JP2016107500A - Adherend having surface protective film adhered thereto - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a subject member in which an adhesive layer side of a surface protective film having an adhesive layer is adhered to an adherend surface having a large surface level difference, which is an adherend having a surface protective film adhered thereto in which, when the surface protective film is peeled off from the adherend once and adhered to the adherend again, the film has sufficient wettability even when the surface level difference is large and, further, can achieve a sufficiently high adhesive rate due to its excellent level difference followability.SOLUTION: The adherend having a surface protective film adhered thereto is a subject member in which an adhesive layer side of the surface protective film including an adhesive layer is adhered to an adherend surface having center line average roughness Ra of 0.2 μm to 2 μm. The adhesive layer comprises as a main component a urethane-based adhesive containing a polyurethane-based resin, and the adhesive layer has an adhesion rate of 80% or more when adhered to the adherend surface with a dead weight only.SELECTED DRAWING: Figure 1

Description

  The present invention relates to an adherend with a surface protective film. The adherend with a surface protective film of the present invention is, for example, a member having a surface protective film bonded to the surface of an optical member or an electronic member.

  In order to prevent scratches on the surface of optical members and electronic members during processing, assembly, inspection, transportation, etc., a surface protective film is generally attached to the exposed surface side. Such a surface protective film is peeled off from the optical member or the electronic member when the surface protection is no longer necessary.

  In many cases, such surface protection films continue to use the same surface protection film from the manufacturing process of optical members and electronic members, through the assembly process, inspection process, transportation process, etc. until final shipment. Yes. In this case, such a surface protective film is often attached, peeled off and reattached manually in each step.

  When the surface protective film is attached manually or when the surface protective film is attached to a large adherend, air bubbles may be caught between the adherend and the surface protective film. For this reason, some techniques which improve the wettability of a surface protection film are reported so that a bubble may not be involved in the case of sticking. For example, a surface protective film using a silicone resin having a high wetting speed as an adhesive layer is known (see, for example, Patent Document 1).

  However, when silicone resin is used for the pressure-sensitive adhesive layer, the pressure-sensitive adhesive component easily contaminates the adherend, and surface protection for protecting the surface of members that require particularly low contamination such as optical members and electronic members. There is a big problem in using it as a film.

  As a surface protective film with little contamination derived from the pressure-sensitive adhesive component, a surface protective film using an acrylic resin for the pressure-sensitive adhesive layer is known (for example, see Patent Document 2). However, the surface protective film using acrylic resin for the adhesive layer is inferior in wettability, so when sticking the surface protective film manually, air bubbles are involved between the adherend and the surface protective film. There is. In addition, when an acrylic resin is used for the adhesive layer, there is a problem that glue residue is likely to be generated at the time of peeling, and a surface protection film for protecting the surface of a member that is particularly apt to be mixed with foreign substances such as an optical member and an electronic member. There is a problem to use as.

  Moreover, when sticking a surface protection film to a to-be-adhered body, it is requested | required that it is excellent in wettability, such as the above initial wettability, and a light peelability is requested | required. This is because the adherend is not damaged at the time of peeling, or after being peeled off, it is reattached to the adherend and used again as a surface protective film. Even if the wettability is good, if the peel is heavy, in the case of a thin and weak adherend, the adherend is destroyed, or the surface protective film is deformed when the surface protective film is peeled off, It can no longer be used as a surface protective film. In order to avoid such problems, the surface protective film used for optical members and electronic members can be stuck many times without entrainment of bubbles, and can be peeled lightly without deformation, so-called reworkability is strong. Desired.

  In order to solve such a problem, a surface protective film having a pressure-sensitive adhesive layer containing a specific urethane-based pressure-sensitive adhesive has recently been reported (see, for example, Patent Documents 3 and 4).

  However, the surface protective film having a pressure-sensitive adhesive layer containing a conventional urethane-based pressure-sensitive adhesive is inferior in step following ability when bonded to an adherend having a large surface step, and a problem that a sufficiently high adhesion rate cannot be achieved. is there.

  In particular, as described above, in the field of optical members and electronic members, the surface protective film is the same surface protective film from the manufacturing process, through the assembly process, inspection process, transportation process, etc. until the final shipment. There are many cases that continue to be used, and in each step, the same surface protective film is often attached, peeled off, and reattached to the adherend manually. In such a case, when the surface protective film is once peeled off from the adherend to which the surface protective film has been pasted and then again attached to the adherend, the surface difference of the adherend is large. As a result, the step following ability is greatly inferior and it becomes difficult to achieve a high adhesion rate.

JP 2006-152266 A JP 2004-051825 A JP 2014-111701 A JP 2004-111702 A

  An object of the present invention is a member in which the pressure-sensitive adhesive layer side of a surface protective film including a pressure-sensitive adhesive layer is bonded to an adherend surface having a large surface step, and once the surface protective film is peeled off from the adherend In addition, when sticking to the adherend again, even if the surface step of the adherend is large, the wettability is excellent, and furthermore, the step following ability is excellent, so that the adhesion rate is sufficiently high. The object is to provide an adherend with a surface protective film that can be achieved.

The adherend with a surface protective film of the present invention comprises:
The pressure-sensitive adhesive layer side of the surface protective film including the pressure-sensitive adhesive layer is a member bonded to the adherend surface having a center line average roughness Ra of 0.2 μm to 2 μm,
The pressure-sensitive adhesive layer contains a urethane-based pressure-sensitive adhesive containing a polyurethane-based resin as a main component,
The pressure-sensitive adhesive layer is a pressure-sensitive adhesive layer having an adhesion rate of 80% or more when bonded to the surface of the adherend with only its own weight.

  In a preferred embodiment, the adherend is an optical member or an electronic member.

  In a preferred embodiment, the polyurethane resin is a polyurethane resin obtained from a composition containing a polyol (A) and a polyfunctional isocyanate compound (B).

  In preferable embodiment, the number average molecular weight Mn of the said polyol (A) is 400-20000.

  In a preferred embodiment, the equivalent ratio of NCO groups to OH groups in the polyol (A) and the polyfunctional isocyanate compound (B) is 0.3 to 1.0 as NCO groups / OH groups.

  In a preferred embodiment, the polyurethane resin is a polyurethane resin obtained from a composition containing a urethane prepolymer (C) and a polyfunctional isocyanate compound (B).

  In a preferred embodiment, the equivalent ratio of NCO groups to OH groups in the urethane prepolymer (C) and the polyfunctional isocyanate compound (B) is 0.3 to 1.0 as NCO groups / OH groups. .

  In preferable embodiment, the said urethane type adhesive contains fatty acid ester.

  In preferable embodiment, the number average molecular weight Mn of the said fatty acid ester is 200-400.

  According to the present invention, the pressure-sensitive adhesive layer side of the surface protective film including the pressure-sensitive adhesive layer is a member bonded to the adherend surface having a large surface step, and once peeled off the surface protective film from the adherend In addition, when sticking to the adherend again, even if the surface step of the adherend is large, the wettability is excellent, and furthermore, the step following ability is excellent, so that the adhesion rate is sufficiently high. An adherend with a surface protective film that can be achieved can be provided.

It is a schematic sectional drawing of the adherend with a surface protection film by preferable embodiment of this invention.

  The adherend with a surface protective film of the present invention is a member in which the pressure-sensitive adhesive layer side of the surface protective film including the pressure-sensitive adhesive layer is bonded to the surface of the adherend having a center line average roughness Ra of 0.2 μm to 2 μm. It is.

  The adherend with the surface protective film of the present invention may be a member in which the pressure-sensitive adhesive layer side of the surface protective film including the pressure-sensitive adhesive layer is bonded to a part of the surface of the adherend. It may be a member bonded to the entire surface. For example, the adherend with a surface protective film of the present invention may be a member in which the pressure-sensitive adhesive layer side of the surface protective film including the pressure-sensitive adhesive layer is bonded to the surface of one side of the adherend, It may be a member bonded to the surfaces on both sides of the body.

  As long as the adherend with a surface protective film of the present invention has a surface protective film and an adherend, it may have any other appropriate member within a range not impairing the effects of the present invention. .

  In the adherend with a surface protective film of the present invention, the center line average roughness Ra of the adherend surface is 0.2 μm to 2 μm.

  If the adherend in the adherend with a surface protective film of the present invention is an adherend having a surface centerline average roughness Ra of 0.2 μm to 2 μm, the effect of the present invention is not impaired. Any suitable adherend may be employed. Such an adherend is preferably an optical member or an electronic member. Examples of the optical member include an LCD, a touch panel using the LCD, a color filter used for the LCD, a polarizing plate, and the like. Examples of the electronic member include a conductive film and electronic paper.

≪Surface protection film≫
The surface protective film includes an adhesive layer. A release liner having releasability may be bonded to the pressure-sensitive adhesive layer side of the pressure-sensitive adhesive layer.

  In the surface protective film, the pressure-sensitive adhesive layer or a pressure-sensitive adhesive layer having a release liner bonded to the pressure-sensitive adhesive surface is preferably positioned in the outermost layer.

  The surface protective film preferably has a base material layer and an adhesive layer. Only one layer may be sufficient as a base material layer, and two or more layers may be sufficient as it. In addition to the base material layer and the pressure-sensitive adhesive layer, the surface protective film of the present invention may have any other appropriate layer as long as the effects of the present invention are not impaired.

  FIG. 1 is a schematic sectional view of an adherend with a surface protective film according to a preferred embodiment of the present invention. The adherend with surface protective film 1000 includes the adherend 100 and the surface protective film 10. In FIG. 1, the surface protective film 10 is bonded only to one surface side of the adherend 100, but the surface protective film 10 may be bonded to both surface sides of the adherend 100. . In FIG. 1, the surface protective film 10 includes a base material layer 1 and an adhesive layer 2. The surface protective film may further include any appropriate other layer as necessary (not shown).

  For the purpose of forming a wound body that can be easily rewound on the surface of the base material layer 1 that is not provided with the pressure-sensitive adhesive layer 2, for example, the base material layer includes a fatty acid amide, polyethyleneimine, and a long-chain alkyl series. A release treatment can be performed by adding an additive or the like, or a coating layer made of any appropriate release agent such as silicone, long-chain alkyl, or fluorine can be provided.

  The thickness of the surface protective film can be set to any appropriate thickness depending on the application. From the viewpoint of sufficiently expressing the effects of the present invention, the thickness is preferably 10 μm to 300 μm, more preferably 15 μm to 250 μm, still more preferably 20 μm to 200 μm, and particularly preferably 25 μm to 150 μm.

≪Adhesive layer≫
The pressure-sensitive adhesive layer contains a urethane-based pressure-sensitive adhesive containing a polyurethane-based resin as a main component. The content of the urethane-based pressure-sensitive adhesive in the pressure-sensitive adhesive layer is preferably 50% by weight to 100% by weight, more preferably 60% by weight to 100% by weight, and further preferably 70% by weight to 100% by weight. Particularly preferably 80% to 100% by weight, most preferably 90% to 100% by weight. By adjusting the content ratio of the urethane-based adhesive in the adhesive layer within the above range, once the surface protective film is peeled off from the adherend having a large surface step, and is again attached to the adherend. To provide an adherend with a surface protective film, which is capable of achieving a sufficiently high adhesion rate because it is excellent in wettability even when the surface step of the adherend is large, and further in step followability. Can do.

  The pressure-sensitive adhesive layer is a pressure-sensitive adhesive layer having an adhesion rate of 80% or more when bonded to the adherend surface with a center line average roughness Ra of 0.2 μm to 2 μm only by its own weight. The adhesion rate when the pressure-sensitive adhesive layer is bonded to the surface of the adherend having a center line average roughness Ra of 0.2 μm to 2 μm with only its own weight is 80% or more. When the surface protective film is peeled off from the adherend and then adhered to the adherend again, even if the adherend has a large surface step, the wettability is excellent, and the step following ability is excellent. Therefore, an adherend with a surface protective film capable of achieving a sufficiently high adhesion rate can be provided.

  The pressure-sensitive adhesive layer has an adhesion rate when bonded to the adherend surface only with its own weight with respect to the surface of the adherend having a center line average roughness Ra of 0.2 μm to 2 μm, in that the effect of the present invention can be further expressed. Preferably it is 82% or more, More preferably, it is 84% or more, More preferably, it is 86% or more, Especially preferably, it is 88% or more, Most preferably, it is 90% or more. The upper limit of the adhesion rate is preferably 100%.

  The adhesive layer preferably has an adhesion rate when it is bonded to the surface of the adherend having a center line average roughness Ra of 0.2 μm only by its own weight in that the effect of the present invention can be more manifested. 80% or more, more preferably 85% or more, still more preferably 88% or more, particularly preferably 90% or more, and most preferably 92% or more. The upper limit of the adhesion rate is preferably 100%.

  The pressure-sensitive adhesive layer preferably has an adhesion rate when it is bonded to the adherend surface with a center line average roughness Ra of 0.3 μm only by its own weight in that the effect of the present invention can be more manifested. It is 80% or more, more preferably 83% or more, still more preferably 86% or more, particularly preferably 88% or more, and most preferably 90% or more. The upper limit of the adhesion rate is preferably 100%.

  The pressure-sensitive adhesive layer preferably has an adhesion rate when bonded to the surface of the adherend having a center line average roughness Ra of 0.8 μm only by its own weight, in that the effect of the present invention can be more manifested. 80% or more, more preferably 82% or more, still more preferably 84% or more, particularly preferably 86% or more, and most preferably 88% or more. The upper limit of the adhesion rate is preferably 100%.

  The pressure-sensitive adhesive layer preferably has an adhesion rate when bonded to the adherend surface with a center line average roughness Ra of 1.1 μm only by its own weight, in that the effect of the present invention can be more manifested. 80% or more, more preferably 82% or more, still more preferably 84% or more, particularly preferably 86% or more, and most preferably 87% or more. The upper limit of the adhesion rate is preferably 100%.

  As the thickness of the pressure-sensitive adhesive layer, any appropriate thickness can be adopted depending on the application. The thickness of the pressure-sensitive adhesive layer is preferably 1 μm to 100 μm, more preferably 3 μm to 50 μm, and still more preferably 5 μm to 30 μm, in that the effect of the present invention can be more manifested. By adjusting the thickness of the pressure-sensitive adhesive layer within the above range, the surface of the adherend is removed when the surface protective film is once peeled off from the adherend having a large surface level difference and then adhered to the adherend again. Even when the level difference is large, it is possible to provide an adherend with a surface protective film that can achieve a sufficiently high adhesion rate because it is more excellent in wettability and more excellent in level-step following capability.

  The pressure-sensitive adhesive layer can be produced by any appropriate production method. Examples of such a production method include a method in which a composition that is a material for forming the pressure-sensitive adhesive layer is applied onto the base material layer, and the pressure-sensitive adhesive layer is formed on the base material layer. Examples of such coating methods include roll coating, gravure coating, reverse coating, roll brushing, spray coating, air knife coating, extrusion coating using a die coater, and the like.

  The pressure-sensitive adhesive layer can contain any appropriate other component in addition to the urethane-based pressure-sensitive adhesive as long as the effects of the present invention are not impaired. Examples of such other components include resin components other than polyurethane resins, tackifiers, inorganic fillers, organic fillers, metal powders, pigments, foils, softeners, anti-aging agents, conductive agents, Examples include ultraviolet absorbers, antioxidants, light stabilizers, surface lubricants, leveling agents, corrosion inhibitors, heat stabilizers, polymerization inhibitors, lubricants, solvents, and catalysts.

  The content of the polyurethane-based resin in the urethane-based adhesive is preferably 50% by weight to 100% by weight, more preferably 70% by weight to 100% by weight, and still more preferably 90% by weight to 100% by weight. Particularly preferably 95% to 100% by weight, most preferably 98% to 100% by weight. When the surface protective film is once peeled off from the adherend having a large surface level difference and then adhered to the adherend again by adjusting the content ratio of the polyurethane resin in the urethane-based adhesive within the above range. To provide an adherend with a surface protective film, which is capable of achieving a sufficiently high adhesion rate because it is excellent in wettability even when the surface step of the adherend is large, and further in step followability. Can do.

  The urethane-based pressure-sensitive adhesive can contain any appropriate other component in addition to the polyurethane-based resin as long as the effects of the present invention are not impaired. Examples of such other components include resin components other than polyurethane resins, tackifiers, inorganic fillers, organic fillers, metal powders, pigments, foils, softeners, anti-aging agents, conductive agents, Examples include ultraviolet absorbers, antioxidants, light stabilizers, surface lubricants, leveling agents, corrosion inhibitors, heat stabilizers, polymerization inhibitors, lubricants, solvents, and catalysts.

  The urethane-based pressure-sensitive adhesive may contain a fatty acid ester. Only one type of fatty acid ester may be used, or two or more types may be used.

  The number average molecular weight Mn of the fatty acid ester is preferably 200 to 400, more preferably 210 to 395, still more preferably 230 to 380, particularly preferably 240 to 360, most preferably 250 to 350. It is. By adjusting the number average molecular weight Mn of the fatty acid ester within the above range, the wetting rate can be further improved. If the number average molecular weight Mn of the fatty acid ester is too small, the wetting rate may not be improved even if the number of added parts is large. If the number average molecular weight Mn of the fatty acid ester is too large, the curability of the pressure-sensitive adhesive at the time of drying deteriorates, and there is a possibility that it may not only affect the wettability but also adversely affect other adhesive properties.

  As the fatty acid ester, any appropriate fatty acid ester can be adopted as long as the effects of the present invention are not impaired. Examples of such fatty acid esters include polyoxyethylene bisphenol A lauric acid ester, butyl stearate, 2-ethylhexyl palmitate, 2-ethylhexyl stearate, monoglyceride behenate, cetyl 2-ethylhexanoate, myristic acid Isopropyl, isopropyl palmitate, cholesteryl isostearate, lauryl methacrylate, coconut fatty acid methyl, methyl laurate, methyl oleate, methyl stearate, myristyl myristate, octyldodecyl myristate, pentaerythritol monooleate, pentaerythritol monostearate , Pentaerythritol tetrapalmitate, stearyl stearate, isotridecyl stearate, triglycera 2-ethylhexanoate De, butyl laurate, and the like octyl oleate.

  The blending ratio of the fatty acid ester when preparing the urethane-based pressure-sensitive adhesive is, for example, preferably 5% to 50% by weight, and more preferably 7% to 45% by weight with respect to the polyol (A). More preferably 8 to 40% by weight, particularly preferably 9 to 35% by weight, most preferably 10 to 30% by weight.

  The urethane-based pressure-sensitive adhesive may contain an ionic liquid containing a fluoro organic anion. When the urethane-based pressure-sensitive adhesive contains an ionic liquid containing a fluoro organic anion, a urethane-based pressure-sensitive adhesive having excellent antistatic properties can be provided. Only one kind of ionic liquid may be used, or two or more kinds may be used.

  In the present invention, the ionic liquid means a molten salt (ionic compound) that is liquid at 25 ° C.

  As the ionic liquid, any appropriate ionic liquid can be adopted as long as it does not impair the effects of the present invention as long as it is an ionic liquid containing a fluoro organic anion. Such an ionic liquid is preferably an ionic liquid composed of a fluoroorganic anion and an onium cation. By adopting an ionic liquid composed of a fluoro organic anion and an onium cation as the ionic liquid, it is possible to provide a urethane-based pressure-sensitive adhesive having extremely excellent antistatic properties.

  Any appropriate onium cation can be adopted as the onium cation capable of constituting the ionic liquid as long as the effects of the present invention are not impaired. Such an onium cation is preferably at least one selected from a nitrogen-containing onium cation, a sulfur-containing onium cation, and a phosphorus-containing onium cation. By selecting these onium cations, it is possible to provide a urethane-based pressure-sensitive adhesive having extremely excellent antistatic properties.

The onium cation capable of constituting the ionic liquid is preferably at least one selected from cations having a structure represented by the general formulas (1) to (5).

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

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

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

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

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

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

  Specific examples of the cation represented by the general formula (1) include, for example, 1-ethylpyridinium cation, 1-butylpyridinium cation, 1-hexylpyridinium cation, 1-ethyl-3-methylpyridinium cation, and 1-butyl. -3-methylpyridinium cation, 1-hexyl-3-methylpyridinium cation, 1-butyl-4-methylpyridinium cation, 1-octyl-4-methylpyridinium cation, 1-butyl-3,4-dimethylpyridinium cation, Pyridinium cations such as 1,1-dimethylpyrrolidinium cation; 1-ethyl-1-methylpyrrolidinium cation, 1-methyl-1-propylpyrrolidinium cation, 1-methyl-1-butylpyrrolidinium cation, 1-methyl-1-pentylpyrrolidini 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, Pyrrolidinium cations such as 1-propyl-1-butylpyrrolidinium cation and 1,1-dibutylpyrrolidinium cation; 1-propylpiperidinium cation, 1-pentylpiperidinium cation, 1-methyl-1- Ethyl piperidinium cation, 1-methyl-1-propyl piperidinium 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-dibutylpi Piperidinium cations such as peridinium cations; 2-methyl-1-pyrroline cations; Til-2-phenylindole cation; 1,2-dimethylindole cation; 1-ethylcarbazole cation;

  Among these, 1-ethylpyridinium cation, 1-butylpyridinium cation, 1-hexylpyridinium cation, 1-ethyl-3-methylpyridinium cation, and 1 are preferable because the effects of the present invention can be further exhibited. -Pyridinium cations such as butyl-3-methylpyridinium cation, 1-hexyl-3-methylpyridinium cation, 1-butyl-4-methylpyridinium cation, 1-octyl-4-methylpyridinium cation; 1-ethyl-1- Methylpyrrolidinium cation, 1-methyl-1-propylpyrrolidinium cation, 1-methyl-1-butylpyrrolidinium cation, 1-methyl-1-pentylpyrrolidinium cation, 1-methyl-1-hexyl Pyrrolidinium cation, 1-methyl-1-he Tylpyrrolidinium cation, 1-ethyl-1-propylpyrrolidinium cation, 1-ethyl-1-butylpyrrolidinium cation, 1-ethyl-1-pentylpyrrolidinium cation, 1-ethyl-1-hexyl Pyrrolidinium cations such as pyrrolidinium cation and 1-ethyl-1-heptylpyrrolidinium cation; 1-methyl-1-ethylpiperidinium cation, 1-methyl-1-propylpiperidinium cation, 1- Methyl-1-butylpiperidinium cation, 1-methyl-1-pentylpiperidinium cation, 1-methyl-1-hexylpiperidinium cation, 1-methyl-1-heptylpiperidinium cation, 1-ethyl -1-propylpiperidinium cation, 1-ethyl-1-butylpiperidinium cut 1-ethyl-1-pentylpiperidinium cation, 1-ethyl-1-hexylpiperidinium cation, 1-ethyl-1-heptylpiperidinium cation, 1-propyl-1-butylpiperidinium cation And more preferably, 1-hexylpyridinium cation, 1-ethyl-3-methylpyridinium cation, 1-butyl-3-methylpyridinium cation, 1-octyl-4-methyl, and the like. Pyridinium cation, 1-methyl-1-propylpyrrolidinium cation, and 1-methyl-1-propylpiperidinium cation.

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

  Specific examples of the cation represented by the general formula (2) include, for example, 1,3-dimethylimidazolium cation, 1,3-diethylimidazolium cation, 1-ethyl-3-methylimidazolium cation, and 1-butyl. -3-methylimidazolium cation, 1-hexyl-3-methylimidazolium cation, 1-octyl-3-methylimidazolium cation, 1-decyl-3-methylimidazolium cation, 1-dodecyl-3-methylimidazole 1-tetradecyl-3-methylimidazolium cation, 1,2-dimethyl-3-propylimidazolium cation, 1-ethyl-2,3-dimethylimidazolium cation, 1-butyl-2,3-dimethylimidazole Lilium cation, 1-hexyl-2,3-dimethylimidazo Imidazolium cations such as um cation; 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, etc. Tetrahydropyrimidinium cation; 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 dihydropyrimidinium cation, such as cations; and the like.

  Among these, from the viewpoint that the effects of the present invention can be further exhibited, 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- Imidazolium cations such as methylimidazolium cation and 1-tetradecyl-3-methylimidazolium cation, more preferably 1-ethyl-3-methylimidazolium cation and 1-hexyl-3-methylimidazolium cation is there.

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

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

  Examples of the cation represented by the general formula (4) include, for example, a tetraalkylammonium cation, a trialkylsulfonium cation, a tetraalkylphosphonium cation, and a part of the alkyl group substituted with an alkenyl group, an alkoxyl group, or an epoxy group. And the like.

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

  Among these, the triethylmethyl ammonium cation, tributyl ethyl ammonium cation, trimethyl decyl ammonium cation, diethyl methyl sulfonium cation, dibutyl ethyl sulfonium cation, dimethyl decyl sulfonium cation, Asymmetric tetraalkylammonium cations such as triethylmethylphosphonium cation, tributylethylphosphonium cation, trimethyldecylphosphonium cation, trialkylsulfonium cation, tetraalkylphosphonium cation, N, N-diethyl-N-methyl-N- (2-methoxy) Ethyl) ammonium cation, glycidyltrimethylammonium cation, diallyldimethylammoni 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- -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, more preferably trimethylpropylammonium cation.

  Any appropriate fluoroorganic anion can be adopted as the fluoroorganic anion capable of constituting the ionic liquid as long as the effects of the present invention are not impaired. Such a fluoroorganic anion may be completely fluorinated (perfluorinated) or partially fluorinated.

  Examples of such fluoroorganic anions include fluorinated aryl sulfonates, perfluoroalkane sulfonates, bis (fluorosulfonyl) imides, bis (perfluoroalkanesulfonyl) imides, cyanoperfluoroalkanesulfonylamides, and bis (cyano). Perfluoroalkanesulfonylmethide, cyano-bis- (perfluoroalkanesulfonyl) methide, tris (perfluoroalkanesulfonyl) methide, trifluoroacetate, perfluoroalchelate, tris (perfluoroalkanesulfonyl) methide, (perfluoroalkane) Sulfonyl) trifluoroacetamide and the like.

  Among these fluoro organic anions, more preferred are perfluoroalkylsulfonate, bis (fluorosulfonyl) imide, bis (perfluoroalkanesulfonyl) imide, and more specifically, for example, trifluoromethanesulfonate, pentafluoroethane. Sulfonate, heptafluoropropane sulfonate, nonafluorobutane sulfonate, bis (fluorosulfonyl) imide, bis (trifluoromethanesulfonyl) imide.

Specific examples of the ionic liquid may be appropriately selected from a combination of the cation component and the anion component. Specific examples of such ionic liquids include, for example, 1-hexylpyridinium bis (fluorosulfonyl) imide, 1-ethyl-3-methylpyridinium trifluoromethanesulfonate, 1-ethyl-3-methylpyridinium pentafluoroethanesulfonate, 1-ethyl-3-methylpyridinium heptafluoropropane sulfonate, 1-ethyl-3-methylpyridinium nonafluorobutane sulfonate, 1-butyl-3-methylpyridinium trifluoromethanesulfonate, 1-butyl-3-methylpyridinium bis (trifluoromethane Sulfonyl) imide, 1-butyl-3-methylpyridinium bis (pentafluoroethanesulfonyl) imide, 1-octyl-4-methylpyridinium bis (fluorosulfonyl) imi 1,1-dimethylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-ethylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-propylpyrrolidinium bis (trifluoromethanesulfonyl) ) Imide, 1-methyl-1-propylpyrrolidinium bis (fluorosulfonyl) imide, 1-methyl-1-butylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-pentylpyrrolidinium bis ( Trifluoromethanesulfonyl) imide, 1-methyl-1-hexylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-heptylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-ethyl-1- Propyl pyro Dinium bis (trifluoromethanesulfonyl) imide, 1-ethyl-1-butylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-ethyl-1-pentylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-ethyl-1- Hexylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-ethyl-1-heptylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1,1-dipropylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1 -Propyl-1-butylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1,1-dibutylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-propylpiperidinium bis (trifluoromethanesulfonyl) Nyl) imide, 1-pentylpiperidinium bis (trifluoromethanesulfonyl) imide, 1,1-dimethylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-ethylpiperidinium bis (trifluoromethanesulfonyl) Imido, 1-methyl-1-propylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-propylpiperidinium bis (fluorosulfonyl) imide, 1-methyl-1-butylpiperidinium bis (trifluoro) Romethanesulfonyl) imide, 1-methyl-1-pentylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-hexylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-heptylpiperi Dinium bis (trifluoromethanesulfonyl) imide, 1-ethyl-1-propylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-ethyl-1-butylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-ethyl-1- Pentylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-ethyl-1-hexylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-ethyl-1-heptylpiperidinium bis (trifluoromethanesulfonyl) imide, 1,1-dipropylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-propyl-1-butylpiperidinium bis (trifluoromethanesulfonyl) imide, 1,1-dibutylpiperidinium bis (trifluoro Tansulfonyl) imide, 1,1-dimethylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-ethylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-propylpyrrolidi Nitrobis (pentafluoroethanesulfonyl) imide, 1-methyl-1-butylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-pentylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1- Methyl-1-hexylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-heptylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-propylpyrrolidinium bis ( Pentafluoroethane Sulfonyl) imide, 1-ethyl-1-butylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-pentylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-hexyl Pyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-heptylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1,1-dipropylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-propyl-1-butylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1,1-dibutylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-propylpiperidinium bis (pentafluoroethanesulfonyl) imide , 1- Pentylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1,1-dimethylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-ethylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1 -Methyl-1-propylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-butylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-pentylpiperidinium bis (penta Fluoroethanesulfonyl) imide, 1-methyl-1-hexylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-heptylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl- 1-propi Piperidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-butylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-pentylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-hexylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-heptylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1,1-dipropylpiperidinium bis (Pentafluoroethanesulfonyl) imide, 1-propyl-1-butylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1,1-dibutylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-3- Methyl imidazoli Mutrifluoroacetate, 1-ethyl-3-methylimidazolium heptafluorobutyrate, 1-ethyl-3-methylimidazolium trifluoromethanesulfonate, 1-ethyl-3-methylimidazolium heptafluoropropanesulfonate, 1-ethyl-3 -Methylimidazolium nonafluorobutanesulfonate, 1-ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide, 1-ethyl-3-methylimidazolium bis (fluorosulfonyl) imide, 1-ethyl-3-methylimidazole Bis (pentafluoroethanesulfonyl) imide, 1-ethyl-3-methylimidazolium tris (trifluoromethanesulfonyl) methide, 1-butyl-3-methylimidazolium trifluoroacetate 1-butyl-3-methylimidazolium heptafluorobutyrate, 1-butyl-3-methylimidazolium trifluoromethanesulfonate, 1-butyl-3-methylimidazolium perfluorobutanesulfonate, 1-butyl-3-methyl Imidazolium bis (trifluoromethanesulfonyl) imide, 1-hexyl-3-methylimidazolium trifluoromethanesulfonate, 1-hexyl-3-methylimidazolium bis (fluorosulfonyl) imide, 1,2-dimethyl-3-propylimidazo Rium bis (trifluoromethanesulfonyl) imide, 1-ethyl-2,3,5-trimethylpyrazolium bis (trifluoromethanesulfonyl) imide, 1-propyl-2,3,5-trimethylpyrazolium bis (trifluoro) Methanesulfonyl) imide, 1-butyl-2,3,5-trimethylpyrazolium bis (trifluoromethanesulfonyl) imide, 1-ethyl-2,3,5-trimethylpyrazolium bis (pentafluoroethanesulfonyl) imide, 1-propyl-2,3,5-trimethylpyrazolium bis (pentafluoroethanesulfonyl) imide, 1-butyl-2,3,5-trimethylpyrazolium bis (pentafluoroethanesulfonyl) imide, 1-ethyl- 2,3,5-trimethylpyrazolium (trifluoromethanesulfonyl) trifluoroacetamide, 1-propyl-2,3,5-trimethylpyrazolium (trifluoromethanesulfonyl) trifluoroacetamide, 1-butyl-2,3 5-trimethylpyrazolium (trifluoro Tansulfonyl) trifluoroacetamide, trimethylpropylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-ethyl-N-propylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-ethyl- N-butylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-ethyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-ethyl-N-hexylammonium bis ( Trifluoromethanesulfonyl) imide, N, N-dimethyl-N-ethyl-N-heptylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-ethyl-N-nonylammonium bis (tri Fluoromethanesulfonyl) imide, N, N-dimethyl-N, N-dipropylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-propyl-N-butylammonium bis (trifluoromethanesulfonyl) imide, N , N-dimethyl-N-propyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-propyl-N-hexylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N -Propyl-N-heptylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-butyl-N-hexylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-butyl-N-heptyla Monium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-pentyl-N-hexylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N, N-dihexylammonium bis (trifluoromethanesulfonyl) imide, Trimethylheptylammonium bis (trifluoromethanesulfonyl) imide, N, N-diethyl-N-methyl-N-propylammonium bis (trifluoromethanesulfonyl) imide, N, N-diethyl-N-methyl-N-pentylammonium bis (trifluoro) Romethanesulfonyl) imide, N, N-diethyl-N-methyl-N, N-heptylammonium bis (trifluoromethanesulfonyl) imide, N, N-diethyl-N-propyl-N-pentylan Ni-bis (trifluoromethanesulfonyl) imide, triethylpropylammonium bis (trifluoromethanesulfonyl) imide, triethylpentylammonium bis (trifluoromethanesulfonyl) imide, triethylheptylammonium bis (trifluoromethanesulfonyl) imide, N, N-dipropyl-N-methyl -N-ethylammonium bis (trifluoromethanesulfonyl) imide, N, N-dipropyl-N-methyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, N, N-dipropyl-N-butyl-N-hexylammonium bis (Trifluoromethanesulfonyl) imide, N, N-dipropyl-N, N-dihexylammonium bis (trifluoromethanesulfonyl) imide, N , N-dibutyl-N-methyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, N, N-dibutyl-N-methyl-N-hexylammonium bis (trifluoromethanesulfonyl) imide, trioctylmethylammonium bis ( Trifluoromethanesulfonyl) imide, N-methyl-N-ethyl-N-propyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, 1-butylpyridinium (trifluoromethanesulfonyl) trifluoroacetamide, 1-butyl-3-methyl Pyridinium (trifluoromethanesulfonyl) trifluoroacetamide, 1-ethyl-3-methylimidazolium (trifluoromethanesulfonyl) trifluoroacetamide, tetrahexylammonium (Trifluoromethanesulfonyl) imide, diallyldimethylammonium trifluoromethanesulfonate, diallyldimethylammonium bis (trifluoromethanesulfonyl) imide, diallyldimethylammonium bis (pentafluoroethanesulfonyl) imide, N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium trifluoromethanesulfonate, N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium bis (trifluoromethanesulfonyl) imide, N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium bis (pentafluoroethanesulfonyl) imide, glycidyltrimethylammonium trifluoromethanesulfonate, glycidyltrimethylammonium Umbis (trifluoromethanesulfonyl) imide, glycidyltrimethylammonium bis (pentafluoroethanesulfonyl) imide, diallyldimethylammonium bis (trifluoromethanesulfonyl) imide, diallyldimethylbis (pentafluoroethanetanesulfonyl) imide, lithium bis (trifluoromethanesulfonyl) Examples thereof include imide and lithium bis (fluorosulfonyl) imide.

  Among these ionic liquids, 1-hexylpyridinium bis (fluorosulfonyl) imide, 1-ethyl-3-methylpyridinium trifluoromethanesulfonate, 1-ethyl-3-methylpyridinium pentafluoroethanesulfonate, Ethyl-3-methylpyridinium heptafluoropropanesulfonate, 1-ethyl-3-methylpyridinium nonafluorobutanesulfonate, 1-butyl-3-methylpyridinium trifluoromethanesulfonate, 1-butyl-3-methylpyridinium bis (trifluoromethanesulfonyl) Imido, 1-octyl-4-methylpyridinium bis (fluorosulfonyl) imide, 1-methyl-1-propylpyrrolidinium bis (trifluoromethanesulfonyl) imi 1-methyl-1-propylpyrrolidinium bis (fluorosulfonyl) imide, 1-methyl-1-propylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-propylpiperidinium bis (fluorosulfonyl) ) Imido, 1-ethyl-3-methylimidazolium trifluoromethanesulfonate, 1-ethyl-3-methylimidazolium heptafluoropropanesulfonate, 1-ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide, 1-ethyl -3-methylimidazolium bis (fluorosulfonyl) imide, 1-hexyl-3-methylimidazolium bis (fluorosulfonyl) imide, trimethylpropylammonium bis (trifluoromethanesulfonyl) imide, Chiumubisu (trifluoromethanesulfonyl) imide, lithium bis (fluorosulfonyl) imide.

  A commercially available ionic liquid may be used, but it can also be synthesized as follows. The method of synthesizing the ionic liquid is not particularly limited as long as the target ionic liquid can be obtained. In general, the document “ionic liquids—the forefront and future of development” (CMC Publishing Co., Ltd.). The halide method, the hydroxide method, the acid ester method, the complex formation method, the neutralization method, and the like are used.

  The synthesis method for the halide method, hydroxide method, acid ester method, complex formation method, and neutralization method will be described below using nitrogen-containing onium salts as examples. Other sulfur-containing onium salts and phosphorus-containing onium salts Other ionic liquids can be obtained by the same method.

  The halide method is a method performed by reactions as shown in reaction formulas (1) to (3). First, a tertiary amine and an alkyl halide are reacted to obtain a halide (reaction formula (1), and chlorine, bromine, and iodine are used as the halogen).

Acid (HA) or salt having the anionic structure (A ⁻ ) of the ionic liquid intended for the obtained halide (MA and M are cations that form a salt with the intended anion such as ammonium, lithium, sodium, potassium, etc.) ) To obtain the desired ionic liquid (R ₄ NA).

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

The target ionic liquid (R ₄ NA) can be obtained by using the reaction of the reaction formulas (7) to (8) in the same manner as the halogenation method for the obtained hydroxide.

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

The target ionic liquid (R ₄ NA) can be obtained by using the reaction of the reaction formulas (10) to (11) in the same manner as the halogenation method for the obtained acid ester. Further, by using methyl trifluoromethanesulfonate, methyl trifluoroacetate or the like as the acid ester, an ionic liquid can be directly obtained.

The neutralization method is a method performed by a reaction as shown in the reaction formula (12). A tertiary amine is reacted with an organic acid such as CF ₃ COOH, CF ₃ SO ₃ H, (CF ₃ SO ₂ ) ₂ NH, (CF ₃ SO ₂ ) ₃ CH, and (C ₂ F ₅ SO ₂ ) ₂ NH. Can be obtained.

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

  The blending amount of the ionic liquid varies depending on the compatibility of the polymer to be used and the ionic liquid, and thus cannot be defined unconditionally. However, in general, the amount is preferably 0.1% with respect to 100 parts by weight of the polyurethane resin. 001 to 50 parts by weight, more preferably 0.01 to 40 parts by weight, still more preferably 0.01 to 30 parts by weight, and particularly preferably 0.01 to 20 parts by weight. Parts by weight, most preferably 0.01 parts by weight to 10 parts by weight. By adjusting the blending amount of the ionic liquid within the above range, it is possible to provide a urethane-based pressure-sensitive adhesive having excellent antistatic properties. If the amount of the ionic liquid is less than 0.01 parts by weight, sufficient antistatic properties may not be obtained. When the amount of the ionic liquid exceeds 50 parts by weight, contamination of the adherend tends to increase.

  The urethane-based pressure-sensitive adhesive may contain a modified silicone oil. By including the modified silicone oil in the urethane pressure-sensitive adhesive, the effects of the present invention can be expressed more effectively.

  When the urethane pressure-sensitive adhesive contains a modified silicone oil, the content ratio is preferably 0.001 to 50 parts by weight, more preferably 0.01 parts by weight to 100 parts by weight of the polyurethane resin. 40 parts by weight, more preferably 0.01 to 30 parts by weight, particularly preferably 0.01 to 20 parts by weight, and most preferably 0.01 to 10 parts by weight. . By adjusting the content ratio of the modified silicone oil within the above range, the effects of the present invention can be expressed more effectively.

  Any appropriate modified silicone oil can be adopted as the modified silicone oil as long as the effects of the present invention are not impaired. Examples of such modified silicone oil include modified silicone oil available from Shin-Etsu Chemical Co., Ltd.

  The modified silicone oil is preferably a polyether-modified silicone oil. By employing the polyether-modified silicone oil, the effects of the present invention can be expressed more effectively.

  Examples of the polyether-modified silicone oil include a side chain-type polyether-modified silicone oil and a both-end-type polyether-modified silicone oil. Among these, a polyether-modified silicone oil of both terminal types is preferable in that the effect of the present invention can be expressed sufficiently more effectively.

  Any appropriate polyurethane resin can be adopted as the polyurethane resin as long as the effects of the present invention are not impaired. The polyurethane resin is preferably a polyurethane resin obtained from a composition containing the polyol (A) and the polyfunctional isocyanate compound (B), or a urethane prepolymer (C) and a polyfunctional isocyanate compound (B). It is a polyurethane-type resin obtained from the composition to contain. By adopting the above as a polyurethane-based resin, when the surface protective film is once peeled off from the adherend having a large surface level difference and then adhered to the adherend again, the surface of the adherend Even when the level difference is large, it is possible to provide an adherend with a surface protective film that can achieve a sufficiently high adhesion rate because it is more excellent in wettability and more excellent in level-step following capability.

  The polyurethane-based resin can contain any appropriate other component as long as the effects of the present invention are not impaired. Examples of such other components include resin components other than polyurethane resins, tackifiers, inorganic fillers, organic fillers, metal powders, pigments, foils, softeners, anti-aging agents, conductive agents, Examples include ultraviolet absorbers, antioxidants, light stabilizers, surface lubricants, leveling agents, corrosion inhibitors, heat stabilizers, polymerization inhibitors, lubricants, solvents, and catalysts.

  The polyurethane-based resin preferably contains a deterioration inhibitor such as an antioxidant, an ultraviolet absorber, and a light stabilizer. When the polyurethane-based resin contains a deterioration preventing agent, the adhesive residue can be prevented from remaining on the adherend, for example, even when the polyurethane resin is attached to the adherend and stored in a heated state, and thus the adhesive residue hardly occurs on the adherend. Therefore, in the surface protective film of the present invention, contamination of the adherend can be reduced. Only one type of deterioration preventing agent may be used, or two or more types may be used. As the deterioration preventing agent, an antioxidant is particularly preferable.

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

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

  Examples of the peroxide decomposer include a sulfur-based antioxidant and a phosphorus-based antioxidant.

  Examples of phenolic antioxidants include monophenolic antioxidants, bisphenolic antioxidants, and high-molecular phenolic antioxidants.

  Examples of the monophenol antioxidant include 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-4-ethylphenol, stearin-β- ( 3,5-di-t-butyl-4-hydroxyphenyl) propionate and the like.

  Examples of the bisphenol antioxidant include 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-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl] 2,4,8,10-tetraoxaspiro [5,5] undecane.

  Examples of the polymeric phenolic antioxidant include 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl-2,4, 6-Tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, tetrakis- [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane Bis [3,3′-bis- (4′-hydroxy-3′-t-butylphenyl) butyric acid] glycol ester, 1,3,5-tris (3 ′, 5′-di-t-butyl) -4′-hydroxybenzyl) -S-triazine-2,4,6- (1H, 3H, 5H) trione, tocophenol and the like.

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

  Examples of phosphorus antioxidants include triphenyl phosphite, diphenylisodecyl phosphite, and phenyl diisodecyl phosphite.

  Examples of UV absorbers include benzophenone UV absorbers, benzotriazole UV absorbers, salicylic acid UV absorbers, oxalic anilide UV absorbers, cyanoacrylate UV absorbers, and triazine UV absorbers. It is done.

  Examples of the benzophenone ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 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.

  Examples of the benzotriazole ultraviolet absorber include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-5′-tert-butylphenyl) benzotriazole, 2- ( 2'-hydroxy-3 ', 5'-di-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2 -(2'-hydroxy-3 ', 5'-di-tert-butylphenyl) 5-chlorobenzotriazole, 2- (2'-hydroxy-3', 5'-di-tert-amylphenyl) benzotriazole, 2- (2′-hydroxy-4′-octoxyphenyl) benzotriazole, 2- [2′-hydroxy-3 ′-(3 ', 4' ', 5' ', 6' ',-tetrahydrophthalimidomethyl) -5'-methylphenyl] benzotriazole, 2,2'methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol], [2 (2′-hydroxy-5′-methacryloxyphenyl) -2H-benzotriazole, and the like.

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

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

  Examples of the light stabilizer include hindered amine light stabilizers and ultraviolet light stabilizers.

  Examples of the hindered amine light stabilizer include [bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate], bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate. Methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacate and the like.

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

<Polyurethane resin obtained from composition containing polyol (A) and polyfunctional isocyanate compound (B)>
Specifically, the polyurethane resin obtained from the composition containing the polyol (A) and the polyfunctional isocyanate compound (B) is preferably a composition containing the polyol (A) and the polyfunctional isocyanate compound (B). Is a polyurethane-based resin obtained by curing.

  The polyol (A) may be one kind or two or more kinds.

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

  Examples of the polyol (A) preferably include polyester polyol, polyether polyol, polycaprolactone polyol, polycarbonate polyol, and castor oil-based polyol. The polyol (A) is more preferably a polyether polyol.

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

  Examples of the polyol component include ethylene glycol, diethylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, and 2-butyl-2-ethyl-1. , 3-propanediol, 2,4-diethyl-1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 2-methyl Examples include -1,8-octanediol, 1,8-decanediol, octadecanediol, glycerin, trimethylolpropane, pentaerythritol, hexanetriol, and polypropylene glycol. Examples of the acid component include succinic acid, methyl succinic 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 , And these acid anhydrides.

  Examples of polyether polyols include water, low molecular weight polyols (propylene glycol, ethylene glycol, glycerin, trimethylolpropane, pentaerythritol, etc.), bisphenols (bisphenol A, etc.), dihydroxybenzenes (catechol, resorcin, hydroquinone, etc.), etc. And polyether polyols obtained by addition polymerization of alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide. Specific examples include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and the like.

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

  Examples of the polycarbonate polyol include a polycarbonate polyol obtained by polycondensation reaction of the polyol component and phosgene; the polyol component, dimethyl carbonate, diethyl carbonate, diprovir carbonate, diisopropyl carbonate, dibutyl carbonate, ethyl butyl carbonate, ethylene carbonate, Polycarbonate polyol obtained by ester exchange condensation with carbonic acid diesters such as propylene carbonate, diphenyl carbonate and dibenzyl carbonate; copolymerized polycarbonate polyol obtained by using two or more of the above polyol components in combination; Polycarbonate polyol obtained by esterification reaction with a compound; the above-mentioned various polycarbonate polyols and a hydroxyl group-containing compound A polycarbonate polyol obtained by a reaction of tellurization; a polycarbonate polyol obtained by a transesterification reaction between the above various polycarbonate polyols and an ester compound; a polycarbonate polyol obtained by a transesterification reaction between the various polycarbonate polyols and a hydroxyl group-containing compound; And polyester polycarbonate polyols obtained by polycondensation reaction of the various polycarbonate polyols with dicarboxylic acid compounds; copolymer polyether polycarbonate polyols obtained by copolymerizing the various polycarbonate polyols and alkylene oxides;

  An example of the castor oil-based polyol is a castor oil-based polyol obtained by reacting a castor oil fatty acid with the polyol component. Specific examples include castor oil-based polyols obtained by reacting castor oil fatty acid with polypropylene glycol.

  The number average molecular weight Mn of the polyol (A) is preferably 400 to 20000, more preferably 500 to 17000, still more preferably 600 to 15000, and particularly preferably 800 to 12000. By adjusting the number average molecular weight Mn of the polyol (A) within the above range, the surface protective film is once peeled off from the adherend having a large surface step, and is again attached to the adherend. Even if the surface level difference of the adherend is large, it is possible to provide an adherend with a surface protective film which is excellent in wettability and further excellent in level-step following property and can achieve a sufficiently high adhesion rate.

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

  The content ratio of the polyol (A1) in the polyol (A) is preferably 70% by weight or more, more preferably 70% by weight to 100% by weight, and further preferably 70% by weight to 90% by weight. When adjusting the content ratio of the polyol (A1) in the polyol (A) within the above range, the surface protective film is once peeled off from the adherend having a large surface level difference, and then adhered to the adherend again. Furthermore, even when the surface level difference of the adherend is large, it is possible to provide an adherend with a surface protective film that can achieve a sufficiently high adhesion rate because it is superior in wettability and further in step followability. be able to.

  The number average molecular weight Mn of the polyol (A1) is preferably 8000 to 20000, more preferably 8000 to 18000, further preferably 8500 to 17000, further preferably 9000 to 16000, and particularly preferably 9500. -15500, most preferably 10000-15000. By adjusting the number average molecular weight Mn of the polyol (A1) within the above range, the surface protective film is once peeled off from the adherend having a large surface level difference and then adhered to the adherend again. Even if the surface level difference of the adherend is large, it is possible to provide an adherend with a surface protective film which is excellent in wettability and further excellent in level-step following property and can achieve a sufficiently high adhesion rate.

  The polyol (A) may contain a polyol (A2) having 3 or more OH groups and a number average molecular weight Mn of 5000 or less. The polyol (A2) may be only one kind or two or more kinds. The number average molecular weight Mn of the polyol (A2) is preferably 500 to 5000, more preferably 800 to 4500, still more preferably 1000 to 4000, particularly preferably 1000 to 3500, and most preferably 1000. ~ 3000. When the number average molecular weight Mn of the polyol (A2) is out of the above range, the adhesive strength may increase with time, and excellent reworkability may not be exhibited. The polyol (A2) is preferably a polyol (triol) having 3 OH groups, a polyol (tetraol) having 4 OH groups, a polyol (pentaol) having 5 OH groups, and 6 OH groups. The polyol (hexaol) which has is mentioned.

  As the polyol (A2), a total amount of at least one of a polyol having 4 OH groups (tetraol), a polyol having 5 OH groups (pentaol), and a polyol having 6 OH groups (hexaol) is: The content ratio in the polyol (A) is preferably 10% by weight or less, more preferably 7% by weight or less, still more preferably 6% by weight or less, and particularly preferably 5% by weight or less. In the polyol (A), as the polyol (A2), at least of a polyol having 4 OH groups (tetraol), a polyol having 5 OH groups (pentaol), and a polyol having 6 OH groups (hexaol) By adjusting 1 type to the said range, the urethane type adhesive which was further excellent in transparency can be provided.

  The content ratio of the polyol (A2) in the polyol (A) is preferably 30% by weight or less, more preferably 0% by weight to 30% by weight. When adjusting the content ratio of the polyol (A2) in the polyol (A) within the above range, the surface protective film is once peeled off from the adherend having a large surface level difference, and then adhered to the adherend again. Furthermore, even when the surface level difference of the adherend is large, it is possible to provide an adherend with a surface protective film that can achieve a sufficiently high adhesion rate because it is superior in wettability and further in step followability. be able to.

  In the polyol (A2), the content ratio of the polyol having a number average molecular weight Mn of 5,000 or less having 4 or more OH groups therein is preferably less than 10% by weight, more preferably based on the whole polyol (A). Is 8% by weight or less, more preferably 7% by weight or less, particularly preferably 6% by weight or less, and most preferably 5% by weight or less. When the content ratio of the polyol having a number average molecular weight Mn of 5000 or less and having 4 or more OH groups in the polyol (A2) is 10% by weight or more with respect to the whole polyol (A), the urethane-based pressure-sensitive adhesive is white. There is a risk that transparency will be reduced.

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

  As the polyfunctional isocyanate compound (B), any appropriate polyfunctional isocyanate compound that can be used in the urethanization reaction can be adopted. Examples of such a polyfunctional isocyanate compound (B) include polyfunctional aliphatic isocyanate compounds, polyfunctional alicyclic isocyanate compounds, polyfunctional aromatic isocyanate compounds, and the like.

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

  Examples of the polyfunctional alicyclic isocyanate compound include 1,3-cyclopentene diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, Examples include hydrogenated tolylene diisocyanate and hydrogenated tetramethylxylylene diisocyanate.

  Examples of the polyfunctional aromatic diisocyanate compound include phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,2′-didiphenylmethane diisocyanate, 4,4′-diphenylmethane diisocyanate, 4 4,4'-toluidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, xylylene diisocyanate and the like.

  Examples of the polyfunctional isocyanate compound (B) include trimethylolpropane adducts of various polyfunctional isocyanate compounds as described above, burettes reacted with water, and trimers having an isocyanurate ring. These may be used in combination.

  In the polyol (A) and the polyfunctional isocyanate compound (B), the equivalent ratio of the NCO group to the OH group is preferably 0.3 to 1.0, more preferably 0.3 to NCO group / OH group. 0.9, more preferably 0.3 to 0.8, particularly preferably 0.3 to 0.7, and most preferably 0.3 to 0.6. When the NCO group / OH group equivalent ratio is adjusted within the above range, the surface protective film is once peeled off from the adherend having a large surface level difference, and then adhered to the adherend again. Even when the surface level difference of the body is large, it is possible to provide an adherend with a surface protective film which is excellent in wettability and further excellent in level-step following property and can achieve a sufficiently high adhesion rate.

  The content ratio of the polyfunctional isocyanate compound (B) is preferably from 2.7% by weight to 8.8% by weight of the polyfunctional isocyanate compound (B) with respect to the polyol (A), more preferably 2. 7 wt% to 8.0 wt%, more preferably 2.7 wt% to 7.1 wt%, particularly preferably 2.7 wt% to 6.2 wt%, and most preferably 2 wt%. 0.7 wt% to 5.3 wt%. When the content ratio of the polyfunctional isocyanate compound (B) is adjusted within the above range, the surface protective film is once peeled off from the adherend having a large surface step, and is again attached to the adherend. Even when the surface level difference of the adherend is large, it is possible to provide an adherend with a surface protective film that can achieve a sufficiently high adhesion rate because it is superior in wettability and further in step followability. .

  Specifically, the polyurethane-based resin is preferably obtained by curing a composition containing the polyol (A) and the polyfunctional isocyanate compound (B).

  As a method for obtaining a polyurethane resin by curing a composition containing a polyol (A) and a polyfunctional isocyanate compound (B), the effects of the present invention, such as a urethanization reaction method using bulk polymerization or solution polymerization, are used. Any appropriate method can be adopted as long as it is not impaired.

  In order to cure the composition containing the polyol (A) and the polyfunctional isocyanate compound (B), a catalyst is preferably used. Examples of such a catalyst include organometallic compounds and tertiary amine compounds.

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

  Examples of iron-based compounds include iron acetylacetonate and iron 2-ethylhexanoate.

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

  Examples of titanium compounds include dibutyltitanium dichloride, tetrabutyltitanate, butoxytitanium trichloride, and the like.

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

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

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

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

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

  Only one type of catalyst may be used, or two or more types of catalysts may be used. Further, a catalyst and a crosslinking retarder may be used in combination. The amount of the catalyst is preferably 0.02% by weight to 0.10% by weight, more preferably 0.02% by weight to 0.08% by weight, and still more preferably 0% with respect to the polyol (A). 0.02 wt% to 0.06 wt%, particularly preferably 0.02 wt% to 0.05 wt%. By adjusting the amount of the catalyst within the above range, when the surface protective film is once peeled off from the adherend having a large surface level difference and adhered to the adherend again, the surface level difference of the adherend is Even when it is large, it is possible to provide an adherend with a surface protective film, which is excellent in wettability and further excellent in step following ability and can achieve a sufficiently high adhesion rate.

  The composition containing the polyol (A) and the polyfunctional isocyanate compound (B) may contain any appropriate other component as long as the effects of the present invention are not impaired. Examples of such other components include resin components other than polyurethane resins, tackifiers, inorganic fillers, organic fillers, metal powders, pigments, foils, softeners, anti-aging agents, conductive agents, Examples include ultraviolet absorbers, antioxidants, light stabilizers, surface lubricants, leveling agents, corrosion inhibitors, heat stabilizers, polymerization inhibitors, lubricants, solvents, and catalysts.

<Polyurethane resin obtained from composition containing urethane prepolymer (C) and polyfunctional isocyanate compound (B)>
The polyurethane resin obtained from the composition containing the urethane prepolymer (C) and the polyfunctional isocyanate compound (B) may be any appropriate one as long as it is a polyurethane resin obtained using a so-called “urethane prepolymer” as a raw material. Any polyurethane resin can be employed.

  The polyurethane resin obtained from the composition containing the urethane prepolymer (C) and the polyfunctional isocyanate compound (B) contains, for example, the polyurethane polyol as the urethane prepolymer (C) and the polyfunctional isocyanate compound (B). Examples thereof include polyurethane resins obtained from the composition. Only one type of urethane prepolymer (C) may be used, or two or more types may be used. Only one type of polyfunctional isocyanate compound (B) may be used, or two or more types may be used.

  The polyurethane polyol as the urethane prepolymer (C) preferably reacts the polyester polyol (a1) and the polyether polyol (a2) with the organic polyisocyanate compound (a3) in the presence or absence of a catalyst. It is something to be made.

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

  The molecular weight of the polyester polyol (a1) can be used from a low molecular weight to a high molecular weight. The molecular weight of the polyester polyol (a1) is preferably a number average molecular weight of 500 to 5,000. When the number average molecular weight is less than 500, the reactivity becomes high and the gelation tends to occur. When the number average molecular weight exceeds 5000, the reactivity is lowered, and the cohesive force of the polyurethane polyol itself may be reduced. The amount of the polyester polyol (a1) used is preferably 10 to 90 mol% in the polyol constituting the polyurethane polyol.

  Any appropriate polyether polyol can be used as the polyether polyol (a2). As such a polyether polyol (a2), for example, a low molecular weight polyol such as water, propylene glycol, ethylene glycol, glycerin, trimethylolpropane or the like is used as an initiator, and ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran or the like is used. The polyether polyol obtained by polymerizing an oxirane compound is mentioned. Specific examples of such polyether polyol (a2) include polyether polyols having 2 or more functional groups such as polypropylene glycol, polyethylene glycol, and polytetramethylene glycol.

  The molecular weight of the polyether polyol (a2) can be used from a low molecular weight to a high molecular weight. As a molecular weight of polyether polyol (a2), a number average molecular weight becomes like this. Preferably it is 1000-5000. When the number average molecular weight is less than 1000, the reactivity is high and the gelation tends to occur. When the number average molecular weight exceeds 5000, the reactivity is lowered, and the cohesive force of the polyurethane polyol itself may be reduced. The amount of the polyether polyol (a2) used is preferably 20 mol% to 80 mol% in the polyol constituting the polyurethane polyol.

  A part of the polyether polyol (a2), if necessary, may be glycols such as ethylene glycol, 1,4-butanediol, neopentyl glycol, butylethylpentanediol, glycerin, trimethylolpropane, pentaerythritol, They can be used in combination with polyamines such as ethylenediamine, N-aminoethylethanolamine, isophoronediamine, and xylylenediamine.

  As the polyether polyol (a2), only a bifunctional polyether polyol may be used, or a polyether having a number average molecular weight of 1000 to 5000 and having at least 3 or more hydroxyl groups in one molecule. A part or all of the polyol may be used. When the polyether polyol (a2) has an average molecular weight of 1000 to 5000 and a part or all of the polyether polyol having at least 3 hydroxyl groups in one molecule, a balance between adhesive force and removability is obtained. Can be good. In such a polyether polyol, if the number average molecular weight is less than 1000, the reactivity becomes high and there is a possibility that gelation tends to occur. Further, in such a polyether polyol, when the number average molecular weight exceeds 5000, the reactivity is lowered, and further, the cohesive force of the polyurethane polyol itself may be reduced. The number average molecular weight of such a polyether polyol is more preferably 2500 to 3500.

  Any appropriate organic polyisocyanate compound can be used as the organic polyisocyanate compound (a3). Examples of such an organic polyisocyanate compound (a3) include aromatic polyisocyanates, aliphatic polyisocyanates, araliphatic polyisocyanates, and alicyclic polyisocyanates.

  Examples of the aromatic polyisocyanate include 1,3-phenylene diisocyanate, 4,4′-diphenyl diisocyanate, 1,4-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6 -Tolylene diisocyanate, 4,4'-toluidine diisocyanate, 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate benzene, dianisidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4 ', 4 "-triphenylmethane triisocyanate and the like.

  Examples of the aliphatic polyisocyanate include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, Examples include 2,4,4-trimethylhexamethylene diisocyanate.

  Examples of the araliphatic polyisocyanate include 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, and the like.

  Examples of the alicyclic polyisocyanate include 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate, 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, and 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, etc. It is done.

  As the organic polyisocyanate compound (a3), a trimethylolpropane adduct, a burette reacted with water, a trimer having an isocyanurate ring, and the like can be used in combination.

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

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

  Examples of organometallic compounds include tin compounds and non-tin compounds.

  Examples of the tin compound include dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin dimaleate, dibutyltin dilaurate (DBTDL), dibutyltin diacetate, dibutyltin sulfide, tributyltin sulfide, tributyltin oxide, tributyl Examples thereof include tin acetate, triethyltin ethoxide, tributyltin ethoxide, dioctyltin oxide, tributyltin chloride, tributyltin trichloroacetate, and tin 2-ethylhexanoate.

  Non-tin compounds include, for example, titanium compounds such as dibutyltitanium dichloride, tetrabutyltitanate, and butoxytitanium trichloride; lead compounds such as lead oleate, lead 2-ethylhexanoate, lead benzoate, and lead naphthenate Iron compounds such as iron 2-ethylhexanoate and iron acetylacetonate; cobalt compounds such as cobalt benzoate and cobalt 2-ethylhexanoate; zinc compounds such as zinc naphthenate and zinc 2-ethylhexanoate; And zirconium-based compounds such as zirconium naphthenate.

  When a catalyst is used in obtaining a polyurethane polyol, in a system in which two types of polyols, a polyester polyol and a polyether polyol, are present, due to the difference in reactivity, in a single catalyst system, gelation or a reaction solution is caused. The problem of becoming cloudy is likely to occur. Therefore, by using two kinds of catalysts when obtaining the polyurethane polyol, the reaction rate, the selectivity of the catalyst and the like can be easily controlled, and these problems can be solved. Examples of such a combination of two types of catalysts include tertiary amine / organometallic, tin / non-tin, and tin / tin, preferably tin / tin, more preferably Is a combination of dibutyltin dilaurate and tin 2-ethylhexanoate. The blending ratio is, by weight ratio, 2-ethylhexanoic acid tin / dibutyltin dilaurate is preferably less than 1, more preferably 0.2 to 0.6. If the blending ratio is 1 or more, gelation tends to occur due to the balance of catalytic activity.

  When a catalyst is used in obtaining the polyurethane polyol, the amount of the catalyst used is preferably 0.01 with respect to the total amount of the polyester polyol (a1), the polyether polyol (a2) and the organic polyisocyanate compound (a3). -1.0 wt%.

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

  When obtaining a polyurethane polyol, it is not necessary to use a catalyst. In that case, reaction temperature becomes like this. Preferably it is 100 degreeC or more, More preferably, it is 110 degreeC or more. Moreover, when obtaining a polyurethane polyol without a catalyst, it is preferable to make it react for 3 hours or more.

  For example, 1) polyester polyol, polyether polyol, catalyst, and organic polyisocyanate are charged in a flask. 2) polyester polyol, polyether polyol, and catalyst are charged in a flask, and organic polyisocyanate is obtained. The method of adding by dripping is mentioned. As a method for obtaining the polyurethane polyol, the method 2) is preferable in controlling the reaction.

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

  What was mentioned above can be used as a polyfunctional isocyanate compound (B).

  The composition containing the urethane prepolymer (C) and the polyfunctional isocyanate compound (B) may contain any appropriate other component as long as the effects of the present invention are not impaired. Examples of such other components include resin components other than polyurethane resins, tackifiers, inorganic fillers, organic fillers, metal powders, pigments, foils, softeners, anti-aging agents, conductive agents, Examples include ultraviolet absorbers, antioxidants, light stabilizers, surface lubricants, leveling agents, corrosion inhibitors, heat stabilizers, polymerization inhibitors, lubricants, solvents, and catalysts.

  As a method for producing a polyurethane resin obtained from a composition containing a urethane prepolymer (C) and a polyfunctional isocyanate compound (B), a method for producing a polyurethane resin using a so-called “urethane prepolymer” as a raw material. Any suitable manufacturing method can be adopted.

  The number average molecular weight Mn of the urethane prepolymer (C) is preferably 1000 to 100,000.

  In the urethane prepolymer (C) and the polyfunctional isocyanate compound (B), the equivalent ratio of the NCO group to the OH group is preferably 0.3 to 1.0 as an NCO group / OH group, more preferably 0.8. It is 3-0.9, More preferably, it is 0.3-0.8, Most preferably, it is 0.3-0.7, Most preferably, it is 0.3-0.6. When the NCO group / OH group equivalent ratio is adjusted within the above range, the surface protective film is once peeled off from the adherend having a large surface level difference, and then adhered to the adherend again. Even when the surface level difference of the body is large, it is possible to provide an adherend with a surface protective film which is excellent in wettability and further excellent in level-step following property and can achieve a sufficiently high adhesion rate.

  The content ratio of the polyfunctional isocyanate compound (B) is preferably 1.1% to 3.6% by weight of the polyfunctional isocyanate compound (B) with respect to the urethane prepolymer (C), and more preferably 1.1 wt% to 3.2 wt%, more preferably 1.1 wt% to 2.9 wt%, particularly preferably 1.1 wt% to 2.5 wt%, and most preferably Is 1.1 wt% to 2.1 wt%. When the content ratio of the polyfunctional isocyanate compound (B) is adjusted within the above range, the surface protective film is once peeled off from the adherend having a large surface step, and is again attached to the adherend. Even when the surface level difference of the adherend is large, it is possible to provide an adherend with a surface protective film that can achieve a sufficiently high adhesion rate because it is superior in wettability and further in step followability. .

≪Base material layer≫
Any appropriate thickness can be adopted as the thickness of the base material layer depending on the application. The thickness of the base material layer is preferably 5 μm to 300 μm, more preferably 10 μm to 250 μm, still more preferably 15 μm to 200 μm, and particularly preferably 20 μm to 150 μm.

  The base material layer may be a single layer or a laminate of two or more layers. The base material layer may be stretched.

  Any appropriate material can be adopted as the material of the base material layer depending on the application. For example, a plastic, paper, a metal film, a nonwoven fabric, etc. are mentioned. Preferably, it is a plastic. The base material layer may be composed of one kind of material, or may be composed of two or more kinds of materials. For example, you may be comprised from 2 or more types of plastics.

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

  The base material layer may contain any appropriate additive as required. Examples of the additive that can be contained in the base material layer include an antioxidant, an ultraviolet absorber, a light stabilizer, an antistatic agent, a filler, and a pigment. The kind, number, and amount of additives that can be contained in the base material layer can be appropriately set according to the purpose. In particular, when the material of the base material layer is plastic, it is preferable to contain some of the above additives for the purpose of preventing deterioration. From the viewpoint of improving weather resistance and the like, particularly preferred additives include antioxidants, ultraviolet absorbers, light stabilizers, and fillers.

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

  Arbitrary appropriate ultraviolet absorbers can be employ | adopted as a ultraviolet absorber. Examples of such UV absorbers include benzotriazole UV absorbers, triazine UV absorbers, and benzophenone UV absorbers. The content ratio of the ultraviolet absorber is preferably 2% by weight or less based on the base resin forming the base layer (when the base layer is a blend, the blend is the base resin), Preferably it is 1 weight% or less, More preferably, it is 0.01 weight%-0.5 weight%.

  Any appropriate light stabilizer can be adopted as the light stabilizer. Examples of such light stabilizers include hindered amine light stabilizers and benzoate light stabilizers. The content ratio of the light stabilizer is preferably 2% by weight or less based on the base resin forming the base layer (when the base layer is a blend, the blend is the base resin). Preferably it is 1 weight% or less, More preferably, it is 0.01 weight%-0.5 weight%.

  Any appropriate filler can be adopted as the filler. Examples of such fillers include inorganic fillers. Specific examples of the inorganic filler include carbon black, titanium oxide, and zinc oxide. The content of the filler is preferably 20% by weight or less with respect to the base resin forming the base layer (when the base layer is a blend, the blend is the base resin), and more preferably Is 10% by weight or less, more preferably 0.01% by weight to 10% by weight.

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

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

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

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to these Examples at all. In addition, the test and evaluation method in an Example etc. are as follows. Note that “parts” means “parts by weight” unless otherwise noted, and “%” means “% by weight” unless otherwise noted.

<Measurement of adhesive strength>
After the surface protective film with a separator is cut to a size of 25 mm in width and 80 mm in length and the separator is peeled off, it is laminated on an AGS1 polarizing plate (manufactured by Nitto Denko Corporation, width 70 mm, length 100 mm) at a pressure of 0.25 MPa. Then, an evaluation sample was produced. After lamination, (1) left in an environment of 23 ° C. × 50% RH for 30 minutes, (2) left in an environment of 50 ° C. for 1 week, and (3) in an environment of 60 ° C. × 90% RH. After being left for 1 week, (4) after being left for 1 week in an environment of 85 ° C., a peeling rate of 300 mm / min was used using a universal tensile tester (manufactured by Minebea Co., Ltd., product name: TCM-1kNB). The adhesive strength when peeled at a peeling angle of 180 ° was measured. The measurement was performed in an environment of 23 ° C. × 50% RH.

<Measurement of wetting speed>
The surface protective film with a separator was cut into a size of 25 mm in width and 100 mm in length to obtain an evaluation sample. Using an AGS1 polarizing plate (manufactured by Nitto Denko Corporation, width 70 mm, length 100 mm) as the adherend, peel off the separator of the evaluation sample, and fix one end of the width side to the width side end of the adherend. Then, the width-side end portion that was not fixed was lifted, and the time from when the hand was released to when it spreaded by 100 mm was measured (unit: s / 2.5 cm × 10 cm). The speed was calculated from the time taken, and the case where the speed was 5 cm ² / s or more was marked as “O” and the case where it was less than 5 cm ² / s as “x”.

<Measurement of peeling voltage>
Cut the surface protective film with a separator into a size of 70mm in width and 130mm in length, peel off the separator, and then just overlap the previously removed acrylic plate (thickness 1mm, width 70mm, length 100mm) One reciprocal pressure was applied to the AGS1 polarizing plate (manufactured by Nitto Denko Corporation, width 70 mm, length 100 mm) with a 2 kg roller. At this time, the surface protective film was in a state of protruding 30 mm from the glass. After being left for 1 day in an environment of 23 ° C. × 50% RH, one end protruding 30 mm from the glass was fixed to an automatic winder, and peeled so that the peeling angle was 150 degrees and the peeling speed was 10 m / min. did. And the stripping voltage was measured with the electric potential measuring device (KSD-0103 by Kasuga Denki Co., Ltd.) fixed to the position 10 cm away from the surface protection film. This measurement was performed in an environment of 23 ° C. × 50% RH.

<Measurement of centerline average roughness Ra>
An AGS1 polarizing plate (manufactured by Nitto Denko Corporation), an aluminum plate, and an aluminum plate whose surface is rubbed with sandpaper of a predetermined grain size are set on the stage of ZYGO New View 7300 (manufactured by Canon Marketing Japan Co., Ltd.). The line average roughness Ra was measured. Note that the particle counts of the sandpaper used for rubbing the aluminum plate are (1) 320 and (2) 100.

<Measurement of adhesion rate when pasting only with its own weight>
Prepare an aluminum plate that has been subjected to roughness measurement with an AGS1 polarizing plate (manufactured by Nitto Denko Corporation, width 70 mm, length 100 mm) and ZYGO New View 7300 (manufactured by Canon Marketing Japan Co., Ltd.). Remove the separator of the surface protection film with the cut separator, fix one end of the width side to the adherend, lift the end of the width side that is not fixed, release it, and release each hand with its own weight It was made to adhere to the adherend. Thereafter, the adhesion area was calculated by VHX-100F (Keyence Corporation), and the adhesion ratio (first time) was calculated by adhesion ratio (%) = (adhesion area / total area). Furthermore, the end portion on the width side that was not fixed was lifted again, and the hand was released to bring it into close contact with each adherend only by its own weight. Similarly, the adhesion rate (second time) was calculated.

[Example 1]
As a polyol, Preminol S3011 (manufactured by Asahi Glass Co., Ltd., Mn = 10000) which is a polyol having 3 OH groups: Sanix GP-3000 (manufactured by Sanyo Chemical Co., Ltd.) which is a polyol having 3 OH groups Mn = 3000): 13 parts by weight, a polyol having three OH groups, Sannix GP-1000 (manufactured by Sanyo Chemical Co., Ltd., Mn = 1000): 2 parts by weight and a polyfunctional alicyclic ring as a polyfunctional isocyanate compound Coronate HX (Nippon Polyurethane Industry Co., Ltd.) which is an aliphatic isocyanate compound: 2.7 parts by weight, catalyst (manufactured by Nippon Chemical Industry Co., Ltd., trade name: Nursem Ferric): 0.04 parts by weight, Irganox 1010 (manufactured by BASF) ): 0.50 parts by weight, ELEXEL AS110 (ionic liquid, Daiichi Kogyo Seiyaku Co., Ltd.) 1.50 parts by weight, KF6004 (polyether-modified silicone, manufactured by Shin-Etsu Chemical Co., Ltd.): 0.01 parts by weight, 241 parts by weight of ethyl acetate as a diluent solvent, stirred with a disper, urethane A system pressure-sensitive adhesive composition was obtained.
The obtained urethane-based pressure-sensitive adhesive composition was applied to a base material “Lumirror S10” (thickness 38 μm, manufactured by Toray Industries, Inc.) made of a polyester resin so that the thickness after drying with a fountain roll was 10 μm. It was cured and dried under the condition of a drying time of 30 seconds. Thus, the adhesive layer which consists of urethane type adhesives (1) on a base material was produced.
Subsequently, the surface of the pressure-sensitive adhesive layer was pasted with a silicone-treated surface of a separator made of a polyester resin having a thickness of 25 μm and subjected to silicone treatment on one surface to obtain a surface protective film (1) with a separator.
Next, three types of aluminum plates were prepared which were measured for roughness with AGS1 polarizing plate (manufactured by Nitto Denko Corporation, width 70 mm, length 100 mm) and ZYGO New View 7300 (manufactured by Canon Marketing Japan Inc.), Remove the separator of the surface protective film (1) with a separator cut to the same size as these, fix one end of the width side to the adherend, lift the end of the unfixed width side, It was released and was made to adhere to each adherend only with its own weight to obtain adherends (1a) to (1d) with a surface protective film.
The results are shown in Table 1.

[Examples 2 to 8]
As the polyfunctional isocyanate compound, except that the blending amount of Coronate HX (Nippon Polyurethane Industry Co., Ltd.), which is a polyfunctional alicyclic isocyanate compound, was changed as shown in Table 1, it was carried out in the same manner as in Example 1 and with a surface protective film. The adherends “(2a) to (2d)” to “(8a) to (8d)” were obtained.
The results are shown in Table 1.

[Examples 9 to 11]
The compounding amount of Coronate HX (Nippon Polyurethane Industry Co., Ltd.), which is a polyfunctional alicyclic isocyanate compound, is changed as shown in Table 2 as the polyfunctional isocyanate compound, and isopropyl myristate (Kao) as the fatty acid ester as shown in Table 2. Co., Ltd., trade name: EXCEPARL IPM, Mn = 270): Except for blending 10 parts by weight, the same procedure as in Example 1 was performed, and the adherends with surface protective film “(9a) to (9d)” to “ (11a) to (11d) ”were obtained.
The results are shown in Table 2.

[Examples 12 to 14]
The compounding amount of Coronate HX (Nippon Polyurethane Industry Co., Ltd.), which is a polyfunctional alicyclic isocyanate compound, is changed as shown in Table 2 as the polyfunctional isocyanate compound, and isopropyl myristate (Kao) as the fatty acid ester as shown in Table 2. Product name: EXCEPARL IPM, Mn = 270): Except for blending 30 parts by weight, the same procedure as in Example 1 was performed, and the adherends with surface protective film “(12a) to (12d)” to “ (14a) to (14d) ”were obtained.
The results are shown in Table 2.

[Examples 15 to 17]
The blending amount of Coronate HX (Nippon Polyurethane Industry Co., Ltd.), which is a polyfunctional alicyclic isocyanate compound, is changed as shown in Table 3 as the polyfunctional isocyanate compound, and 2-ethylhexanoic acid is used as the fatty acid ester as shown in Table 3. Cetyl (Nisshin Oillio Group, trade name: Saracos 816T, Mn = 368): Except for blending 10 parts by weight, the same procedure as in Example 1 was performed, and the adherend with surface protective film “(15a) ˜ (15d) ”to“ (17a) to (17d) ”were obtained.
The results are shown in Table 3.

[Examples 18 to 20]
The blending amount of Coronate HX (Nippon Polyurethane Industry Co., Ltd.), which is a polyfunctional alicyclic isocyanate compound, is changed as shown in Table 3 as the polyfunctional isocyanate compound, and 2-ethylhexanoic acid is used as the fatty acid ester as shown in Table 3. Cetyl (Nisshin Oillio Group, trade name: Saracos 816T, Mn = 368): Except for blending 30 parts by weight, the same procedure as in Example 1 was performed, and the adherend with surface protective film “(18a) ˜ (18d) ”to“ (20a) to (20d) ”were obtained.
The results are shown in Table 3.

Example 21
100 parts by weight of “Siavine SH-109H” (54% solids, fatty acid ester contained, manufactured by Toyo Ink) as the urethane prepolymer, Coronate HX (Nippon Polyurethane Industry Co., Ltd.), which is a polyfunctional alicyclic isocyanate compound as the polyfunctional isocyanate compound Company): 1.4 parts by weight, Elexel AS110 (ionic liquid, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.): 1.50 parts by weight, KF6004 (polyether-modified silicone, manufactured by Shin-Etsu Chemical Co., Ltd.): 0.01% by weight Part and toluene: 208 parts by weight as a diluent solvent were mixed and stirred with a disper to obtain a urethane-based pressure-sensitive adhesive composition.
The obtained urethane-based pressure-sensitive adhesive composition was applied to a base material “Lumirror S10” (thickness 38 μm, manufactured by Toray Industries, Inc.) made of a polyester resin so that the thickness after drying with a fountain roll was 10 μm. It was cured and dried under the condition of a drying time of 30 seconds. Thus, the adhesive layer which consists of urethane type adhesives (21) on a base material was produced.
Subsequently, the surface of the pressure-sensitive adhesive layer was pasted with a silicone-treated surface of a separator made of a polyester resin having a thickness of 25 μm and subjected to silicone treatment on one surface to obtain a surface protective film (21) with a separator.
Next, three types of aluminum plates were prepared which were measured for roughness with AGS1 polarizing plate (manufactured by Nitto Denko Corporation, width 70 mm, length 100 mm) and ZYGO New View 7300 (manufactured by Canon Marketing Japan Inc.), Remove the separator of the surface protective film (21) with a separator cut to the same size as these, fix one end of the width side to the adherend, lift the end of the unfixed width side, It was released and was made to adhere to each adherend only with its own weight to obtain adherends (21a) to (21d) with a surface protective film.
The results are shown in Table 4.

[Examples 22 to 25]
As the polyfunctional isocyanate compound, except that the blending amount of Coronate HX (Nippon Polyurethane Industry Co., Ltd.), which is a polyfunctional alicyclic isocyanate compound, was changed as shown in Table 4, it was carried out in the same manner as in Example 21, with a surface protective film. The adherends “(22a) to (22d)” to “(25a) to (25d)” were obtained.
The results are shown in Table 4.

[Comparative Examples 1-3]
As the polyfunctional isocyanate compound, except that the blending amount of Coronate HX (Nippon Polyurethane Industry Co., Ltd.), which is a polyfunctional alicyclic isocyanate compound, was changed as shown in Table 5, it was carried out in the same manner as in Example 1 and with a surface protective film. The adherends “(C1a) to (C1d)” to “(C3a) to (C3d)” were obtained.
The results are shown in Table 5.

[Comparative Example 4]
As the polyfunctional isocyanate compound, except that the blending amount of Coronate HX (Nippon Polyurethane Industry Co., Ltd.), which is a polyfunctional alicyclic isocyanate compound, was changed as shown in Table 5, it was carried out in the same manner as in Example 21, with a surface protective film. The adherends (C4a) to (C4d) were obtained.
The results are shown in Table 5.

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

DESCRIPTION OF SYMBOLS 1 Base material layer 2 Adhesive layer 10 Surface protective film 100 Adhering body 1000 Adhering body with a surface protective film

Claims (9)

The pressure-sensitive adhesive layer side of the surface protective film including the pressure-sensitive adhesive layer is a member bonded to the adherend surface having a center line average roughness Ra of 0.2 μm to 2 μm,
The pressure-sensitive adhesive layer contains a urethane-based pressure-sensitive adhesive containing a polyurethane-based resin as a main component,
The pressure-sensitive adhesive layer is a pressure-sensitive adhesive layer having an adhesion rate of 80% or more when bonded to the adherend surface only by its own weight.
An adherend with a surface protective film.   The adherend with a surface protective film according to claim 1, wherein the adherend is an optical member or an electronic member.   The adherend with a surface protective film according to claim 1 or 2, wherein the polyurethane-based resin is a polyurethane-based resin obtained from a composition containing a polyol (A) and a polyfunctional isocyanate compound (B).   The adherend with a surface protective film according to claim 3, wherein the polyol (A) has a number average molecular weight Mn of 400 to 20000.   The equivalent ratio of an NCO group and an OH group in the polyol (A) and the polyfunctional isocyanate compound (B) is 0.3 to 1.0 as an NCO group / OH group. An adherend with a surface protective film.   The adherend with a surface protective film according to claim 1 or 2, wherein the polyurethane resin is a polyurethane resin obtained from a composition containing a urethane prepolymer (C) and a polyfunctional isocyanate compound (B).   The equivalent ratio of NCO group and OH group in the urethane prepolymer (C) and the polyfunctional isocyanate compound (B) is 0.3 to 1.0 as NCO group / OH group. An adherend with a surface protective film.   The adherend with a surface protective film according to any one of claims 1 to 7, wherein the urethane-based pressure-sensitive adhesive contains a fatty acid ester.   The adherend with a surface protective film according to claim 8, wherein the fatty acid ester has a number average molecular weight Mn of 200 to 400.

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