-571 (manufactured by DIC Corporation) 0.5 parts by weight, 1-ethyl-3-methylimidazolium tris(fluoromethylsulfonyl) imide (AS110, manufactured by the First Industrial Co., Ltd.) 0.10 parts by weight as an ionic compound, Irganox 1010 (manufactured by BASF Corporation) 0.5 parts by weight as an antioxidant, acetylacetone iron (manufactured by Japan Chemical Industry Co., Ltd.) 0.03 parts by weight as a catalyst were diluted with ethyl acetate so that the total solid content was 50% by weight, to obtain a urethane-based adhesive solution. Then, the urethane-based adhesive solution was applied to a substrate (trade name "T100-75S", thickness 75 μm, manufactured by Mitsubishi Chemical Corporation) formed of a polyester resin so that the thickness after drying was 75 μm, and cured and dried under conditions of a drying temperature of 130°C and a drying time of 3 minutes, to produce an adhesive layer formed of an adhesive composition. Next, a release liner (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Corporation) formed of a polyester resin having a silicone-treated surface and having a thickness of 25 μm was attached to the surface of the obtained adhesive layer with the silicone-treated surface, to obtain a surface protection film (24). Aging was performed at normal temperature for 5 days, and evaluation was performed.

[0380] [Example 25]

[0381] A urethane prepolymer A100 100 parts by weight, an isocyanate compound (Coronate HX: C / HX, manufactured by Japan Polyurethane Co., Ltd.) 3.2 parts by weight as a crosslinking agent, a fluorine-based oligomer Megafac F-571 (manufactured by DIC Corporation) 0.5 parts by weight, 1-ethyl-3-methylimidazolium tris(fluoromethylsulfonyl) imide (AS110, manufactured by the First Industrial Co., Ltd.) 0.50 parts by weight as an ionic compound, Irganox 1010 (manufactured by BASF Corporation) 0.5 parts by weight as an antioxidant, acetylacetone iron (manufactured by Japan Chemical Industry Co., Ltd.) 0.03 parts by weight as a catalyst were diluted with ethyl acetate so that the total solid content was 50% by weight, to obtain a urethane-based adhesive solution. Then, the urethane-based adhesive solution was applied to a substrate (trade name "T100-75S", thickness 75 μm, manufactured by Mitsubishi Chemical Corporation) formed of a polyester resin so that the thickness after drying was 75 μm, and cured and dried under conditions of a drying temperature of 130°C and a drying time of 3 minutes, to produce an adhesive layer formed of an adhesive composition. Next, a release liner (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Corporation) formed of a polyester resin having a silicone-treated surface and having a thickness of 25 μm was attached to the surface of the obtained adhesive layer with the silicone-treated surface, to obtain a surface-protective film (25). Aging was performed at normal temperature for 5 days, and evaluation was performed.

[0382] [Example 26]

[0383] The urethane prepolymer A100 100 parts by weight, an isocyanate compound (Coronate HX: C / HX, manufactured by Japan Urethane Corp.) 3.2 parts by weight as a crosslinking agent, a fluorine-based oligomer Megafac F-571 (manufactured by DIC Corp.) 0.5 parts by weight, 1-ethyl-3-methylimidazolium tris(fluoromethylsulfonyl) imide (AS110, manufactured by the First Industrial Co., Ltd.) 1.00 parts by weight as an ionic compound, Irganox 1010 (manufactured by BASF Corp.) 0.5 parts by weight as an antioxidant, acetylacetone iron (manufactured by Japan Chemical Industry Co., Ltd.) 0.03 parts by weight as a catalyst were diluted with ethyl acetate so that the total solid content would be 50% by weight, to obtain a urethane-based adhesive solution. Then, the urethane-based adhesive solution was applied to a substrate (trade name "T100-75S", thickness 75 μm, manufactured by Mitsubishi Chemical Corp.) formed of a polyester resin so that the thickness after drying would be 75 μm, and cured and dried under conditions of a drying temperature of 130°C and a drying time of 3 minutes, to produce an adhesive layer formed of an adhesive composition. Next, a release liner (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Corp.) formed of a polyester resin having a silicone-treated surface and having a thickness of 25 μm was attached to the surface of the obtained adhesive layer with the silicone-treated surface, to obtain a surface-protective film (26). Aging was performed at ordinary temperature for 5 days, and evaluation was performed.

[0384] [Example 27]

[0385] The urethane prepolymer A100 100 parts by weight, an isocyanate compound (Coronate HX: C / HX, manufactured by Japan Polyurethane Co., Ltd.) 3.2 parts by weight as a crosslinking agent, a fluorine-based oligomer Megafac F-563 (manufactured by DIC Corporation) 0.5 parts by weight, 1-ethyl-3-methylimidazolium tris(fluoromethylsulfonyl) imide (AS110, manufactured by the First Industrial Co., Ltd.) 0.50 parts by weight as an ionic compound, Irganox 1010 (manufactured by BASF Corporation) 0.5 parts by weight as an antioxidant, acetylacetone iron (manufactured by Japan Chemical Industry Co., Ltd.) 0.03 parts by weight as a catalyst were diluted with ethyl acetate so that the total solid content was 50% by weight, to obtain a urethane-based adhesive solution. Then, the urethane-based adhesive solution was applied to a substrate (trade name "T100-75S", thickness 75 μm, manufactured by Mitsubishi Chemical Corporation) formed of a polyester resin so that the thickness after drying was 75 μm, and cured and dried under conditions of a drying temperature of 130°C and a drying time of 3 minutes, to produce an adhesive layer formed of an adhesive composition. Next, a release liner (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Corporation) formed of a polyester resin having a silicone-treated surface and having a thickness of 25 μm was attached to the surface of the obtained adhesive layer with the silicone-treated surface, to obtain a surface-protective film (27). Aging was performed at normal temperature for 5 days, and evaluation was performed.

[0386] [Example 28]

[0387] The urethane prepolymer A100 100 parts by weight, an isocyanate compound (Coronate HX: C / HX, manufactured by Japan Polyurethane Co., Ltd.) 3.2 parts by weight as a crosslinking agent, a fluorine-based oligomer Megafac F-477 (manufactured by DIC Corporation) 0.5 parts by weight, 1-ethyl-3-methylimidazolium tris(fluoromethylsulfonyl) imide (AS110, manufactured by the First Industrial Co., Ltd.) 0.50 parts by weight as an ionic compound, Irganox 1010 (manufactured by BASF Corporation) 0.5 parts by weight as an antioxidant, acetylacetone iron (manufactured by Japan Chemical Industry Co., Ltd.) 0.03 parts by weight as a catalyst were diluted with ethyl acetate so that the total solid content was 50% by weight, to obtain a urethane-based adhesive solution. Then, the urethane-based adhesive solution was applied to a substrate (trade name "T100-75S", thickness 75 μm, manufactured by Mitsubishi Chemical Corporation) formed of a polyester resin so that the thickness after drying was 75 μm, and cured and dried under conditions of a drying temperature of 130°C and a drying time of 3 minutes, to produce an adhesive layer formed of an adhesive composition. Subsequently, a release liner (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Corporation) formed of a polyester resin having a silicone-treated surface with a thickness of 25 μm was attached to the surface of the obtained adhesive layer with the silicone-treated surface, to obtain a surface protection film (28). Aging was performed at normal temperature for 5 days, and evaluation was performed.

[0388] [Example 29]

[0389] The urethane prepolymer A100 100 parts by weight, an isocyanate compound (Coronate HX: C / HX, manufactured by Japan Polyurethane Co., Ltd.) 3.2 parts by weight as a crosslinking agent, a fluorine-based oligomer Megafac F-556 (manufactured by DIC Corporation) 0.5 parts by weight, 1-ethyl-3-methylimidazolium tris(fluoromethylsulfonyl) imide (AS110, manufactured by the First Industrial Co., Ltd.) 0.50 parts by weight as an ionic compound, Irganox 1010 (manufactured by BASF Corporation) 0.5 parts by weight as an antioxidant, acetylacetone iron (manufactured by Japan Chemical Industry Co., Ltd.) 0.03 parts by weight as a catalyst were diluted with ethyl acetate so that the total solid content was 50% by weight, to obtain a urethane-based adhesive solution. Then, the urethane-based adhesive solution was applied to a substrate (trade name "T100-75S", thickness 75 μm, manufactured by Mitsubishi Chemical Corporation) formed of a polyester resin so that the thickness after drying was 75 μm, and cured and dried under conditions of a drying temperature of 130°C and a drying time of 3 minutes, to produce an adhesive layer formed of an adhesive composition. Next, a release liner (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Corporation) formed of a polyester resin having a silicone-treated surface and having a thickness of 25 μm was attached to the surface of the obtained adhesive layer with the silicone-treated surface, to obtain a surface protection film (29). Aging was performed at normal temperature for 5 days, and evaluation was performed.

[0390] [Example 30]

[0391] A urethane prepolymer A95 95 parts by weight, Preminol S3011 (manufactured by Asahi Glass Company, Ltd., Mn = 10000) 3.5 parts by weight as a polyol having 3 hydroxyl groups, Sannix GP3000 (manufactured by Sanyo Chemical Industries, Ltd., Mn = 3000) 1.5 parts by weight as a polyol having 3 hydroxyl groups, an isocyanate compound (Coronate HX: C / HX, manufactured by Japan Polyurethane Co., Ltd.) 3.8 parts by weight as a crosslinking agent, a fluorine-based oligomer Megafac F-571 (manufactured by DIC Corporation) 0.5 parts by weight, 1-ethyl-3-methylimidazolium tris(fluoromethylsulfonyl) imide (AS110, manufactured by the First Industrial Co., Ltd.) 0.50 parts by weight as an ionic compound, Irganox 1010 (manufactured by BASF Corporation) 0.5 parts by weight as an antioxidant, acetylacetone iron (manufactured by Japan Chemical Industries, Ltd.) 0.03 parts by weight as a catalyst were diluted with ethyl acetate so that the solid content of the whole would be 50% by weight, to obtain a urethane-based adhesive solution. Then, the urethane-based adhesive solution was applied to a substrate (trade name "T100-75S", thickness 75 μm, manufactured by Mitsubishi Chemical Corporation) formed of a polyester resin so that the thickness after drying would be 75 μm, and cured and dried under conditions of a drying temperature of 130°C and a drying time of 3 minutes, to produce an adhesive layer formed of an adhesive composition. Subsequently, a release liner (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Corporation) formed of a polyester resin having a thickness of 25 μm and having a silicone-treated surface on one face was attached to the surface of the obtained adhesive layer with the silicone-treated surface, to obtain a surface protection film (30). Aging was performed at ordinary temperature for 5 days, and evaluation was performed.

[0392] [Example 31]

[0393] A urethane prepolymer A95 95 parts by weight, Preminol S3011 (manufactured by Asahi Glass Co., Ltd., Mn = 10000) as a polyol having 3 hydroxyl groups 3 parts by weight, Sannix GP3000 (manufactured by Sanyo Chemical Industries, Ltd., Mn = 3000) as a polyol having 3 hydroxyl groups 2 parts by weight, an isocyanate compound (Coronate HX: C / HX, manufactured by Japan Polyurethane Co., Ltd.) as a crosslinking agent 3.9 parts by weight, a fluorine-based oligomer Megafac F-571 (manufactured by DIC Corporation) 0.5 parts by weight, 1-ethyl-3-methylimidazolium tris (fluoromethylsulfonyl) imide (AS110, manufactured by the First Industrial Co., Ltd.) as an ionic compound 0.50 parts by weight, Irganox 1010 (manufactured by BASF Corporation) as an antioxidant 0.5 parts by weight, acetylacetone iron (manufactured by Japan Chemical Industries, Ltd.) as a catalyst 0.03 parts by weight were diluted with ethyl acetate so that the solid content of the whole would be 50% by weight, to obtain a urethane-based adhesive solution. Then, the urethane-based adhesive solution was applied to a substrate (trade name "T100-75S", thickness 75 μm, manufactured by Mitsubishi Chemical Corporation) formed of a polyester resin so that the thickness after drying would be 75 μm, and cured and dried under conditions of a drying temperature of 130°C and a drying time of 3 minutes, to produce an adhesive layer formed of an adhesive composition. Next, a release liner (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Corporation) formed of a polyester resin having a silicone-treated surface of 25 μm in thickness was attached to the surface of the obtained adhesive layer with the silicone-treated surface, to obtain a surface protection film (31). Aging was performed at ordinary temperature for 5 days, and evaluation was performed.

[0394] [Example 32]

[0395] A urethane prepolymer A80 80 parts by weight, Preminol S3011 (manufactured by Asahi Glass Company, Ltd., Mn = 10000) as a polyol having 3 hydroxyl groups 12 parts by weight, Sannix GP3000 (manufactured by Sanyo Chemical Industries, Ltd., Mn = 3000) as a polyol having 3 hydroxyl groups 8 parts by weight, an isocyanate compound (Coronate HX: C / HX, manufactured by Japan Polyurethane Co., Ltd.) as a crosslinking agent 6.0 parts by weight, a fluorine-based oligomer Megafac F-571 (manufactured by DIC Corporation) 0.5 parts by weight, 1-ethyl-3-methylimidazolium tris (fluoromethylsulfonyl) imide (AS110, manufactured by the First Industrial Co., Ltd.) as an ionic compound 0.50 parts by weight, Irganox 1010 (manufactured by BASF Corporation) as an antioxidant 0.5 parts by weight, acetylacetone iron (manufactured by Japan Chemical Industries, Ltd.) as a catalyst 0.03 parts by weight were diluted with ethyl acetate so that the solid content of the whole would be 50% by weight, to obtain a urethane-based adhesive solution. Then, the urethane-based adhesive solution was applied to a substrate (trade name "T100-75S", thickness 75 μm, manufactured by Mitsubishi Chemical Corporation) formed of a polyester resin so that the thickness after drying would be 75 μm, and cured and dried under conditions of a drying temperature of 130°C and a drying time of 3 minutes, to produce an adhesive layer formed of an adhesive composition. Subsequently, a release liner (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Corporation) formed of a polyester resin having a thickness of 25 μm and having a silicone-treated surface on one face was attached to the surface of the obtained adhesive layer with the silicone-treated surface, to obtain a surface-protective film (32). Aging was performed at ordinary temperature for 5 days, and evaluation was performed.

[0396] [Example 33]

[0397] A urethane prepolymer A60 60 parts by weight, Preminol S3011 (manufactured by Asahi Glass Company, Ltd., Mn = 10000) as a polyol having 3 hydroxyl groups 28 parts by weight, Sannix GP3000 (manufactured by Sanyo Chemical Industries, Ltd., Mn = 3000) as a polyol having 3 hydroxyl groups 12 parts by weight, an isocyanate compound (Coronate HX: C / HX, manufactured by Japan Polyurethane Co., Ltd.) as a crosslinking agent 8.0 parts by weight, a fluorine-based oligomer Megafac F-571 (manufactured by DIC Corporation) 0.5 parts by weight, 1-ethyl-3-methylimidazolium tris (fluoromethylsulfonyl) imide (AS110, manufactured by the First Industrial Co., Ltd.) as an ionic compound 0.50 parts by weight, Irganox 1010 (manufactured by BASF Corporation) as an antioxidant 0.5 parts by weight, acetylacetone iron (manufactured by Japan Chemical Industries, Ltd.) as a catalyst 0.03 parts by weight were diluted with ethyl acetate so that the solid content of the whole would be 50% by weight, to obtain a urethane-based adhesive solution. Then, the urethane-based adhesive solution was applied to a substrate (trade name "T100-75S", thickness 75 μm, manufactured by Mitsubishi Chemical Corporation) formed of a polyester resin so that the thickness after drying would be 75 μm, and cured and dried under conditions of a drying temperature of 130°C and a drying time of 3 minutes, to produce an adhesive layer formed of an adhesive composition. Subsequently, a release liner (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Corporation) formed of a polyester resin having a thickness of 25 μm and having a silicone-treated surface on one face was attached to the surface of the obtained adhesive layer with the silicone-treated surface, to obtain a surface-protective film (33). Aging was performed at ordinary temperature for 5 days, and evaluation was performed.

[0398] [Example 34]

[0399] A urethane prepolymer A60 60 parts by weight, Preminol S3011 (manufactured by Asahi Glass Company, Ltd., Mn = 10000) as a polyol having 3 hydroxyl groups, 25 parts by weight, Sannix GP3000 (manufactured by Sanyo Chemical Industries, Ltd., Mn = 3000) as a polyol having 3 hydroxyl groups, 15 parts by weight, an isocyanate compound (Coronate HX: C / HX, manufactured by Japan Polyurethane Co., Ltd.) as a crosslinking agent, 8.6 parts by weight, a fluorine-based oligomer Megafac F-571 (manufactured by DIC Corporation) 0.5 parts by weight, 1-ethyl-3-methylimidazolium tris (fluoromethylsulfonyl) imide (AS110, manufactured by the First Industrial Co., Ltd.) as an ionic compound, 0.50 parts by weight, Irganox 1010 (manufactured by BASF Corporation) as an antioxidant, 0.5 parts by weight, acetylacetone iron (manufactured by Japan Chemical Industries, Ltd.) as a catalyst, 0.03 parts by weight were diluted with ethyl acetate so that the total solid content was 50% by weight, to obtain a urethane-based adhesive solution. Then, the urethane-based adhesive solution was applied to a substrate (trade name "T100-75S", thickness 75 μm, manufactured by Mitsubishi Chemical Corporation) formed of a polyester resin so that the thickness after drying was 75 μm, and cured and dried under conditions of a drying temperature of 130°C and a drying time of 3 minutes, to produce an adhesive layer formed of an adhesive composition. Subsequently, a release liner (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Corporation) formed of a polyester resin having a thickness of 25 μm and having a silicone-treated surface on one face was attached to the surface of the obtained adhesive layer with the silicone-treated surface, to obtain a surface protection film (34). Aging was performed at normal temperature for 5 days, and evaluation was performed.

[0400] [Example 35]

[0401] A urethane prepolymer A50 50 parts by weight, Preminol S3011 (manufactured by Asahi Glass Company, Ltd., Mn = 10000) as a polyol having 3 hydroxyl groups 30 parts by weight, Sannix GP4000 (manufactured by Sanyo Chemical Industries, Ltd., Mn = 4000) as a polyol having 3 hydroxyl groups 20 parts by weight, an isocyanate compound (Coronate HX: C / HX, manufactured by Japan Polyurethane Corporation) as a crosslinking agent 8.7 parts by weight, a fluorine-based oligomer Megafac F-571 (manufactured by DIC Corporation) 0.5 parts by weight, 1-ethyl-3-methylimidazolium tris(fluoromethylsulfonyl) imide (AS110, manufactured by the First Industrial Co., Ltd.) as an ionic compound 0.50 parts by weight, Irganox 1010 (manufactured by BASF Corporation) as an antioxidant 0.5 parts by weight, acetylacetone iron (manufactured by Japan Chemical Industries, Ltd.) as a catalyst 0.03 parts by weight were diluted with ethyl acetate so that the total solid content would be 50% by weight, to obtain a urethane-based adhesive solution. Then, the urethane-based adhesive solution was applied to a substrate (trade name "T100-75S", thickness 75 μm, manufactured by Mitsubishi Chemical Corporation) formed of a polyester resin so that the thickness after drying would be 75 μm, and cured and dried under conditions of a drying temperature of 130°C and a drying time of 3 minutes, to produce an adhesive layer formed of an adhesive composition. Subsequently, a release liner (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Corporation) formed of a polyester resin having a silicone-treated surface and having a thickness of 25 μm was attached to the surface of the obtained adhesive layer with the silicone-treated surface facing outward, to obtain a surface-protective film (35). Aging was performed at normal temperature for 5 days, and evaluation was performed.

[0402] [Comparative Example 1]

[0403] A urethane prepolymer A100 parts by weight, an isocyanate compound (Coronate HX: C / HX, manufactured by Japan Polyurethane Co., Ltd.) 3.2 parts by weight as a crosslinking agent, Irganox 1010 (manufactured by BASF Corporation) 0.5 parts by weight as an antioxidant, iron acetylacetone (manufactured by Japan Chemical Industry Co., Ltd.) 0.03 parts by weight as a catalyst were diluted with ethyl acetate so that the solid content of the whole would be 50% by weight, to obtain a urethane adhesive solution. Then, the urethane adhesive solution was applied to a substrate (trade name "T100-75S", thickness 75 μm, manufactured by Mitsubishi Chemical Corporation) formed of a polyester resin so that the dried thickness would be 75 μm, and cured and dried under conditions of a drying temperature of 130°C and a drying time of 3 minutes, to produce an adhesive layer formed of an adhesive composition. Next, a release liner (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Corporation) formed of a polyester resin, the silicone-treated surface of which had been treated with silicone, was attached to the surface of the obtained adhesive layer with the silicone-treated surface facing outward, to obtain a surface protection film (C1). Aging was performed at ordinary temperature for 5 days, and evaluation was performed.

[0404] [Comparative Example 2]

[0405] A urethane prepolymer B100 parts by weight, an isocyanate compound (Coronate HX: C / HX, manufactured by Japan Polyurethane Co., Ltd.) 2.9 parts by weight as a crosslinking agent, Irganox 1010 (manufactured by BASF Corporation) 0.5 parts by weight as an antioxidant, iron acetylacetone (manufactured by Japan Chemical Industry Co., Ltd.) 0.03 parts by weight as a catalyst were diluted with ethyl acetate so that the solid content of the whole would be 50% by weight, to obtain a urethane adhesive solution. Then, the urethane adhesive solution was applied to a substrate (trade name "T100-75S", thickness 75 μm, manufactured by Mitsubishi Chemical Corporation) formed of a polyester resin so that the dried thickness would be 75 μm, and cured and dried under conditions of a drying temperature of 130°C and a drying time of 3 minutes, to produce an adhesive layer formed of an adhesive composition. Next, a release liner (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Corporation) formed of a polyester resin, the silicone-treated surface of which had been treated with silicone, was attached to the surface of the obtained adhesive layer with the silicone-treated surface facing outward, to obtain a surface protection film (C2). Aging was performed at ordinary temperature for 5 days, and evaluation was performed.

[0406] [Comparative Example 3]

[0407] A urethane prepolymer A50 50 parts by weight, Preminol S3011 (manufactured by Asahi Glass Co., Ltd., Mn = 10000) as a polyol having 3 hydroxyl groups 35 parts by weight, Sannix GP3000 (manufactured by Sanyo Chemical Industries, Ltd., Mn = 3000) as a polyol having 3 hydroxyl groups 15 parts by weight, an isocyanate compound (Coronate HX: C / HX, manufactured by Japan Polyurethane Co., Ltd.) as a crosslinking agent 9.2 parts by weight, a fluorine-based oligomer Megafac F-571 (manufactured by DIC Corporation) 0.5 parts by weight, Irganox 1010 (manufactured by BASF Corporation) as an antioxidant 0.5 parts by weight, iron acetylacetone (manufactured by Japan Chemical Industries Co., Ltd.) as a catalyst 0.03 parts by weight were diluted with ethyl acetate so that the solid content of the whole would be 50% by weight, to obtain a urethane adhesive solution. Then, the urethane adhesive solution was applied to a substrate (trade name "T100-75S", thickness 75 μm, manufactured by Mitsubishi Chemical Corporation) formed of a polyester resin so that the thickness after drying would be 75 μm, and cured and dried under conditions of a drying temperature of 130°C and a drying time of 3 minutes, to produce an adhesive layer formed of an adhesive composition. Subsequently, a release liner (trade name "MRF25", thickness 25 μm, manufactured by Mitsubishi Chemical Corporation) formed of a polyester resin having a silicone-treated surface of 25 μm in thickness was attached to the surface of the obtained adhesive layer with the silicone-treated surface, to obtain a surface protection film (C3). Evaluation was performed after aging for 5 days at ordinary temperature.

[0408] [Comparative Example 4]

[0409] A urethane prepolymer A50 (30 parts by weight), Preminol S3011 (Asahi Glass Co., Ltd., Mn = 10,000) as a polyol having 3 hydroxyl groups (30 parts by weight), Sannix GP3000 (Sanyo Chemical Industries, Ltd., Mn = 3,000) as a polyol having 3 hydroxyl groups (20 parts by weight), an isocyanate compound (Coronate HX: C / HX, Japan Polyurethane Co., Ltd.) as a crosslinking agent (10.1 parts by weight), a fluorine-based oligomer Megafac F-571 (DIC Corporation) (0.5 parts by weight), Irganox 1010 (BASF Corporation) as an antioxidant (0.5 parts by weight), iron acetylacetone (Japan Chemical Industries Co., Ltd.) as a catalyst (0.03 parts by weight) were diluted with ethyl acetate so that the solid content of the whole would be 50% by weight, to obtain a urethane adhesive solution. Then, the urethane adhesive solution was applied to a substrate (trade name "T100-75S", thickness 75 μm, Mitsubishi Chemical Corporation) formed of a polyester resin so that the thickness after drying would be 75 μm, and cured and dried under conditions of a drying temperature of 130°C and a drying time of 3 minutes, to produce an adhesive layer formed of an adhesive composition. Next, a release liner (trade name "MRF25", thickness 25 μm, Mitsubishi Chemical Corporation) formed of a polyester resin, the silicone-treated surface of which had been subjected to silicone treatment, was attached to the surface of the obtained adhesive layer, to obtain a surface-protective film (C4). Aging was performed at ordinary temperature for 5 days, and evaluation was performed.

[0410] [Examples 36 to 70]

[0411] As to each of the surface-protective films obtained in Examples 1 to 35, the release liner was peeled off, and attached to a polarizing plate (Nippon Sheet Glass Co., Ltd., trade name "TEG1465DUHC") as an optical member, to obtain an optical member to which a surface-protective film was attached.

[0412] [Examples 71 to 105]

[0413] As to each of the surface-protective films obtained in Examples 1 to 35, the release liner was peeled off, and attached to a conductive film (Nippon Sheet Glass Co., Ltd., trade name "ELECRYSTA V270L-TFMP") as an electronic member, to obtain an electronic member to which a surface-protective film was attached.

[0414] [Table 1]

[0415]

[0416] [Table 2]

[0417]

[0418] [Table 3]

[0419]

[0420] Industrial applicability

[0421] The surface protective film of the present application can be used for any appropriate use. Preferably, the surface protective film of the present application is preferably used for surface protection of optical members, electronic members.

[0422] Explanation of reference numerals

[0423] 1 substrate layer

[0424] 2 adhesive layer

[0425] 10 surface protective film

Claims

1. A surface protective film comprising an adhesive layer, The adhesive layer is composed of a urethane-based adhesive, which is formed from a urethane-based adhesive composition. This urethane-based adhesive composition comprises a base polymer and a fluorinated compound. The base polymer contains urethane prepolymers. The base polymer contains a polyol that is not a urethane prepolymer. The ratio of the urethane prepolymer to the polyol in the urethane-based adhesive composition, by weight, is urethane prepolymer: polyol = 70:30 to 95:

5. The proportion of hydroxyl groups in this urethane-based adhesive composition is less than 30 mmol per 100g of the base polymer.

2. The surface protective film according to claim 1, wherein, The base polymer comprises a polyoxyalkylene structure represented by general formula (1). In general formula (1), R 1 It indicates that it is selected from the group consisting of hydrogen atoms, alkyl groups having 1 to 4 carbon atoms, and hydroxyalkyl groups having 1 to 6 carbon atoms, with multiple Rs. 1 Choose any two numbers that are the same or different from each other, where n represents an integer from 1 to 4 and m represents an integer from 1 to 200.

3. The surface protective film according to claim 2, wherein, The urethane prepolymer comprises the polyoxyalkylene structure represented by the general formula (1).

4. The surface protective film according to claim 1, wherein, The polyol comprises a polyoxyalkylene structure represented by general formula (1). In general formula (1), R 1 It indicates that it is selected from the group consisting of hydrogen atoms, alkyl groups having 1 to 4 carbon atoms, and hydroxyalkyl groups having 1 to 6 carbon atoms, with multiple Rs. 1 Choose any two numbers that are the same or different from each other, where n represents an integer from 1 to 4 and m represents an integer from 1 to 200.

5. The surface protective film according to claim 1, wherein, The haze of the adhesive layer is below 3.5%.

6. The surface protective film according to claim 1, wherein, The surface tension of the fluorinated compound when prepared as a 0.1% propylene glycol monomethyl ether solution is above 23 mN / m.

7. The surface protective film according to claim 1, wherein, The urethane-based adhesive composition comprises an ionic compound in an amount of 0.05 parts by weight or more relative to 100 parts by weight of the base polymer.

8. An optical component having a surface protective film attached to it according to any one of claims 1 to 7.

9. An electronic component having a surface protective film attached to it according to any one of claims 1 to 7.

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