KR102285701B1 - Adherend with surface protection film - Google Patents

Abstract

When the pressure-sensitive adhesive layer side of the surface protection film including the pressure-sensitive adhesive layer is a member bonded to the surface of the adherend having a large surface step, the surface protection film is peeled off from the adherend and adhered to the adherend again, Provided is an adherend with a surface protection film that can achieve a sufficiently high adhesion rate even when the surface level of the adherend is large, because it is excellent in wettability and also in step followability.
The adherend with a surface protection film of the present invention is a member in which the pressure-sensitive adhesive layer side of the surface protection film including the pressure-sensitive adhesive layer is bonded to the surface of the adherend having a centerline average roughness Ra of 0.2 µm to 2 µm, and the pressure-sensitive adhesive layer , a urethane-based pressure-sensitive adhesive containing a polyurethane-based resin as a main component, and the pressure-sensitive adhesive layer is a pressure-sensitive adhesive layer having an adhesion rate of 80% or more when the pressure-sensitive adhesive layer is bonded only by its own weight to the surface of the adherend.

Description

To-be-adhered body with a surface protection film {ADHEREND WITH SURFACE PROTECTION FILM}

The present invention relates to an adherend with a surface protection film. The to-be-adhered body with a surface protection film of this invention is a member by which the surface protection film was bonded by the surface of an optical member or an electronic member, for example.

Generally, a surface protection film is adhered to an exposed surface side of an optical member or an electronic member in order to prevent the occurrence of scratches on the surface during processing, assembly, inspection, transportation, and the like. Such a surface protection film peels from an optical member or an electronic member when the need for surface protection is no longer needed.

As for such a surface protection film, from the manufacturing process of an optical member or an electronic member, through an assembly process, an inspection process, a transport process, etc., until the final shipment, the case which continues using the same surface protection film has come to increase. In this case, in each process, such a surface protection film is adhere|attached, peeled, and re-adhesive by manual operation in many cases.

When sticking a surface protection film by hand or when bonding a surface protection film to a large to-be-adhered body, air bubbles may be entrapped between a to-be-adhered body and a surface protection film. For this reason, several techniques for improving the wettability of the surface protection film have been reported so that air bubbles do not become entrained at the time of adhesion. For example, the surface protection film which used the silicone resin with a quick wetting rate for an adhesive layer is known (for example, refer patent document 1).

However, when a silicone resin is used for the pressure-sensitive adhesive layer, the pressure-sensitive adhesive component tends to contaminate the adherend, so it is a big problem for use as a surface protection film for protecting the surface of a member requiring particularly low contamination, such as an optical member or an electronic member. there is

As a surface protection film with little contamination originating in an adhesive component, the surface protection film which used acrylic resin for an adhesive layer is known (for example, refer patent document 2). However, since the surface protection film using an acrylic resin for an adhesive layer is inferior in wettability, when sticking a surface protection film manually, air bubbles may be entrapped between a to-be-adhered body and a surface protection film. In addition, when an acrylic resin is used for the pressure-sensitive adhesive layer, there is a problem that pressure-sensitive adhesive residue is easily generated during peeling, and as a surface protection film for protecting the surface of a member that does not particularly like the mixing of foreign substances, such as an optical member or an electronic member. there is a problem.

In addition, when the surface protection film is adhered to an adherend, it is required to be excellent in wettability such as initial wettability as described above, and light peelability is required. This is in order not to give damage to a to-be-adhered body when peeling, and to re-adhere to a to-be-adhered body after peeling, and to use it again as a surface protection film. If the peeling is heavy even with good wettability, in the case of a thin and brittle adherend, the adherend is destroyed, or the surface protection film is deformed when the surface protection film is peeled off, and it cannot be used again as a surface protection film. In order to avoid such a problem, the so-called rework property, which can be adhered many times without entrapment of air bubbles, and can be lightly peeled without deformation, is strong on a surface protection film used for an optical member or an electronic member. is required

In order to solve such a problem, the surface protection film which has an adhesive layer containing a specific urethane-type adhesive is reported in recent years (for example, refer patent documents 3, 4).

However, the conventional surface protection film having a pressure-sensitive adhesive layer containing a urethane-based pressure-sensitive adhesive has a problem in that a sufficiently high adhesion rate cannot be achieved due to poor followability to steps when bonded to an adherend having a large surface level.

In particular, as described above, in the fields of optical members and electronic members, the surface protection film continues the same surface protection film from the manufacturing process, through the assembly process, inspection process, transport process, etc., until finally shipped. In many cases, the same surface protection film is manually adhered, peeled, and re-adhesive to an adherend in each process. In such a case, if the surface protection film is peeled from the adherend to which the surface protection film was once bonded, and then again adheres to the adherend, if the surface step of the adherend is large, the step followability is greatly reduced, resulting in high adhesion. A problem arises that it becomes difficult to achieve the rate.

Japanese Patent Laid-Open No. 2006-152266 Japanese Patent Laid-Open No. 2004-051825 Japanese Patent Laid-Open No. 2014-111701 Japanese Patent Laid-Open No. 2004-111702

The subject of the present invention is a member in which the pressure-sensitive adhesive layer side of a surface protection film including an pressure-sensitive adhesive layer is bonded to the surface of an adherend having a large surface step, and the surface protection film is once peeled from the adherend, and then again the adherend To provide an adherend with a surface protection film, which can achieve a sufficiently high adhesion rate because of excellent wettability and excellent step followability, even when the surface step of the adherend is large. there is.

An adherend with a surface protection film of the present invention comprises:

The adhesive layer side of the surface protection film containing an adhesive layer is a member joined to the to-be-adhered body surface whose centerline average roughness Ra is 0.2 micrometer - 2 micrometers,

The pressure-sensitive adhesive layer contains a urethane-based pressure-sensitive adhesive containing a polyurethane-based resin as a main component,

The adhesive layer is a pressure-sensitive adhesive layer having an adhesion rate of 80% or more when the pressure-sensitive adhesive layer is bonded only by its own weight to the surface of the adherend.

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

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

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

In a preferable embodiment, in the said polyol (A) and the said polyfunctional isocyanate compound (B), the equivalent ratio of NCO group and OH group is 0.3-1.0 as NCO group/OH group.

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

In a preferable embodiment, the equivalent ratio of NCO group and OH group in the said urethane prepolymer (C) and the said polyfunctional isocyanate compound (B) is 0.3-1.0 as NCO group/OH group.

In a preferred embodiment, the urethane-based pressure-sensitive adhesive contains a fatty acid ester.

In a preferable embodiment, the number average molecular weights Mn of the said fatty acid ester are 200-400.

According to the present invention, the pressure-sensitive adhesive layer side of the surface protection film including the pressure-sensitive adhesive layer is a member bonded to the surface of the adherend having a large surface step, and the surface protection film is once peeled from the adherend, and then again to the adherend. In the case of adhesion, even when the surface step of the adherend is large, the adherend with a surface protection film can be provided, which can achieve a sufficiently high adhesion rate because it is excellent in wettability and also has excellent step followability. .

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

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

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

As long as the to-be-adhered body with a surface protection film of this invention has a surface protection film and a to-be-adhered body, it may have any suitable other member in the range which does not impair the effect of this invention.

The to-be-adhered body with a surface protection film of this invention is 0.2 micrometer - 2 micrometers in centerline average roughness Ra of the to-be-adhered body surface.

The adherend in the adherend with a surface protection film of the present invention may be any suitable adherend as long as it does not impair the effects of the present invention, as long as the surface centerline average roughness Ra of the adherend is 0.2 µm to 2 µm. can be employed As such an adherend, Preferably, it is an optical member or an electronic member. As an optical member, the color filter used for LCD, the touch panel using LCD, LCD etc., LCD, a polarizing plate, etc. are mentioned, for example. As an electronic member, an electroconductive film, electronic paper, etc. are mentioned, for example.

≪Surface protection film≫

A surface protection film contains an adhesive layer. A release liner having releasability may be bonded to the pressure-sensitive adhesive surface side of the pressure-sensitive adhesive layer.

In the surface protection film, the pressure-sensitive adhesive layer or the pressure-sensitive adhesive layer to which a release liner having releasability is preferably bonded to the pressure-sensitive adhesive surface side is located in the outermost layer.

The surface protection film, Preferably, it has a base material layer and an adhesive layer. One layer may be sufficient as a base material layer, and two or more layers may be sufficient as it. The surface protection film of this invention may have arbitrary appropriate other layers other than a base material layer and an adhesive layer in the range which does not impair the effect of this invention.

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

About the surface on which the adhesive layer 2 of the base material layer 1 is not laid, for the purpose of formation of a wound body etc. which are easy to rewind, for example, fatty acid amide, polyethyleneimine, a long-chain alkyl type to a base material layer. It is possible to perform a release treatment by adding an additive or the like, or to form a coating layer containing any appropriate release agent such as a silicone-based, long-chain alkyl-based, or fluorine-based release agent.

The thickness of a surface protection film can be set to arbitrary appropriate thickness according to a use. From a viewpoint for fully expressing the effect of this invention, Preferably it is 10 micrometers - 300 micrometers, More preferably, it is 15 micrometers - 250 micrometers, More preferably, it is 20 micrometers - 200 micrometers, Especially preferably, it is 25 micrometers. to 150 μm.

≪Adhesive layer≫

The pressure-sensitive adhesive layer includes a urethane-based pressure-sensitive adhesive containing a polyurethane-based resin as a main component. The content rate of the urethane-type adhesive in an adhesive layer becomes like this. Preferably they are 50 weight% - 100 weight%, More preferably, they are 60 weight% - 100 weight%, More preferably, they are 70 weight% - 100 weight%, Especially preferably It is preferably 80% to 100% by weight, and most preferably 90% to 100% by weight. By adjusting the content ratio of the urethane-based pressure-sensitive adhesive in the pressure-sensitive adhesive layer within the above range, once the surface protection film is peeled off from the adherend having a large surface step, and then adhered to the adherend again, even when the surface step of the adherend is large Since it is more excellent in wettability and also more excellent in followability to a step, it is possible to provide an adherend with a surface protection film that can achieve a sufficiently high adhesion rate.

An adhesive layer is an adhesive layer whose adhesion rate at the time of bonding only by dead weight with respect to the to-be-adhered body surface whose centerline average roughness Ra is 0.2 micrometer - 2 micrometers is 80 % or more. When the adhesive layer is bonded only by its own weight to the surface of the adherend having a center line average roughness Ra of 0.2 µm to 2 µm, the adhesion rate is 80% or more, so that the surface protection film is once peeled from the adherend having a large surface step, and again When adhering to an adherend, even when the surface level of the adherend is large, the adherend with a surface protection film can achieve a sufficiently high adhesion rate because of its excellent wettability and excellent step followability. can provide

Since the effect of the present invention can be more expressed, the adhesive layer has an adhesion rate when joined only by its own weight to the surface of an adherend having a center line average roughness Ra of 0.2 µm to 2 µm, preferably 82% or more. , more preferably 84% 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 ratio is preferably 100%.

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

Since the effect of the present invention can be more expressed, the adhesive layer has an adhesion rate when bonded only by its own weight to the surface of an adherend having a center line average roughness Ra of 0.3 µm, preferably 80% or more, more preferably It is preferably 83% or more, more preferably 86% or more, particularly preferably 88% or more, and most preferably 90% or more. The upper limit of the adhesion ratio is preferably 100%.

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

Since the effect of the present invention can be more expressed, the adhesive layer has an adhesion rate when bonded only by its own weight to the surface of an adherend having a center line average roughness Ra of 1.1 µm, preferably 80% or more, more preferably It is preferably 82% or more, more preferably 84% or more, particularly preferably 86% or more, and most preferably 87% or more. The upper limit of the adhesion ratio is preferably 100%.

As thickness of an adhesive layer, arbitrary appropriate thickness is employable according to a use. Since the thickness of an adhesive layer can express the effect of this invention more, Preferably they are 1 micrometer - 100 micrometers, More preferably, they are 3 micrometers - 50 micrometers, More preferably, they are 5 micrometers - 30 micrometers . By adjusting the thickness of the pressure-sensitive adhesive layer within the above range, once the surface protection film is peeled off from the adherend having a large surface step, and then adhered to the adherend again, even when the surface step of the adherend is large, the wettability is improved It is excellent, and since it is more excellent in step|step difference followability|trackability, the to-be-adhered body with a surface protection film which can achieve a more fully high adhesion rate can be provided.

An adhesive layer can be manufactured by arbitrary appropriate manufacturing methods. As such a manufacturing method, the method of apply|coating the composition which is a forming material of an adhesive layer on a base material layer, and forming an adhesive layer on a base material layer is mentioned, for example. Examples of the coating method include roll coating, gravure coating, reverse coating, roll brushing, spray coating, air knife coating, extrusion coating by a die coater, and the like.

The pressure-sensitive adhesive layer may contain any appropriate other components other than the urethane pressure-sensitive adhesive within a range that does not impair the effects of the present invention. Examples of such other components include resin components other than polyurethane-based resins, tackifiers, inorganic fillers, organic fillers, metal powders, pigments, thin products, softeners, antioxidants, conductive agents, ultraviolet absorbers, antioxidants, light stabilizers. , a surface lubricant, a leveling agent, a corrosion inhibitor, a heat-resistant stabilizer, a polymerization inhibitor, a lubricant, a solvent, a catalyst, and the like.

The content rate of the polyurethane-type resin in a urethane-type adhesive becomes like this. Preferably it is 50 weight% - 100 weight%, More preferably, it is 70 weight% - 100 weight%, More preferably, it is 90 weight% - 100 weight%, Especially It is preferably 95% to 100% by weight, and most preferably 98% to 100% by weight. By adjusting the content ratio of the polyurethane-based resin in the urethane-based pressure-sensitive adhesive within the above range, the surface protection film is once peeled from the adherend having a large surface step, and then adhered to the adherend again. When the surface step of the adherend is large It is also possible to provide an adherend with a surface protection film that is more excellent in wettability and more excellent in step-difference followability, which can achieve a sufficiently high adhesion rate.

A urethane-type adhesive can contain arbitrary appropriate other components other than a polyurethane-type resin in the range which does not impair the effect of this invention. Examples of such other components include resin components other than polyurethane-based resins, tackifiers, inorganic fillers, organic fillers, metal powders, pigments, thin products, softeners, antioxidants, conductive agents, ultraviolet absorbers, antioxidants, light stabilizers. , a surface lubricant, a leveling agent, a corrosion inhibitor, a heat-resistant stabilizer, a polymerization inhibitor, a lubricant, a solvent, a catalyst, and the like.

The urethane-type adhesive may contain the fatty acid ester. The number of fatty acid esters may be one, and 2 or more types may be sufficient as them.

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, and most preferably 250 to It is 350. By adjusting the number average molecular weight Mn of the fatty acid ester within the above range, the wetting rate can be further improved. When the number average molecular weight Mn of fatty acid ester is too small, even if there are many addition parts, there exists a possibility that a wet rate may not improve. When the number average molecular weight Mn of fatty acid ester is too large, sclerosis|hardenability of the adhesive at the time of drying deteriorates, and there exists a possibility that it may exert a bad influence on other adhesive characteristics not only a wet characteristic.

As fatty acid ester, arbitrary appropriate fatty acid ester can be employ|adopted in the range which does not impair the effect of this invention. As such fatty acid ester, for example, polyoxyethylene bisphenol A lauric acid ester, butyl stearate, 2-ethylhexyl palmitic acid, 2-ethylhexyl stearate, monoglyceride behenic acid, 2-ethylhexanoic acid wash tyl, isopropyl myristate, isopropyl palmitate, cholesteryl isostearate, lauryl methacrylate, methyl palm fatty acid, methyl laurate, methyl oleate, methyl stearate, myristyl myristate, myristate Octyldodecyl acid, pentaerythritol monooleate, pentaerythritol monostearate, pentaerythritol tetrapalmitate, stearyl stearate, isotridecyl stearate, 2-ethylhexanoate triglyceride, butyl laurate, Octyl oleate, etc. are mentioned.

When producing the urethane pressure-sensitive adhesive, the blending ratio of the fatty acid ester is, for example, preferably 5% by weight to 50% by weight, more preferably 7% by weight to 45% by weight relative to the polyol (A), More preferably, it is 8 weight% - 40 weight%, Especially preferably, it is 9 weight% - 35 weight%, Most preferably, it is 10 weight% - 30 weight%.

The urethane pressure-sensitive adhesive may contain an ionic liquid containing a fluoroorganic anion. Since the urethane-based pressure-sensitive adhesive contains an ionic liquid containing a fluoroorganic anion, it is possible to provide a urethane-based pressure-sensitive adhesive having excellent antistatic properties. The number of ionic liquids may be one, and 2 or more types may be sufficient as them.

In this invention, an ionic liquid means the molten salt (ionic compound) which shows a liquid phase at 25 degreeC.

As the ionic liquid, any suitable ionic liquid can be employed as long as it is an ionic liquid containing a fluoroorganic anion as long as it does not impair the effects of the present invention. The ionic liquid is preferably an ionic liquid composed of a fluoroorganic anion and an onium cation. By employing an ionic liquid composed of a fluoroorganic 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.

As the onium cation capable of constituting the ionic liquid, any suitable onium cation can be employed within a range that does not impair the effects of the present invention. The onium cation is preferably at least one selected from a nitrogen-containing onium cation, a sulfur-containing onium cation, and a phosphorus-containing onium cation. By selecting this onium cation, a urethane pressure-sensitive adhesive having extremely excellent antistatic properties can be provided.

As an onium cation which can comprise an ionic liquid, Preferably, it is at least 1 sort(s) selected from the cation which has a structure represented by General formula (1)-(5).

In the general formula (1), R _a represents a hydrocarbon group having 4 to 20 carbon atoms, may contain a hetero atom, R _b and R _c are the same or different, and hydrogen or a hydrocarbon group having 1 to 16 carbon atoms shown, and may contain a hetero atom. However, when the nitrogen atom contains a double bond, R _c is absent.

In the general formula (2), R _d represents a hydrocarbon group having 2 to 20 carbon atoms, and may contain a hetero atom, and R _e , R _f , and R _g are the same or different, and are hydrogen or carbon number 1 to It represents the hydrocarbon group of 16 and may contain the hetero atom.

In the general formula (3), R _h represents a hydrocarbon group having 2 to 20 carbon atoms, and may contain a hetero atom, and R _i , R _j , and R _k are the same or different, and are hydrogen or carbon number 1 to It represents the hydrocarbon group of 16 and may contain the hetero atom.

In the general formula (4), Z represents a nitrogen atom, a sulfur atom, or a phosphorus atom, and R ₁ , R _m , R _n , and R _o are the same or different and represent a hydrocarbon group having 1 to 20 carbon atoms. , may contain a hetero atom. provided that when Z is a sulfur atom, R _o is absent.

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

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

Specific examples of the cation represented by the general formula (1) include 1-ethylpyridinium cation, 1-butylpyridinium cation, 1-hexylpyridinium cation, 1-ethyl-3-methylpyridinium cation, 1-butyl-3-methylpyridinium cation, 1-hexyl-3-methylpyridinium cation, 1-butyl-4-methylpyridinium cation, 1-octyl-4-methylpyridinium cation, 1-butyl-3, pyridinium cations such as 4-dimethylpyridinium cation and 1,1-dimethylpyrrolidinium cation; 1-ethyl-1-methylpyrrolidinium cation, 1-methyl-1-propylpyrrolidinium cation, 1-methyl-1-butylpyrrolidinium cation, 1-methyl-1-pentylpyrrolidinium cation, 1- Methyl-1-hexylpyrrolidinium cation, 1-methyl-1-heptylpyrrolidinium cation, 1-ethyl-1-propylpyrrolidinium cation, 1-ethyl-1-butylpyrrolidinium cation, 1-ethyl- 1-pentylpyrrolidinium cation, 1-ethyl-1-hexylpyrrolidinium cation, 1-ethyl-1-heptylpyrrolidinium cation, 1,1-dipropylpyrrolidinium cation, 1-propyl-1-butyl pyrrolidinium cations such as pyrrolidinium cation and 1,1-dibutylpyrrolidinium cation; 1-propylpiperidinium cation, 1-pentylpiperidinium cation, 1-methyl-1-ethylpiperidinium cation, 1-methyl-1-propylpiperidinium cation, 1-methyl-1-butylpiperidinium cation, 1-methyl-1-pentylpiperidinium cation, 1-methyl-1-hexylpiperidinium cation, 1-methyl-1-heptylpiperidinium cation, 1-ethyl-1-propylpiperidinium cation, 1-ethyl-1-butylpiperidinium cation, 1-ethyl-1-pentylpiperidinium cation, 1-ethyl-1-hexylpiperidinium cation, 1-ethyl-1-heptylpiperidinium cation, 1- piperidinium cations such as propyl-1-butylpiperidinium cation, 1,1-dimethylpiperidinium cation, 1,1-dipropylpiperidinium cation, and 1,1-dibutylpiperidinium cation; 2-methyl-1-pyroin cation; 1-ethyl-2-phenylindole cation; 1,2-dimethylindole cation; 1-ethylcarbazole cation; and the like.

Among these, since the effect of this invention can be expressed further, Preferably, 1-ethylpyridinium cation, 1-butylpyridinium cation, 1-hexylpyridinium cation, 1-ethyl-3-methyl pyridinium cation, 1-butyl-3-methylpyridinium cation, 1-hexyl-3-methylpyridinium cation, 1-butyl-4-methylpyridinium cation, 1-octyl-4-methylpyridinium cation, etc. dinium cation; 1-ethyl-1-methylpyrrolidinium cation, 1-methyl-1-propylpyrrolidinium cation, 1-methyl-1-butylpyrrolidinium cation, 1-methyl-1-pentylpyrrolidinium cation, 1- Methyl-1-hexylpyrrolidinium cation, 1-methyl-1-heptylpyrrolidinium cation, 1-ethyl-1-propylpyrrolidinium cation, 1-ethyl-1-butylpyrrolidinium cation, 1-ethyl- pyrrolidinium cations such as 1-pentylpyrrolidinium cation, 1-ethyl-1-hexylpyrrolidinium cation, and 1-ethyl-1-heptylpyrrolidinium cation; 1-methyl-1-ethylpiperidinium cation, 1-methyl-1-propylpiperidinium cation, 1-methyl-1-butylpiperidinium cation, 1-methyl-1-pentylpiperidinium cation, 1- Methyl-1-hexylpiperidinium cation, 1-methyl-1-heptylpiperidinium cation, 1-ethyl-1-propylpiperidinium cation, 1-ethyl-1-butylpiperidinium cation, 1-ethyl- piperidinium cations such as 1-pentylpiperidinium cation, 1-ethyl-1-hexylpiperidinium cation, 1-ethyl-1-heptylpiperidinium cation, and 1-propyl-1-butylpiperidinium cation; and the like, more preferably 1-hexylpyridinium cation, 1-ethyl-3-methylpyridinium cation, 1-butyl-3-methylpyridinium cation, 1-octyl-4-methylpyridinium cation, 1-methyl-1-propylpyrrolidinium cation, 1-methyl-1-propylpiperidinium cation.

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

Specific examples of the cation represented by the general formula (2) include, for example, 1,3-dimethylimidazolium cation, 1,3-diethylimidazolium cation, 1-ethyl-3-methylimidazolium cation, 1-Butyl-3-methylimidazolium cation, 1-hexyl-3-methylimidazolium cation, 1-octyl-3-methylimidazolium cation, 1-decyl-3-methylimidazolium cation, 1- dodecyl-3-methylimidazolium cation, 1-tetradecyl-3-methylimidazolium cation, 1,2-dimethyl-3-propylimidazolium cation, 1-ethyl-2,3-dimethylimidazolium imidazolium cations such as cations, 1-butyl-2,3-dimethylimidazolium cations and 1-hexyl-2,3-dimethylimidazolium cations; 1,3-dimethyl-1,4,5,6-tetrahydropyrimidinium cation, 1,2,3-trimethyl-1,4,5,6-tetrahydropyrimidinium cation, 1,2,3, Tetrahydropyri such as 4-tetramethyl-1,4,5,6-tetrahydropyrimidinium cation and 1,2,3,5-tetramethyl-1,4,5,6-tetrahydropyrimidinium cation medium cation; 1,3-dimethyl-1,4-dihydropyrimidinium cation, 1,3-dimethyl-1,6-dihydropyrimidinium cation, 1,2,3-trimethyl-1,4-dihydropyrimidi nium cation, 1,2,3-trimethyl-1,6-dihydropyrimidinium cation, 1,2,3,4-tetramethyl-1,4-dihydropyrimidinium cation, 1,2,3, dihydropyrimidinium cations such as 4-tetramethyl-1,6-dihydropyrimidinium cation; and the like.

Among these, 1,3-dimethylimidazolium cation, 1,3-diethylimidazolium cation, and 1-ethyl-3-methyl are preferably 1,3-dimethylimidazolium cation, from which the effect of the present invention can be further expressed. Midazolium cation, 1-butyl-3-methylimidazolium cation, 1-hexyl-3-methylimidazolium cation, 1-octyl-3-methylimidazolium cation, 1-decyl-3-methylimidazolium imidazolium cations such as a cation, 1-dodecyl-3-methylimidazolium cation, and 1-tetradecyl-3-methylimidazolium cation, more preferably 1-ethyl-3-methylimidazolium cation, 1-hexyl-3-methylimidazolium cation.

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

As a specific example of the cation represented by General formula (3), For example, 1-methylpyrazolium cation, 3-methylpyrazolium cation, 1-ethyl-2-methylpyrazolinium cation, 1-ethyl-2,3 pyrazolium cations such as ,5-trimethylpyrazolium cation, 1-propyl-2,3,5-trimethylpyrazolium cation, and 1-butyl-2,3,5-trimethylpyrazolium cation; Pyra such as 1-ethyl-2,3,5-trimethylpyrazolinium cation, 1-propyl-2,3,5-trimethylpyrazolinium cation, and 1-butyl-2,3,5-trimethylpyrazolinium cation zolinium cation; and the like.

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

As a specific example of the cation represented by General formula (4), For example, tetramethylammonium cation, tetraethylammonium cation, tetrabutylammonium cation, tetrapentylammonium cation, tetrahexylammonium cation, tetraheptylammonium cation, triethylmethyl Ammonium cation, tributylethylammonium cation, trimethylpropylammonium cation, trimethyldecylammonium cation, N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium cation, glycidyltrimethylammonium cation, trimethyl Sulfonium cation, triethylsulfonium cation, tributylsulfonium cation, trihexylsulfonium cation, diethylmethylsulfonium cation, dibutylethylsulfonium cation, dimethyldecylsulfonium cation, tetramethylphosphonium cation, tetraethyl Phosphonium cation, tetrabutylphosphonium cation, tetrahexylphosphonium cation, tetraoctylphosphonium cation, triethylmethylphosphonium cation, tributylethylphosphonium cation, trimethyldecylphosphonium cation, diallyldimethylammonium cation, etc. are mentioned. can

Among these, from the viewpoint of being able to further express the effect of the present invention, preferably triethylmethylammonium cation, tributylethylammonium cation, trimethyldecylammonium cation, diethylmethylsulfonium cation, dibutylethylsulfonium Asymmetric tetraalkylammonium cations, such as cation, dimethyldecylsulfonium cation, triethylmethylphosphonium cation, tributylethylphosphonium cation, trimethyldecylphosphonium cation, trialkylsulfonium cation, tetraalkylphosphonium cation, N ,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium cation, glycidyltrimethylammonium cation, diallyldimethylammonium cation, N,N-dimethyl-N-ethyl-N-propylammonium cation , N,N-dimethyl-N-ethyl-N-butylammonium cation, N,N-dimethyl-N-ethyl-N-pentylammonium cation, N,N-dimethyl-N-ethyl-N-hexylammonium cation, N ,N-dimethyl-N-ethyl-N-heptylammonium cation, N,N-dimethyl-N-ethyl-N-nonylammonium cation, N,N-dimethyl-N,N-dipropylammonium cation, N,N- Diethyl-N-propyl-N-butylammonium cation, N,N-dimethyl-N-propyl-N-pentylammonium cation, N,N-dimethyl-N-propyl-N-hexylammonium cation, N,N-dimethyl -N-propyl-N-heptylammonium cation, N,N-dimethyl-N-butyl-N-hexylammonium cation, N,N-diethyl-N-butyl-N-heptylammonium cation, N,N-dimethyl- N-pentyl-N-hexylammonium cation, N,N-dimethyl-N,N-dihexylammonium cation, trimethylheptylammonium cation, N,N-diethyl-N-methyl-N-propylammonium cation, N,N -diethyl-N-methyl-N-pentylammonium cation, N,N-diethyl-N-methyl-N-heptylammonium cation, N,N-diethyl-N-propyl-N-pentylammonium cation, triethyl Propylammonium 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-Me tyl-N-hexylammonium cation, trioctylmethylammonium cation, N-methyl-N-ethyl-N-propyl-N-pentylammonium cation, etc. are mentioned, More preferably, it is a trimethylpropylammonium cation.

As the fluoroorganic anion capable of constituting the ionic liquid, any suitable fluoroorganic anion can be employed as long as the effects of the present invention are not impaired. Such fluoroorganic anions may be completely fluorinated (perfluorinated) or partially fluorinated.

Examples of such fluoroorganic anions include fluorinated arylsulfonate, perfluoroalkanesulfonate, bis(fluorosulfonyl)imide, bis(perfluoroalkanesulfonyl)imide, cyanoperfluoro Roalkanesulfonylamide, bis(cyano)perfluoroalkanesulfonylmethide, cyano-bis-(perfluoroalkanesulfonyl)methide, tris(perfluoroalkanesulfonyl)methide, trifluoro and acetate, perfluoroalkylate, tris(perfluoroalkanesulfonyl)methide, and (perfluoroalkanesulfonyl)trifluoroacetamide.

Among these fluoroorganic anions, more preferably, they are perfluoroalkylsulfonate, bis(fluorosulfonyl)imide, and bis(perfluoroalkanesulfonyl)imide, and more specifically, for example, , trifluoromethanesulfonate, pentafluoroethanesulfonate, heptafluoropropanesulfonate, nonafluorobutanesulfonate, bis(fluorosulfonyl)imide, bis(trifluoromethanesulfonyl)imide am.

As a specific example of an ionic liquid, it can be used, selecting suitably from the combination of the said cation component and the said anion component. Specific examples of the ionic liquid include 1-hexylpyridiniumbis(fluorosulfonyl)imide, 1-ethyl-3-methylpyridinium trifluoromethanesulfonate, 1-ethyl-3- Methylpyridinium pentafluoroethanesulfonate, 1-ethyl-3-methylpyridinium heptafluoropropanesulfonate, 1-ethyl-3-methylpyridinium nonafluorobutanesulfonate, 1-butyl-3-methylpyri dinium trifluoromethanesulfonate, 1-butyl-3-methylpyridiniumbis(trifluoromethanesulfonyl)imide, 1-butyl-3-methylpyridiniumbis(pentafluoroethanesulfonyl)imide; 1-octyl-4-methylpyridiniumbis(fluorosulfonyl)imide, 1,1-dimethylpyrrolidiniumbis(trifluoromethanesulfonyl)imide, 1-methyl-1-ethylpyrrolidiniumbis (trifluoromethanesulfonyl)imide, 1-methyl-1-propylpyrrolidiniumbis(trifluoromethanesulfonyl)imide, 1-methyl-1-propylpyrrolidiniumbis(fluorosulfonyl) Imid, 1-methyl-1-butylpyrrolidiniumbis(trifluoromethanesulfonyl)imide, 1-methyl-1-pentylpyrrolidiniumbis(trifluoromethanesulfonyl)imide, 1-methyl -1-hexylpyrrolidiniumbis(trifluoromethanesulfonyl)imide, 1-methyl-1-heptylpyrrolidiniumbis(trifluoromethanesulfonyl)imide, 1-ethyl-1-propylpyrroly Diniumbis(trifluoromethanesulfonyl)imide, 1-ethyl-1-butylpyrrolidiniumbis(trifluoromethanesulfonyl)imide, 1-ethyl-1-pentylpyrrolidiniumbis(trifluoro Methanesulfonyl)imide, 1-ethyl-1-hexylpyrrolidiniumbis(trifluoromethanesulfonyl)imide, 1-ethyl-1-heptylpyrrolidiniumbis(trifluoromethanesulfonyl)imide , 1,1-dipropylpyrrolidiniumbis(trifluoromethanesulfonyl)imide, 1-propyl-1-butylpyrrolidiniumbis(trifluoromethanesulfonyl)imide, 1,1-dibutyl Pyrrolidiniumbis(trifluoromethanesulfonyl)imide, 1-propylpiperidiniumbis(trifluoromethanesulfonyl)imide, 1-pentylpiperidiniumbis(trifluoromethanesulfonyl)imide , 1,1-Dimethylpiperidiniumbis(trifluoromethanesulfonyl)imide, 1-methyl-1-ethylpiperidiniumbis(trifluoromethanesulfonyl)imide, 1-methyl-1-propyl Piperidiniumbis(trifluoromethanesulfonyl)imide, 1-methyl-1-propylpiperidi Niumbis(fluorosulfonyl)imide, 1-methyl-1-butylpiperidiniumbis(trifluoromethanesulfonyl)imide, 1-methyl-1-pentylpiperidiniumbis(trifluoromethanesulfonyl) Ponyl)imide, 1-methyl-1-hexylpiperidiniumbis(trifluoromethanesulfonyl)imide, 1-methyl-1-heptylpiperidiniumbis(trifluoromethanesulfonyl)imide, 1 -Ethyl-1-propylpiperidiniumbis(trifluoromethanesulfonyl)imide, 1-ethyl-1-butylpiperidiniumbis(trifluoromethanesulfonyl)imide, 1-ethyl-1-pentyl Piperidinium bis(trifluoromethanesulfonyl)imide, 1-ethyl-1-hexylpiperidiniumbis(trifluoromethanesulfonyl)imide, 1-ethyl-1-heptylpiperidiniumbis(tri Fluoromethanesulfonyl)imide, 1,1-dipropylpiperidiniumbis(trifluoromethanesulfonyl)imide, 1-propyl-1-butylpiperidiniumbis(trifluoromethanesulfonyl)imide De, 1,1-dibutylpiperidiniumbis(trifluoromethanesulfonyl)imide, 1,1-dimethylpyrrolidiniumbis(pentafluoroethanesulfonyl)imide, 1-methyl-1-ethyl Pyrrolidiniumbis(pentafluoroethanesulfonyl)imide, 1-methyl-1-propylpyrrolidiniumbis(pentafluoroethanesulfonyl)imide, 1-methyl-1-butylpyrrolidiniumbis(penta Fluoroethanesulfonyl)imide, 1-methyl-1-pentylpyrrolidiniumbis(pentafluoroethanesulfonyl)imide, 1-methyl-1-hexylpyrrolidiniumbis(pentafluoroethanesulfonyl) Imide, 1-methyl-1-heptylpyrrolidiniumbis(pentafluoroethanesulfonyl)imide, 1-ethyl-1-propylpyrrolidiniumbis(pentafluoroethanesulfonyl)imide, 1-ethyl -1-Butylpyrrolidiniumbis(pentafluoroethanesulfonyl)imide, 1-ethyl-1-pentylpyrrolidiniumbis(pentafluoroethanesulfonyl)imide, 1-ethyl-1-hexylpyrroly Diniumbis(pentafluoroethanesulfonyl)imide, 1-ethyl-1-heptylpyrrolidiniumbis(pentafluoroethanesulfonyl)imide, 1,1-dipropylpyrrolidiniumbis(pentafluoroethane) Sulfonyl)imide, 1-propyl-1-butylpyrrolidiniumbis(pentafluoroethanesulfonyl)imide, 1,1-dibutylpyrrolidiniumbis(pentafluoroethanesulfonyl)imide, 1 -Propylpiperidiniumbis(pentafluoroethanesulfonyl)imide, 1-pentylpiperidiniumbis(pentafluoroethanesulfonyl)imide, 1,1-dimethyl pipe Lidiniumbis(pentafluoroethanesulfonyl)imide, 1-methyl-1-ethylpiperidiniumbis(pentafluoroethanesulfonyl)imide, 1-methyl-1-propylpiperidiniumbis(pentafluoro Loethanesulfonyl)imide, 1-methyl-1-butylpiperidiniumbis(pentafluoroethanesulfonyl)imide, 1-methyl-1-pentylpiperidiniumbis(pentafluoroethanesulfonyl)imide De, 1-methyl-1-hexylpiperidiniumbis(pentafluoroethanesulfonyl)imide, 1-methyl-1-heptylpiperidiniumbis(pentafluoroethanesulfonyl)imide, 1-ethyl- 1-propylpiperidiniumbis(pentafluoroethanesulfonyl)imide, 1-ethyl-1-butylpiperidiniumbis(pentafluoroethanesulfonyl)imide, 1-ethyl-1-pentylpiperidinium Bis(pentafluoroethanesulfonyl)imide, 1-ethyl-1-hexylpiperidiniumbis(pentafluoroethanesulfonyl)imide, 1-ethyl-1-heptylpiperidiniumbis(pentafluoroethane) Sulfonyl)imide, 1,1-dipropylpiperidiniumbis(pentafluoroethanesulfonyl)imide, 1-propyl-1-butylpiperidiniumbis(pentafluoroethanesulfonyl)imide, 1 , 1-dibutylpiperidinium bis(pentafluoroethanesulfonyl)imide, 1-ethyl-3-methylimidazolium trifluoroacetate, 1-ethyl-3-methylimidazolium heptafluorobutyrate; 1-ethyl-3-methylimidazolium trifluoromethanesulfonate, 1-ethyl-3-methylimidazolium heptafluoropropanesulfonate, 1-ethyl-3-methylimidazolium nonafluorobutanesulfonate , 1-ethyl-3-methylimidazoliumbis(trifluoromethanesulfonyl)imide, 1-ethyl-3-methylimidazoliumbis(fluorosulfonyl)imide, 1-ethyl-3-methyl Imidazoliumbis(pentafluoroethanesulfonyl)imide, 1-ethyl-3-methylimidazoliumtris(trifluoromethanesulfonyl)methide, 1-butyl-3-methylimidazoliumtrifluoro Acetate, 1-butyl-3-methylimidazolium heptafluorobutyrate, 1-butyl-3-methylimidazolium trifluoromethanesulfonate, 1-butyl-3-methylimidazolium perfluorobutanesulfonate , 1-Butyl-3-methylimidazoliumbis(trifluoromethanesulfonyl)imide, 1-hexyl-3-methylimidazoliumtrifluoromethanesulfonate, 1-hexyl-3-methylimidazolium Bis(fluorosulfonyl)imide, 1,2-dimethyl-3-propylimidazoliumbis(t Lifluoromethanesulfonyl)imide, 1-ethyl-2,3,5-trimethylpyrazoliumbis(trifluoromethanesulfonyl)imide, 1-propyl-2,3,5-trimethylpyrazoliumbis( Trifluoromethanesulfonyl)imide, 1-butyl-2,3,5-trimethylpyrazoliumbis(trifluoromethanesulfonyl)imide, 1-ethyl-2,3,5-trimethylpyrazoliumbis( Pentafluoroethanesulfonyl)imide, 1-propyl-2,3,5-trimethylpyrazoliumbis(pentafluoroethanesulfonyl)imide, 1-butyl-2,3,5-trimethylpyrazoliumbis( Pentafluoroethanesulfonyl)imide, 1-ethyl-2,3,5-trimethylpyrazolium (trifluoromethanesulfonyl)trifluoroacetamide, 1-propyl-2,3,5-trimethylpyrazolium (trifluoromethanesulfonyl)trifluoroacetamide, 1-butyl-2,3,5-trimethylpyrazolium (trifluoromethanesulfonyl)trifluoroacetamide, trimethylpropylammoniumbis(trifluoromethane Sulfonyl)imide, N,N-dimethyl-N-ethyl-N-propylammoniumbis(trifluoromethanesulfonyl)imide, N,N-dimethyl-N-ethyl-N-butylammoniumbis(trifluoro Romethanesulfonyl)imide, N,N-dimethyl-N-ethyl-N-pentylammoniumbis(trifluoromethanesulfonyl)imide, N,N-dimethyl-N-ethyl-N-hexylammoniumbis( Trifluoromethanesulfonyl)imide, N,N-dimethyl-N-ethyl-N-heptylammoniumbis(trifluoromethanesulfonyl)imide, N,N-dimethyl-N-ethyl-N-nonylammonium Bis(trifluoromethanesulfonyl)imide, N,N-dimethyl-N,N-dipropylammoniumbis(trifluoromethanesulfonyl)imide, N,N-dimethyl-N-propyl-N-butyl Ammoniumbis(trifluoromethanesulfonyl)imide, N,N-dimethyl-N-propyl-N-pentylammoniumbis(trifluoromethanesulfonyl)imide, N,N-dimethyl-N-propyl-N -Hexylammoniumbis(trifluoromethanesulfonyl)imide, N,N-dimethyl-N-propyl-N-heptylammoniumbis(trifluoromethanesulfonyl)imide, N,N-dimethyl-N-butyl -N-Hexylammoniumbis(trifluoromethanesulfonyl)imide, N,N-dimethyl-N-butyl-N-heptylammoniumbis(trifluoromethanesulfonyl)imide, N,N-dimethyl-N -pentyl-N-hexylammoniumbis(trifluoromethanesulfonyl)imide, N,N-dimethyl-N,N-dihexyl Ammonium bis(trifluoromethanesulfonyl)imide, trimethylheptylammoniumbis(trifluoromethanesulfonyl)imide, N,N-diethyl-N-methyl-N-propylammoniumbis(trifluoromethanesulfonyl)imide Ponyl)imide, N,N-diethyl-N-methyl-N-pentylammoniumbis(trifluoromethanesulfonyl)imide, N,N-diethyl-N-methyl-N,N-heptylammoniumbis (trifluoromethanesulfonyl)imide, N,N-diethyl-N-propyl-N-pentylammoniumbis(trifluoromethanesulfonyl)imide, triethylpropylammoniumbis(trifluoromethanesulfonyl) ) imide, triethylpentylammoniumbis(trifluoromethanesulfonyl)imide, triethylheptylammoniumbis(trifluoromethanesulfonyl)imide, N,N-dipropyl-N-methyl-N-ethyl Ammoniumbis(trifluoromethanesulfonyl)imide, N,N-dipropyl-N-methyl-N-pentylammoniumbis(trifluoromethanesulfonyl)imide, N,N-dipropyl-N-butyl -N-Hexylammoniumbis(trifluoromethanesulfonyl)imide, N,N-dipropyl-N,N-dihexylammoniumbis(trifluoromethanesulfonyl)imide, N,N-dibutyl- N-methyl-N-pentylammoniumbis(trifluoromethanesulfonyl)imide, N,N-dibutyl-N-methyl-N-hexylammoniumbis(trifluoromethanesulfonyl)imide, trioctylmethyl Ammoniumbis(trifluoromethanesulfonyl)imide, N-methyl-N-ethyl-N-propyl-N-pentylammoniumbis(trifluoromethanesulfonyl)imide, 1-butylpyridinium (trifluoro Methanesulfonyl)trifluoroacetamide, 1-butyl-3-methylpyridinium (trifluoromethanesulfonyl)trifluoroacetamide, 1-ethyl-3-methylimidazolium (trifluoromethanesulfonyl) ) Trifluoroacetamide, tetrahexylammonium bis(trifluoromethanesulfonyl)imide, diallyldimethylammonium trifluoromethanesulfonate, diallyldimethylammonium bis(trifluoromethanesulfonyl)imide, di Allyldimethylammonium bis(pentafluoroethanesulfonyl)imide, N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium trifluoromethanesulfonate, N,N-diethyl- N-methyl-N-(2-methoxyethyl)ammoniumbis(trifluoromethanesulfonyl)imide, N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammoniumbis(penta Fluoroethanesulfonyl)imide, glycidyltrimethylammonium trifluoromethanesulfonyl Phonate, glycidyltrimethylammonium bis(trifluoromethanesulfonyl)imide, glycidyltrimethylammoniumbis(pentafluoroethanesulfonyl)imide, diallyldimethylammonium bis(trifluoromethanesulfonyl) imide, diallyldimethylbis(pentafluoroethanesulfonyl)imide, lithium bis(trifluoromethanesulfonyl)imide, lithium bis(fluorosulfonyl)imide, and the like.

Among these ionic liquids, more preferably 1-hexylpyridiniumbis(fluorosulfonyl)imide, 1-ethyl-3-methylpyridinium trifluoromethanesulfonate, 1-ethyl-3-methyl Pyridinium pentafluoroethanesulfonate, 1-ethyl-3-methylpyridinium heptafluoropropanesulfonate, 1-ethyl-3-methylpyridinium nonafluorobutanesulfonate, 1-butyl-3-methylpyridinium Trifluoromethanesulfonate, 1-butyl-3-methylpyridiniumbis(trifluoromethanesulfonyl)imide, 1-octyl-4-methylpyridiniumbis(fluorosulfonyl)imide, 1-methyl -1-propylpyrrolidiniumbis(trifluoromethanesulfonyl)imide, 1-methyl-1-propylpyrrolidiniumbis(fluorosulfonyl)imide, 1-methyl-1-propylpiperidiniumbis (trifluoromethanesulfonyl)imide, 1-methyl-1-propylpiperidiniumbis(fluorosulfonyl)imide, 1-ethyl-3-methylimidazoliumtrifluoromethanesulfonate, 1- Ethyl-3-methylimidazoliumheptafluoropropanesulfonate, 1-ethyl-3-methylimidazoliumbis(trifluoromethanesulfonyl)imide, 1-ethyl-3-methylimidazoliumbis(fluoro Rosulfonyl)imide, 1-hexyl-3-methylimidazoliumbis(fluorosulfonyl)imide, trimethylpropylammoniumbis(trifluoromethanesulfonyl)imide, lithium bis(trifluoromethanesulfonyl) phonyl) imide and lithium bis (fluorosulfonyl) imide.

A commercially available ionic liquid may be used, but it is also possible to synthesize|combine it as follows. The method for synthesizing the ionic liquid is not particularly limited as long as the desired ionic liquid is obtained, but in general, it is described in the document "Ionic liquid - the front line and future of development -" (published by CMC Publishing Co., Ltd.) A halide method, a hydroxide method, an acid ester method, a complex formation method, a neutralization method, and the like are used.

For the halide method, the hydroxide method, the acid ester method, the complex formation method, and the neutralization method, the synthesis method will be described using nitrogen-containing onium salt as an example, but other sulfur-containing onium salts, phosphorus-containing onium salts, etc.; Other ionic liquids can be obtained by the same method.

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

The obtained halide is an acid (HA) or salt (MA and M are cations that form a salt with the target anion such as ammonium, lithium, sodium, potassium, etc.) having ^{an anionic structure (A -} ) of an ionic liquid for the purpose; It is made to react, and the target ionic liquid (R ₄ NA) is obtained.

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

_{The target ionic liquid (R 4} NA) is obtained by using the reactions of the reaction formulas (7) to (8) in the same manner as the above halogenation method for the obtained hydroxide.

The acid ester method is a method performed by the reaction as shown in Schemes (9) to (11). First, a tertiary amine (R ₃ N) is reacted with an acid ester to obtain an acid ester (reaction formula (9)) esters of organic acids such as phonic acid and formic acid).

_{The target ionic liquid (R 4} NA) is obtained by using the reactions of the reaction formulas (10) to (11) in the same manner as in the above halogenation method for the obtained acid ester. Moreover, an ionic liquid can also be obtained directly by using methyltrifluoromethanesulfonate, methyltrifluoroacetate, etc. as an acid ester.

The neutralization method is a method performed by a reaction as shown in the reaction formula (12). It can be obtained by reacting a tertiary amine with an organic acid such _{as CF 3} COOH, CF ₃ SO ₃ H, (CF ₃ SO ₂ ) ₂ NH, (CF ₃ SO ₂ ) ₃ CH, (C ₂ F ₅ SO ₂ ) _{2 NH, etc.} there is.

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

The blending amount of the ionic liquid cannot be defined uniformly because it changes depending on the compatibility of the polymer and the ionic liquid to be used, but in general, it is preferably 0.001 parts by weight to 50 parts by weight with respect to 100 parts by weight of the polyurethane-based resin. , More preferably 0.01 parts by weight to 40 parts by weight, still more preferably 0.01 parts by weight to 30 parts by weight, particularly preferably 0.01 parts by weight to 20 parts by weight, most preferably 0.01 parts by weight to 10 parts by weight is wealth 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 very excellent antistatic properties. When the amount of the ionic liquid is less than 0.01 part by weight, there is a fear that sufficient antistatic properties cannot be obtained. When the above compounding amount of the ionic liquid exceeds 50 parts by weight, contamination on the adherend tends to increase.

The urethane-based pressure-sensitive adhesive may contain a modified silicone oil. When the urethane pressure-sensitive adhesive contains the modified silicone oil, the effect of the present invention can be more effectively expressed.

When the urethane pressure-sensitive adhesive contains a modified silicone oil, the content thereof is preferably 0.001 parts by weight to 50 parts by weight, more preferably 0.01 parts by weight to 40 parts by weight, and further Preferably it is 0.01 weight part - 30 weight part, Especially preferably, it is 0.01 weight part - 20 weight part, Most preferably, it is 0.01 weight part - 10 weight part. By adjusting the content rate of the modified silicone oil within the above range, the effect of the present invention can be more effectively expressed.

As the modified silicone oil, any appropriate modified silicone oil can be employed as long as the effects of the present invention are not impaired. As such a modified silicone oil, the modified silicone oil available from Shin-Etsu Chemical Co., Ltd. is mentioned, for example.

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

Examples of the polyether-modified silicone oil include side-chain polyether-modified silicone oil and both terminal polyether-modified silicone oil. Among these, the polyether-modified silicone oil of both terminal type is preferable at the point which can fully express the effect of this invention more effectively.

As the polyurethane-based resin, any appropriate polyurethane-based resin can be employed as long as the effects of the present invention are not impaired. As the polyurethane-based resin, preferably, a polyurethane-based resin obtained from a composition containing a polyol (A) and a polyfunctional isocyanate compound (B), or a urethane prepolymer (C) and a polyfunctional isocyanate compound (B) containing It is a polyurethane-type resin obtained from a composition. By employing the polyurethane-based resin as described above, when the surface protection film is once peeled off from an adherend having a large surface step, and adhered to the adherend again, wettability is improved even when the surface step of the adherend is large. It is excellent, and since it is more excellent in step|step difference followability|trackability, the to-be-adhered body with a surface protection film which can achieve a more fully high adhesion rate can be provided.

Polyurethane-type resin can contain arbitrary appropriate other components in the range which does not impair the effect of this invention. Examples of such other components include resin components other than polyurethane-based resins, tackifiers, inorganic fillers, organic fillers, metal powders, pigments, thin products, softeners, antioxidants, conductive agents, ultraviolet absorbers, antioxidants, and light stabilizers. , a surface lubricant, a leveling agent, a corrosion inhibitor, a heat-resistant stabilizer, a polymerization inhibitor, a lubricant, a solvent, a catalyst, and the like.

The polyurethane-based resin preferably contains a deterioration inhibitor such as an antioxidant, an ultraviolet absorber, or a light stabilizer. When the polyurethane-based resin contains a deterioration inhibitor, the adhesive residue prevention property can be improved, such as it is difficult to generate adhesive residue on the adherend even after being adhered to the adherend and then stored in a warm state. Therefore, in the surface protection film of this invention, it can reduce by the contamination with respect to a to-be-adhered body. The number of deterioration inhibitors may be one, and 2 or more types may be sufficient as them. As a deterioration inhibitor, Especially preferably, it is antioxidant.

As antioxidant, a radical chain inhibitor, a peroxide decomposing agent, etc. are mentioned, for example.

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

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

As a phenolic antioxidant, a monophenolic antioxidant, a bisphenol-type antioxidant, a polymeric type phenolic antioxidant, etc. are mentioned, for example.

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

Examples of the bisphenol-based antioxidant include 2,2'-methylenebis(4-methyl-6-t-butylphenol), 2,2'-methylenebis(4-ethyl-6-t-butylphenol); 4,4'-thiobis(3-methyl-6-t-butylphenol), 4,4'-butylidenebis(3-methyl-6-t-butylphenol), 3,9-bis[1, 1-dimethyl-2-[β-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl]2,4,8,10-tetraoxaspiro[5,5]undecane, etc. can be heard

Examples of the high molecular weight phenolic antioxidant include 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane, 1,3,5-trimethyl-2,4, 6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, tetrakis-[methylene-3-(3',5'-di-t-butyl-4'-hydroxyphenyl) 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, etc. are mentioned.

As the sulfur-based antioxidant, for example, dilauryl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate, distearyl 3,3'-thiodipropionate, etc. can be heard

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

Examples of the ultraviolet absorber include a benzophenone-based ultraviolet absorber, a benzotriazole-based ultraviolet absorber, a salicylic acid-based ultraviolet absorber, an oxalic acid anilide-based ultraviolet absorber, a cyanoacrylate-based ultraviolet absorber, and a triazine-based ultraviolet absorber.

As a benzophenone type|system|group ultraviolet absorber, For example, 2, 4- dihydroxybenzophenone, 2-hydroxy-4- methoxybenzophenone, 2-hydroxy-4- octoxybenzophenone, 2-hydroxy- 4-dodecyloxy benzophenone, 2,2'-dihydroxy-4-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4- Methoxy-5-sulfobenzophenone, bis(2-methoxy-4-hydroxy-5-benzoyl phenyl)methane, etc. are mentioned.

Examples of the benzotriazole-based ultraviolet absorber include 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-5'-tert-butylphenyl)benzotriazole; 2-(2'-hydroxyl-3',5'-di-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5- Chlorobenzotriazole, 2-(2'-hydroxyl-3',5'-di-tert-butylphenyl)5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di -tert-amylphenyl)benzotriazole, 2-(2'-hydroxy-4'-octoxyphenyl)benzotriazole, 2-[2'-hydroxy-3'-(3",4",5 ",6",-tetrahydrophthalimidemethyl)-5'-methylphenyl]benzotriazole, 2,2'methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-( 2H-benzotriazol-2-yl)phenol], [2(2'-hydroxy-5'-methacryloxyphenyl)-2H-benzotriazole, etc. are mentioned.

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

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

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

As the hindered amine light stabilizer, for example, [bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate], bis(1,2,2,6,6-pentamethyl) -4-piperidyl) sebacate, methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacate, and the like.

Examples of the ultraviolet stabilizer include nickelbis(octylphenyl)sulfide, [2,2'-thiobis(4-tert-octylphenolate)]-n-butylamine nickel, nickel complex-3,5-di -tert-butyl-4-hydroxybenzyl-phosphoric acid monoethyrate, nickel- dibutyl dithiocarbamate, benzoate type nitrate, nickel- dibutyl dithiocarbamate, etc. are mentioned.

<Polyurethane-based resin obtained from a composition containing a polyol (A) and a polyfunctional isocyanate compound (B)>

The polyurethane-based resin obtained from the composition containing the polyol (A) and the polyfunctional isocyanate compound (B) is specifically, preferably, by curing the composition containing the polyol (A) and the polyfunctional isocyanate compound (B). It is the polyurethane-type resin obtained.

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

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

As polyol (A), For example, Preferably, polyester polyol, polyether polyol, polycaprolactone polyol, polycarbonate polyol, and a castor oil-type polyol are mentioned. As a polyol (A), More preferably, it is a polyether polyol.

As a polyester polyol, it can obtain by the esterification reaction of a polyol component and an acidic component, for example.

Examples of the polyol component include ethylene glycol, diethylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2-butyl-2-ethyl- 1,3-propanediol, 2,4-diethyl-1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 2 -methyl-1,8-octanediol, 1,8-decanediol, octadecanediol, glycerin, trimethylolpropane, pentaerythritol, hexanetriol, polypropylene glycol, etc. are mentioned. Examples of the acid component include succinic acid, methylsuccinic acid, adipic acid, pimelic acid, azelaic acid, sebacic acid, 1,12-dodecanedioic acid, 1,14-tetradecanedioic acid, dimer acid, 2-methyl- 1,4-cyclohexanedicarboxylic acid, 2-ethyl-1,4-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, isophthalic acid, terephthalic acid, 1,4-naphthalenedicarboxylic acid, 4, 4'-biphenyldicarboxylic acid, these acid anhydrides, etc. are mentioned.

Examples of the polyether polyol include water, low molecular weight polyols (propylene glycol, ethylene glycol, glycerin, trimethylolpropane, pentaerythritol, etc.), bisphenols (bisphenol A, etc.), dihydroxybenzene (catechol, resorcin) , hydroquinone, etc.) as an initiator, and polyether polyols obtained by addition polymerization of alkylene oxides such as ethylene oxide, propylene oxide and butylene oxide. Specifically, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, etc. are mentioned, for example.

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

As polycarbonate polyol, For example, polycarbonate polyol obtained by making the said polyol component and phosgene polycondensate; The polyol component and dicarbonate such as dimethyl carbonate, diethyl carbonate, dipropyl carbonate, diisopropyl carbonate, dibutyl carbonate, ethylbutyl carbonate, ethylene carbonate, propylene carbonate, diphenyl carbonate, and dibenzyl carbonate polycarbonate polyols obtained by transesterifying esters; Copolymerization polycarbonate polyol obtained by using together 2 or more types of said polyol component; polycarbonate polyols obtained by esterifying the various polycarbonate polyols with a carboxyl group-containing compound; polycarbonate polyols obtained by etherifying the above various polycarbonate polyols with a hydroxyl group-containing compound; a polycarbonate polyol obtained by transesterifying the various polycarbonate polyols with an ester compound; polycarbonate polyols obtained by transesterifying the various polycarbonate polyols with a hydroxyl group-containing compound; polyester-based polycarbonate polyols obtained by polycondensation reaction of the various polycarbonate polyols and dicarboxylic acid compounds; copolymerized polyether-based polycarbonate polyols obtained by copolymerizing the various polycarbonate polyols with alkylene oxides; and the like.

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

The number average molecular weight Mn of a polyol (A) becomes like this. Preferably it is 400-20000, More preferably, it is 500-17000, More preferably, it is 600-15000, Especially preferably, it is 800-12000. By adjusting the number average molecular weight Mn of the polyol (A) within the above range, when the surface protection film is once peeled off from an adherend having a large surface step, and adhered to the adherend again, when the surface step of the adherend is large It is also possible to provide an adherend with a surface protection film that is more excellent in wettability and more excellent in step difference followability, which can achieve a sufficiently high adhesion rate.

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

The content of the polyol (A1) in the polyol (A) is preferably 70% by weight or more, more preferably 70% by weight to 100% by weight, and still more preferably 70% by weight to 90% by weight. By adjusting the content ratio of the polyol (A1) in the polyol (A) to be within the above range, when the surface protection film is once peeled from an adherend having a large surface step and then adhered to the adherend again, the surface level difference of the adherend It is possible to provide an adherend with a surface protection film that can achieve a sufficiently high adhesion rate because even when ?

The number average molecular weight Mn of the polyol (A1) is preferably 8000 to 20000, more preferably 8000 to 18000, still more preferably 8500 to 17000, still more preferably 9000 to 16000, particularly preferably 9500 to 15500, and most preferably 10000 to 15000. By adjusting the number average molecular weight Mn of the polyol (A1) within the above range, when the surface protection film is once peeled from an adherend having a large surface step, and then adhered to the adherend again, when the surface step of the adherend is large It is also possible to provide an adherend with a surface protection film that is more excellent in wettability and more excellent in step difference followability, which can achieve a sufficiently high adhesion rate.

The polyol (A) may contain the polyol (A2) whose number average molecular weight Mn which has 3 or more OH groups is 5000 or less. The number of polyols (A2) may be one, and 2 or more types may be sufficient as them. 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 to 3000. When the number average molecular weight Mn of the polyol (A2) deviates from within the above range, there is a fear that particularly, the synergism of the adhesive force over time may increase, and there is a fear that excellent reworkability may not be expressed. The polyol (A2) is preferably a polyol having three OH groups (triol), a polyol having four OH groups (tetraol), a polyol having five OH groups (pentaol), and a polyol having six OH groups ( hexanol).

As the polyol (A2), the 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 (hexanol) is polyol (A) As a content rate in it, Preferably it is 10 weight% or less, More preferably, it is 7 weight% or less, More preferably, it is 6 weight% or less, Especially preferably, it is 5 weight% or less. In the polyol (A), as the polyol (A2), 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 (hexanol) as above By adjusting to the range, it is possible to provide a urethane-based pressure-sensitive adhesive having further excellent transparency.

The content of the polyol (A2) in the polyol (A) is preferably 30 wt% or less, and more preferably 0 wt% to 30 wt%. By adjusting the content ratio of the polyol (A2) in the polyol (A) within the above range, when the surface protection film is once peeled off from an adherend having a large surface step, and then adhered to the adherend again, the surface level difference of the adherend It is possible to provide an adherend with a surface protection film that can achieve a sufficiently high adhesion rate because even when ?

In the polyol (A2), the content ratio of the polyol having 4 or more OH groups and having a number average molecular weight Mn of 5000 or less is preferably less than 10% by weight with respect to the entire polyol (A), more preferably 8% by weight. % or less, more preferably 7 wt% or less, particularly preferably 6 wt% or less, and most preferably 5 wt% or less. If the content ratio of the polyol having 4 or more OH groups and having a number average molecular weight Mn of 5000 or less in the polyol (A2) is 10% by weight or more with respect to the total polyol (A), the urethane pressure-sensitive adhesive tends to whiten, and transparency may decrease there is

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

As the polyfunctional isocyanate compound (B), any appropriate polyfunctional isocyanate compound that can be used in the urethanation reaction can be employed. As such a polyfunctional isocyanate compound (B), a polyfunctional aliphatic type isocyanate compound, a polyfunctional alicyclic type isocyanate, a polyfunctional aromatic type isocyanate compound, etc. are mentioned, for example.

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

Examples of the polyfunctional alicyclic isocyanate compound include 1,3-cyclopentene diisocyanate, 1,3-cyclohexanediisocyanate, 1,4-cyclohexanediisocyanate, isophorone diisocyanate, hydrogenated diphenylmethanedi. Isocyanate, hydrogenated xylylene diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated tetramethylxylylene diisocyanate, etc. are mentioned.

Examples of the polyfunctional aromatic diisocyanate compound include phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,2'-diphenylmethane diisocyanate, 4,4'-di phenylmethane diisocyanate, 4,4'-toluidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, xylylene diisocyanate, etc. can

As a polyfunctional isocyanate compound (B), the trimethylol propane adduct body of the above various polyfunctional isocyanate compounds, the biuret body which reacted with water, the trimer etc. which have an isocyanurate ring are mentioned. Moreover, you may use these together.

The equivalent ratio of the NCO group and the OH group in the polyol (A) and the polyfunctional isocyanate compound (B) is, as NCO group/OH group, preferably 0.3 to 1.0, more preferably 0.3 to 0.9, still more preferably preferably 0.3 to 0.8, particularly preferably 0.3 to 0.7, and most preferably 0.3 to 0.6. By adjusting the equivalent ratio of NCO groups / OH groups within the above range, once the surface protection film is peeled off from the adherend having a large surface step, and then adhered to the adherend again, even when the surface step of the adherend is large, It is possible to provide an adherend with a surface protection film, which is more excellent in wettability and more excellent in step difference followability, which can achieve a sufficiently high adhesion rate.

The content of the polyfunctional isocyanate compound (B) is preferably 2.7 wt% to 8.8 wt%, more preferably 2.7 wt% to 8.0 wt%, based on the polyol (A). , more preferably 2.7 wt% to 7.1 wt%, particularly preferably 2.7 wt% to 6.2 wt%, and most preferably 2.7 wt% to 5.3 wt%. By adjusting the content ratio of the polyfunctional isocyanate compound (B) within the above range, when the surface protection film is once peeled from an adherend having a large surface step, and then adhered to the adherend again, the surface step of the adherend is large. Even in this case, it is possible to provide an adherend with a surface protection film that is more excellent in wettability and more excellent in step difference followability, which can achieve a sufficiently high adhesion rate.

Polyurethane-type resin is specifically, Preferably, it hardens|cures the composition containing a polyol (A) and a polyfunctional isocyanate compound (B), and is obtained.

As a method for obtaining a polyurethane-based resin by curing a composition containing a polyol (A) and a polyfunctional isocyanate compound (B), a urethanation reaction method using bulk polymerization, solution polymerization, etc., within a range that does not impair the effects of the present invention Any suitable method may be employed.

In order to cure the composition containing the polyol (A) and the polyfunctional isocyanate compound (B), a catalyst is preferably used. As such a catalyst, an organometallic compound, a tertiary amine compound, etc. are mentioned, for example.

Examples of the organometallic compound include an iron-based compound, a tin-based compound, a titanium-based compound, a zirconium-based compound, a lead-based compound, a cobalt-based compound, and a zinc-based compound. Among these, an iron-based compound and a tin-based compound are preferable from the viewpoint of the reaction rate and the pot life of the pressure-sensitive adhesive layer.

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

Examples of the tin-based compound include dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin maleate, dibutyltin dilaurate, dibutyltin diacetate, and dibutyltin sulfide. , tributyltin methoxide, tributyltin acetate, triethyltin ethoxide, tributyltin ethoxide, dioctyltin oxide, dioctyltin dilaurate, tributyltin chloride, tributyltin trichloroacetate, 2-ethylhexanoate tin etc. are mentioned.

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

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

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

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

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

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

The number of catalysts may be one, and 2 or more types may be sufficient as them. Moreover, you may use together a catalyst, a crosslinking retarder, etc. The amount of the catalyst is preferably 0.02 wt% to 0.10 wt%, more preferably 0.02 wt% to 0.08 wt%, further preferably 0.02 wt% to 0.06 wt%, with respect to the polyol (A), particularly preferably Preferably, it is 0.02 wt% to 0.05 wt%. By adjusting the amount of the catalyst within the above range, when the surface protection film is once peeled from the adherend having a large surface step and then adhered to the adherend again, even when the surface step of the adherend is large, the wettability is better Moreover, since it is more excellent in step|step difference followability|trackability, the to-be-adhered body with a surface protection film which can achieve a more fully high adhesion rate can be provided.

In the composition containing the polyol (A) and the polyfunctional isocyanate compound (B), any appropriate other components may be included within a range that does not impair the effects of the present invention. Examples of such other components include resin components other than polyurethane-based resins, tackifiers, inorganic fillers, organic fillers, metal powders, pigments, thin products, softeners, antioxidants, conductive agents, ultraviolet absorbers, antioxidants, and light eyes. A tablet, a surface lubricant, a leveling agent, a corrosion inhibitor, a heat-resistant stabilizer, a polymerization inhibitor, a lubricant, a solvent, a catalyst, etc. are mentioned.

<Polyurethane resin obtained from a composition containing a urethane prepolymer (C) and a polyfunctional isocyanate compound (B)>

If the polyurethane-based resin obtained from the composition containing the urethane prepolymer (C) and the polyfunctional isocyanate compound (B) is a polyurethane-based resin obtained by using a so-called “urethane prepolymer” as a raw material, any appropriate polyurethane-based resin is employed. can do.

A polyurethane resin obtained from a composition containing a urethane prepolymer (C) and a polyfunctional isocyanate compound (B) is, for example, a polyurethane polyol as a urethane prepolymer (C) and a polyfunctional isocyanate compound (B) containing Polyurethane-type resin obtained from a composition is mentioned. The number of urethane prepolymers (C) may be one, and 2 or more types may be sufficient as them. The number of polyfunctional isocyanate compounds (B) may be one, and 2 or more types may be sufficient as them.

The polyurethane polyol as the urethane prepolymer (C) is preferably formed by reacting a polyester polyol (a1) and a polyether polyol (a2) with an organic polyisocyanate compound (a3) in the presence of a catalyst or in the absence of a catalyst will be.

As the polyester polyol (a1), any suitable polyester polyol can be used. As such a polyester polyol (a1), the polyester polyol obtained by making an acidic component and a glycol component react is mentioned, for example. As an acid component, terephthalic acid, adipic acid, azelaic acid, sebacic acid, phthalic anhydride, isophthalic acid, trimellitic acid, etc. are mentioned, for example. As the glycol component, for example, ethylene glycol, propylene glycol, diethylene glycol, butylene glycol, 1,6-hexane glycol, 3-methyl-1,5-pentanediol, 3,3'-dimethylolheptane, poly Glycerin, trimethylolpropane, pentaerythritol, etc. are mentioned as oxyethylene glycol, polyoxypropylene glycol, 1, 4- butanediol, neopentyl glycol, butyl ethyl pentanediol, and a polyol component. Examples of the polyester polyol (a1) include a polyester polyol obtained by ring-opening polymerization of lactones such as polycaprolactone, poly(β-methyl-γ-valerolactone), and polyvalerolactone.

As the molecular weight of the polyester polyol (a1), it is possible to use from a low molecular weight to a high molecular weight. As molecular weight of polyester polyol (a1), a number average molecular weight becomes like this. Preferably it is 500-5000. When the number average molecular weight is less than 500, the reactivity becomes high and there exists a possibility that it may become easy to gelatinize. When the number average molecular weight exceeds 5000, the reactivity may become low, and there exists a possibility that the cohesive force of polyurethane polyol itself may become small further. The amount of the polyester polyol (a1) used is preferably 10 to 90 mol% in the polyol constituting the polyurethane polyol.

As the polyether polyol (a2), any appropriate polyether polyol can be used. As such a polyether polyol (a2), for example, water, propylene glycol, ethylene glycol, glycerin, trimethylolpropane, etc. are used as an initiator using low molecular weight polyols such as ethylene oxide, propylene oxide, butylene oxide, tetra Polyether polyol obtained by superposing|polymerizing oxirane compounds, such as hydrofuran, is mentioned. Specific examples of the polyether polyol (a2) include polyether polyols having two or more functional groups, such as polypropylene glycol, polyethylene glycol, and polytetramethylene glycol.

As molecular weight of polyether polyol (a2), it can use from low molecular weight to high molecular weight. As molecular weight of polyether polyol (a2), 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 becomes high, and there is a possibility that gelation becomes easy. When the number average molecular weight exceeds 5000, the reactivity may become low, and there exists a possibility that the cohesive force of polyurethane polyol itself may become small further. The usage-amount of polyether polyol (a2) becomes like this in the polyol which comprises a polyurethane polyol, Preferably it is 20 mol% - 80 mol%.

The polyether polyol (a2) may be partially removed as needed, glycols such as ethylene glycol, 1,4-butanediol, neopentyl glycol, butylethylpentanediol, glycerin, trimethylolpropane, pentaerythritol, ethylenediamine, N - It can be used together by substituting with polyvalent amines, such as aminoethylethanolamine, isophoronediamine, and xylylenediamine.

As the polyether polyol (a2), only a bifunctional polyether polyol may be used, and a polyether polyol having a number average molecular weight of 1000 to 5000 and having at least 3 or more hydroxyl groups in one molecule may be partially or entirely used. . As the polyether polyol (a2), when some or all of the polyether polyol having an average molecular weight of 1000 to 5000 and having at least 3 or more hydroxyl groups in one molecule is used, the balance between adhesive strength and re-peelability can be improved. . In such a polyether polyol, when the number average molecular weight is less than 1000, the reactivity becomes high, and there exists a possibility that it may become easy to gelatinize. Moreover, in such a polyether polyol, when a number average molecular weight exceeds 5000, there exists a possibility that reactivity may become low and the cohesive force of polyurethane polyol itself may become small. The number average molecular weight of such polyether polyol becomes like this. More preferably, it is 2500-3500.

As the organic polyisocyanate compound (a3), any appropriate organic polyisocyanate compound can be used. As such an organic polyisocyanate compound (a3), aromatic polyisocyanate, aliphatic polyisocyanate, aromatic aliphatic polyisocyanate, alicyclic polyisocyanate etc. are mentioned, for example.

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, diinisidine diisocyanate, 4,4 '-diphenyl ether diisocyanate, 4,4',4"-triphenylmethane triisocyanate, etc. are mentioned.

Examples of the aliphatic polyisocyanate include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, and 1,3-butyl Rendiisocyanate, dodecamethylenediisocyanate, 2,4,4-trimethylhexamethylenediisocyanate, etc. are mentioned.

Examples of the aromatic polyisocyanate include ω,ω'-diisocyanate-1,3-dimethylbenzene, ω,ω'-diisocyanate-1,4-dimethylbenzene, ω,ω'-diisocyanate-1, 4-diethylbenzene, 1, 4- tetramethyl xylylene diisocyanate, 1, 3- tetramethyl xylylene diisocyanate, etc. are mentioned.

As an alicyclic polyisocyanate, 3-isocyanate methyl-3, 5, 5- trimethylcyclohexyl isocyanate, 1, 3- cyclopentane diisocyanate, 1, 3- cyclohexane diisocyanate, 1, 4- cyclohexane is, for example. Diisocyanate, methyl-2,4-cyclohexanediisocyanate, methyl-2,6-cyclohexanediisocyanate, 4,4'-methylenebis(cyclohexylisocyanate), 1,4-bis(isocyanatemethyl)cyclohexane; 1,4-bis(isocyanatemethyl)cyclohexane etc. are mentioned.

As an organic polyisocyanate compound (a3), a trimethylol propane adduct body, the biuret body which reacted with water, the trimer etc. which have an isocyanurate ring can also be used together.

Any suitable catalyst can be used as a catalyst which can be used when obtaining a polyurethane polyol. As such a catalyst, a tertiary amine compound, an organometallic compound, etc. are mentioned, for example.

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

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

Examples of the tin-based compound include dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin dimaleate, dibutyltin dilaurate (DBTDL), dibutyltin diacetate, and dibutyltin diacetate. Butyl tin sulfide, tributyl tin sulfide, tributyl tin oxide, tributyl tin acetate, triethyl tin ethoxide, tributyl tin ethoxide, dioctyl tin oxide, tributyl tin chloride, tributyl tin trichloro Acetate, 2-ethyl tin hexanoate, etc. are mentioned.

Examples of the non-tin-based compound include titanium-based compounds such as dibutyl titanium dichloride, tetrabutyl titanate and butoxytitanium trichloride; lead compounds such as lead oleate, lead 2-ethylhexanoate, lead benzoate, and lead naphthenate; iron-based compounds such as iron 2-ethylhexanoate and iron acetylacetonate; cobalt compounds such as cobalt benzoate and cobalt 2-ethylhexanoate; zinc-based compounds such as zinc naphthenate and zinc 2-ethylhexanoate; zirconium-based compounds such as zirconium naphthenate; and the like.

When a catalyst is used to obtain a polyurethane polyol, in a system in which two types of polyols, a polyester polyol and a polyether polyol, exist, because of the difference in their reactivity, in a single catalyst system, gelation or the reaction solution becomes cloudy. problem is likely to occur. Therefore, by using two types of catalysts when obtaining a polyurethane polyol, it becomes easy to control the reaction rate, the selectivity of a catalyst, etc., and this problem can be solved. Examples of the combination of these two catalysts include tertiary amine/organometallic, tin/non-tin, and tin/tin, preferably tin/tin, and more preferably It is a combination of dibutyltin dilaurate and 2-ethyl tin hexanoate. The compounding ratio is, in terms of weight ratio, 2-ethylhexanoate tin/dibutyltin dilaurate, preferably less than 1, more preferably 0.2 to 0.6. When the compounding ratio is 1 or more, there is a possibility that gelation becomes easy due to the balance of catalyst activity.

When using a catalyst when obtaining a polyurethane polyol, the usage-amount of a catalyst becomes like this with respect to the total amount of polyester polyol (a1), polyether polyol (a2), and organic polyisocyanate compound (a3) Preferably 0.01 to 1.0 weight%. am.

When using a catalyst when obtaining a polyurethane polyol, the reaction temperature becomes like this. Preferably it is less than 100 degreeC, More preferably, it is 85 degreeC - 95 degreeC. When it becomes 100 degreeC or more, there exists a possibility that control of a reaction rate and a crosslinked structure may become difficult, and there exists a possibility that it may become difficult to obtain the polyurethane polyol which has a predetermined molecular weight.

When obtaining a polyurethane polyol, it is not necessary to use a catalyst. In that case, reaction temperature becomes like this. Preferably it is 100 degreeC or more, More preferably, it is 110 degreeC or more. Moreover, when obtaining a polyurethane polyol under no catalyst, it is preferable to make it react for 3 hours or more.

As a method for obtaining the polyurethane polyol, for example, 1) a method of adding polyester polyol, polyether polyol, catalyst, and organic polyisocyanate to the flask, 2) adding polyester polyol, polyether polyol, and catalyst to the flask and the method of adding organic polyisocyanate dropwise is mentioned. As a method of obtaining a polyurethane polyol, in controlling reaction, the method of 2) is preferable.

When obtaining a polyurethane polyol, arbitrary appropriate solvents can be used. As such a solvent, methyl ethyl ketone, ethyl acetate, toluene, xylene, acetone etc. are mentioned, for example. Among these solvents, toluene is preferable.

As a polyfunctional isocyanate compound (B), the thing mentioned above can be used.

In the composition containing the urethane prepolymer (C) and the polyfunctional isocyanate compound (B), any appropriate other components can be included within a range that does not impair the effects of the present invention. Examples of such other components include resin components other than polyurethane-based resins, tackifiers, inorganic fillers, organic fillers, metal powders, pigments, thin products, softeners, antioxidants, conductive agents, ultraviolet absorbers, antioxidants, and light eyes. A tablet, a surface lubricant, a leveling agent, a corrosion inhibitor, a heat-resistant stabilizer, a polymerization inhibitor, a lubricant, a solvent, a catalyst, etc. are mentioned.

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

The number average molecular weight Mn of the urethane prepolymer (C) is preferably 1000 to 100000.

The equivalent ratio of the NCO group and the OH group in the urethane prepolymer (C) and the polyfunctional isocyanate compound (B) is preferably 0.3 to 1.0, more preferably 0.3 to 0.9, as NCO group/OH group, More preferably, it is 0.3-0.8, Especially preferably, it is 0.3-0.7, Most preferably, it is 0.3-0.6. By adjusting the equivalent ratio of NCO groups / OH groups within the above range, once the surface protection film is peeled off from the adherend having a large surface step, and then adhered to the adherend again, even when the surface step of the adherend is large, It is possible to provide an adherend with a surface protection film, which is more excellent in wettability and more excellent in step difference followability, which can achieve a sufficiently high adhesion rate.

As for the content rate of a polyfunctional isocyanate compound (B) with respect to a urethane prepolymer (C), Preferably the polyfunctional isocyanate compound (B) is 1.1 weight% - 3.6 weight%, More preferably, it is 1.1 weight% - 3.2 weight% %, more preferably 1.1 wt% to 2.9 wt%, particularly preferably 1.1 wt% to 2.5 wt%, and most preferably 1.1 wt% to 2.1 wt%. By adjusting the content ratio of the polyfunctional isocyanate compound (B) within the above range, when the surface protection film is once peeled from an adherend having a large surface step, and then adhered to the adherend again, the surface step of the adherend is large. Even in this case, it is possible to provide an adherend with a surface protection film that is more excellent in wettability and more excellent in step difference followability, which can achieve a sufficiently high adhesion rate.

≪Base layer≫

As thickness of a base material layer, according to a use, arbitrary appropriate thickness is employable. The thickness of the base 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.

A single layer may be sufficient as a base material layer, and the laminated body of two or more layers may be sufficient as it. The substrate layer may be stretched.

As a material of a base material layer, arbitrary appropriate materials can be employ|adopted according to a use. For example, plastics, paper, a metal film, a nonwoven fabric, etc. are mentioned. Preferably, it is plastic. A base material layer may be comprised from 1 type of material, and may be comprised from 2 or more types of materials. For example, you may be comprised from 2 or more types of plastics.

As said plastics, polyester-type resin, polyamide-type resin, polyolefin resin etc. are mentioned, for example. Examples of the polyester-based resin include polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate. As polyolefin resin, the homopolymer of an olefin monomer, the copolymer of an olefin monomer, etc. are mentioned, for example. Specific examples of the polyolefin-based resin include homopolypropylene; propylene-based copolymers having an ethylene component as a copolymerization component, such as block-based, random-based, and graft-based copolymers; Reactor TPO; ethylene polymers such as low density, high density, linear low density, and ultra low density; Ethylene/propylene copolymer, ethylene/vinyl acetate copolymer, ethylene/methyl acrylate copolymer, ethylene/ethyl acrylate copolymer, ethylene/butyl acrylate copolymer, ethylene/methacrylic acid copolymer, ethylene/methyl methacrylate copolymer ethylene-based copolymers such as; and the like.

The base layer may contain any appropriate additives as needed. As an additive which may be contained in a base material layer, antioxidant, a ultraviolet absorber, a light stabilizer, an antistatic agent, a filler, a pigment, etc. are mentioned, for example. The type, number, and amount of additives that may be contained in the base layer may be appropriately set according to the purpose. In particular, when the material of the base layer is plastic, it is preferable to contain some of the above additives for the purpose of preventing deterioration or the like. From a viewpoint of a weather resistance improvement etc., Especially preferably, antioxidant, a ultraviolet absorber, a light stabilizer, and a filler are mentioned as an additive.

As antioxidant, any suitable antioxidant can be employ|adopted. Examples of such antioxidants include phenol-based antioxidants, phosphorus-based processing heat stabilizers, lactone-based processing thermal stabilizers, sulfur-based heat-resistant stabilizers, and phenol/phosphorus-based antioxidants. The content of the antioxidant is preferably 1% by weight or less, more preferably 0.5% by weight or less, with respect to the base resin of the base layer (when the base layer is a blend, the blend is the base resin), further Preferably it is 0.01 weight% - 0.2 weight%.

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

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

As the filler, any suitable filler can be employed. As such a filler, an inorganic filler etc. are mentioned, for example. Specific examples of the inorganic filler include carbon black, titanium oxide, and zinc oxide. The content of the filler is preferably 20% by weight or less, more preferably 10% by weight or less, with respect to the base resin forming the base layer (when the base layer is a blend, the blend is the base resin), More preferably, it is 0.01 weight% - 10 weight%.

Moreover, as an additive, for the purpose of providing antistatic property, inorganic type antistatic agents, such as surfactant, an inorganic salt, polyhydric alcohol, a metal compound, and carbon, a low molecular weight type, and a high molecular weight type antistatic agent are mentioned preferably. In particular, a high molecular weight antistatic agent and carbon are preferable from a viewpoint of stain|pollution|contamination and adhesive maintenance.

≪Method for producing surface protection film≫

A surface protection film can be manufactured by arbitrary appropriate methods. As such a manufacturing method, for example,

(1) a method of applying a solution of a material for forming the pressure-sensitive adhesive layer or a hot melt solution on the base layer;

(2) a method of transferring the pressure-sensitive adhesive layer applied and formed in a separator type on the base material layer according thereto;

(3) a method of extruding the forming material of the pressure-sensitive adhesive layer on the base layer to form and apply;

(4) a method of extruding the substrate layer and the pressure-sensitive adhesive layer in two or multiple layers;

(5) a method of laminating a pressure-sensitive adhesive layer in a single layer on a base layer or a method of laminating a pressure-sensitive adhesive layer together with a laminate layer in two layers;

(6) a method of laminating a pressure-sensitive adhesive layer and a base material layer-forming material such as a film or a laminate layer in two or multiple layers;

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

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

[Example]

Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited at all to these Examples. In addition, the test and evaluation method in an Example etc. are as follows. In addition, when it describes as "part", unless there is a special notice, "weight part" is meant, and when it describes as "%", it means "weight%" unless there is a special notice.

<Measurement of adhesive force>

A surface protection film with a separator was cut into a size of 25 mm in width and 80 mm in length, the separator was peeled off, and then laminated on an AGS1 polarizing plate (manufactured by Nitto Denko Co., Ltd., width 70 mm, length 100 mm) at a pressure of 0.25 MPa, to obtain an evaluation sample produced. After lamination, (1) left to stand in an environment of 23°C x 50% RH for 30 minutes, (2) left to stand in an environment of 50°C for 1 week, and (3) left to stand in an environment of 60°C x 90% RH for 1 week (4) After standing for one week in an environment of 85 ° C., in each, using a universal tensile tester (Minebea Co., Ltd., product name: TCM-1kNB), peeling rate 300 mm / min, peeling angle 180 The adhesive force at the time of peeling at ° was measured. The measurement was performed in the environment of 23 degreeC x 50%RH.

<Measurement of wetting rate>

The surface protection film with a separator was cut into the magnitude|size of 25 mm in width and 100 mm in length, and it was set as the evaluation sample. An AGS1 polarizing plate (manufactured by Nitto Denko Co., Ltd., width 70 mm, length 100 mm) was used as the adherend, the separator of the evaluation sample was peeled off, and one of the width side ends was fixed to the width side end of the adherend, and not fixed. The time until the 100 mm spread after lifting the edge part of the width side which was not removed and releasing a hand was measured (unit: s/2.5 cm x 10 cm). The speed was calculated from the time taken, and the case where the speed was 5 cm 2 /s or more was denoted by ○, and the case where the velocity was less than 5 cm 2 /s was denoted as ×.

<Measurement of peel electrification voltage>

AGS1 polarizing plate (Nitto Denko), which was attached so that the surface protection film with a separator was cut to a size of 70 mm in width and 130 mm in length, the separator was peeled off, and then exactly overlapped with an acrylic plate (thickness 1 mm, width 70 mm, length 100 mm) that had been statically removed. Co., Ltd. make, width 70mm, length 100mm) was pressed for one reciprocating press with a 2 kg roller. At this time, the surface protection film had protruded from the glass by 30 mm. After leaving it to stand in the environment of 23 degreeC x 50%RH for 1 day, the one end which protruded 30 mm from the glass was fixed to the automatic winding machine, and it peeled so that it might become a peeling angle of 150 degrees and a peeling speed of 10 m/min. And the peeling electrification voltage was measured with the electric potential measuring device (Kasuga Electric Co., Ltd. make, KSD-0103) fixed at the position 10 cm away from the surface protection film. This measurement was performed in the environment of 23 degreeC x 50%RH.

<Measurement of center line average roughness Ra>

AGS1 polarizing plate (manufactured by Nitto Denko Co., Ltd.), an aluminum plate, and an aluminum plate whose surface was rubbed with sandpaper of a predetermined particle size were set on the stage of ZYGO New View 7300 (manufactured by Canon Marketing Japan Co., Ltd.), and the center line average roughness Ra was measured. In addition, the particle size counts of the sandpaper used to rub the aluminum plate were (1) 320 and (2) 100.

<Measurement of adhesion rate when bonding only by its own weight>

An aluminum plate 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.) was prepared, and the surface with a separator cut to the same size as these The separator of the protective film was peeled off, and one of the width-side end portions was fixed to the adherend, the unfixed width-side end portion was lifted, the hand was released, and each adherend was brought into close contact with only the film's own weight. Then, the adhesion area was computed by VHX-100F (Keyence Co., Ltd.), and the adhesion rate (1st time) was computed by adhesion ratio (%) = (adherence area/total area). Moreover, the edge part of the width side which is not fixed was lifted again, and it was made to adhere to each to-be-adhered body only with the dead weight of a film by releasing, and the adhesion rate (2nd time) was computed similarly.

[Example 1]

As a polyol, Preminol S3011 (manufactured by Asahi Glass Co., Ltd., Mn=10000), which is a polyol having three OH groups: 85 parts by weight, Sannics GP-3000, a polyol having three OH groups (manufactured by Sanyo Chemical Co., Ltd.) , Mn = 3000): 13 parts by weight, San Nix GP-1000, a polyol having three OH groups (manufactured by Sanyo Kasei Co., Ltd., Mn = 1000): 2 parts by weight, using 2 parts by weight of a polyfunctional isocyanate compound as a polyfunctional alicyclic compound. Coronate HX (Nippon Polyurethane Kogyo Co., Ltd.) which is an isocyanate compound: 2.7 parts by weight, catalyst (manufactured by Nippon Chemical Industries, Ltd., trade name: ferric acetylacetonate): 0.04 parts by weight, Irganox 1010 (manufactured by BASF) : 0.50 parts by weight, Elexel AS110 (ionic liquid, manufactured by Daiichi Kogyo Seyaku Co., Ltd.): 1.50 parts by weight, KF6004 (polyether-modified silicone, manufactured by Shin-Etsu Chemical Co., Ltd.): 0.01 parts by weight, dilution Ethyl acetate:241 weight part was mix|blended as a solvent, it stirred with a disper, and obtained the urethane type adhesive composition.

The obtained urethane-based pressure-sensitive adhesive composition is applied to a base material "Lumiror S10" (thickness 38 µm, manufactured by Toray Corporation) containing a polyester resin so that the thickness after drying is 10 µm with a fountain roll, and a drying temperature of 130 ° C., a drying time of 30 seconds It was cured under the conditions and dried. In this way, the adhesive layer containing the urethane-type adhesive (1) on a base material was produced.

Then, the silicone-treated surface of the separator containing the 25-micrometer-thick polyester resin which silicone-treated on the surface of the adhesive layer was bonded to the surface of the adhesive layer, and the surface protection film (1) with a separator was obtained.

Next, three types of aluminum plates subjected to roughness measurement with an AGS1 polarizing plate (manufactured by Nitto Denko Co., Ltd., width 70 mm, length 100 mm) and ZYGO New View 7300 (manufactured by Canon Marketing Japan Co., Ltd.) were prepared, and in the same size as these Peel the separator of the cut surface protection film with a separator (1), fix one of the ends on the width side to the adherend, lift the end of the width side that is not fixed, release the hand, and adhere to each adherend only with the film's own weight Thus, adherends (1a) to (1d) with a surface protection film were obtained.

The results are shown in Table 1.

[Examples 2 to 8]

As the polyfunctional isocyanate compound, the polyfunctional alicyclic isocyanate compound, Coronate HX (Nippon Polyurethane Kogyo Co., Ltd.), was changed as shown in Table 1 in the same manner as in Example 1, except that the adherend with a surface protection film " (2a) to (2d)" to "(8a) to (8d)" were obtained.

The results are shown in Table 1.

[Examples 9 to 11]

As the polyfunctional isocyanate compound, the blending amount of Coronate HX (Nippon Polyurethane Kogyo Co., Ltd.), which is a polyfunctional alicyclic isocyanate compound, was changed as shown in Table 2, and further, as shown in Table 2, isopropyl myristate as a fatty acid ester (Gao Co., Ltd.) The same procedure as in Example 1 was carried out, except that 10 parts by weight were blended, trade name: Exepal IPM, Mn = 270), and adherends with surface protection film "(9a) to (9d)" to "(11a)" to (11d)" was obtained.

The results are shown in Table 2.

[Examples 12 to 14]

As the polyfunctional isocyanate compound, the blending amount of Coronate HX (Nippon Polyurethane Kogyo Co., Ltd.), which is a polyfunctional alicyclic isocyanate compound, was changed as shown in Table 2, and further, as shown in Table 2, isopropyl myristic acid as a fatty acid ester (Gao Co., Ltd.) The same procedure as in Example 1 was carried out except that 30 parts by weight were blended, trade name: Exepal IPM, Mn = 270), and adherends with surface protection film "(12a) to (12d)" to "(14a)" to (14d)" was obtained.

The results are shown in Table 2.

[Examples 15 to 17]

As the polyfunctional isocyanate compound, the blending amount of Coronate HX (Nippon Polyurethane Kogyo Co., Ltd.), which is a polyfunctional alicyclic isocyanate compound, is changed as shown in Table 3, and, as shown in Table 3, as a fatty acid ester, cetyl 2-ethylhexanoate (Nissin Oilio Group Co., Ltd. product name: Salacos 816T, Mn = 368): The same procedure as in Example 1 was followed except that 10 parts by weight were blended, and adherends with surface protection film "(15a) to (15d)" to "(17a) to (17d)" were obtained.

The results are shown in Table 3.

[Examples 18 to 20]

As the polyfunctional isocyanate compound, the blending amount of Coronate HX (Nippon Polyurethane Kogyo Co., Ltd.), which is a polyfunctional alicyclic isocyanate compound, is changed as shown in Table 3, and, as shown in Table 3, as a fatty acid ester, cetyl 2-ethylhexanoate (Nissin Oilio Group Co., Ltd. product name: Salacos 816T, Mn = 368): The same procedure as in Example 1 was carried out except that 30 parts by weight were blended, and adherends with surface protection film “(18a) to (18d)” to "(20a) to (20d)" were obtained.

The results are shown in Table 3.

[Example 21]

100 parts by weight of "Cyabain SH-109H" (solid content 54%, fatty acid ester contained, manufactured by Toyo Ink) as a urethane prepolymer, Coronate HX (Nippon Polyurethane Kogyo Co., Ltd.) which is a polyfunctional alicyclic isocyanate compound as a polyfunctional isocyanate compound Shiki Corporation): 1.4 parts by weight, Elexel AS110 (ionic liquid, manufactured by Daiichi Kogyo Seyaku Co., Ltd.): 1.50 parts by weight, KF6004 (polyether modified silicone, manufactured by Shin-Etsu Chemical Co., Ltd.): 0.01 weight Toluene:208 weight part was mix|blended as part and a dilution solvent, and it stirred with a disper, and obtained the urethane type adhesive composition.

The obtained urethane-based pressure-sensitive adhesive composition is applied to a base material "Lumiror S10" (thickness 38 µm, manufactured by Toray Corporation) containing a polyester resin so that the thickness after drying is 10 µm with a fountain roll, and a drying temperature of 130 ° C., a drying time of 30 seconds It was cured under the conditions and dried. In this way, the adhesive layer containing the urethane-type adhesive 21 was produced on the base material.

Then, the silicone-treated surface of the separator containing the 25-micrometer-thick polyester resin which silicone-treated on the surface of the adhesive layer was bonded to the surface of the adhesive layer, and the surface protection film 21 with a separator was obtained.

Next, three types of aluminum plates subjected to roughness measurement with an AGS1 polarizing plate (manufactured by Nitto Denko Co., Ltd., width 70 mm, length 100 mm) and ZYGO New View 7300 (manufactured by Canon Marketing Japan Co., Ltd.) were prepared, and in the same size as these Peel the separator of the cut surface protection film 21 with a separator, fix one of the width side end portions to the adherend, lift the unfixed width side end portion, release the hand, and adhere to each adherend only with the film's own weight Thus, adherends (21a) to (21d) with a surface protection film were obtained.

The results are shown in Table 4.

[Examples 22 to 25]

As the polyfunctional isocyanate compound, the polyfunctional alicyclic isocyanate compound, Coronate HX (Nippon Polyurethane Kogyo Co., Ltd.), was changed as shown in Table 4 in the same manner as in Example 21, except that the adherend with a surface protection film " (22a) to (22d)" to "(25a) to (25d)" were obtained.

The results are shown in Table 4.

[Comparative Examples 1 to 3]

As the polyfunctional isocyanate compound, the polyfunctional alicyclic isocyanate compound, Coronate HX (Nippon Polyurethane Kogyo Co., Ltd.), was changed as shown in Table 5 in the same manner as in Example 1, except that the adherend with a surface protection film " (C1a) to (C1d)" to "(C3a) to (C3d)" were obtained.

The results are shown in Table 5.

[Comparative Example 4]

As the polyfunctional isocyanate compound, the polyfunctional alicyclic isocyanate compound, Coronate HX (Nippon Polyurethane Kogyo Co., Ltd.), was changed as shown in Table 5 in the same manner as in Example 21, except that the adherend with a surface protection film ( C4a) to (C4d) were obtained.

The results are shown in Table 5.

The to-be-adhered body with a surface protection film of this invention can be used for arbitrary appropriate uses. Preferably, the to-be-adhered body with a surface protection film of this invention is used suitably in the field|area of an optical member and an electronic member.

1: base layer
2: adhesive layer
10: surface protection film
100: adherend
1000: an adherend with a surface protection film

Claims (9)

The pressure-sensitive adhesive layer side of the surface protection film including the pressure-sensitive adhesive layer is a member bonded to the surface of the adherend having a center line average roughness Ra of 0.2 µm to 2 µm,
The pressure-sensitive adhesive layer contains 50% to 100% by weight of a urethane-based pressure-sensitive adhesive containing a polyurethane-based resin,
The polyurethane-based resin is a polyurethane-based resin obtained from a composition containing a polyol (A) and a polyfunctional isocyanate compound (B),
In the polyol (A) and the polyfunctional isocyanate compound (B), the equivalent ratio of NCO group and OH group is 0.3 to 0.9 as NCO group/OH group,
The polyol (A) contains 70% by weight to 100% by weight of a polyol (A1) having three OH groups and having a number average molecular weight Mn of 8000 to 20000,
The adhesive layer is an adhesive layer having an adhesion rate of 80% or more when the adhesive layer is bonded only by its own weight to the surface of the adherend,
An adherend with a surface protection film. The adherend with a surface protection film according to claim 1, wherein the polyol (A) has a number average molecular weight Mn of 400 to 20000. The adherend with a surface protection film according to claim 1 or 2, wherein the urethane pressure-sensitive adhesive contains a fatty acid ester. The adherend with a surface protection film according to claim 3, wherein the number average molecular weight Mn of the fatty acid ester is 200 to 400. The pressure-sensitive adhesive layer side of the surface protection film including the pressure-sensitive adhesive layer is a member bonded to the surface of the adherend having a center line average roughness Ra of 0.2 µm to 2 µm,
The pressure-sensitive adhesive layer contains 50% to 100% by weight of a urethane-based pressure-sensitive adhesive containing a polyurethane-based resin,
The polyurethane-based resin is a polyurethane-based resin obtained from a composition containing a urethane prepolymer (C) and a polyfunctional isocyanate compound (B),
In the urethane prepolymer (C) and the polyfunctional isocyanate compound (B), the equivalent ratio of NCO group and OH group is 0.3 to 0.9 as NCO group/OH group,
The urethane-based pressure-sensitive adhesive contains a fatty acid ester,
The adhesive layer is an adhesive layer having an adhesion rate of 80% or more when the adhesive layer is bonded only by its own weight to the surface of the adherend,
An adherend with a surface protection film. The adherend with a surface protection film according to claim 5, wherein the number average molecular weight Mn of the fatty acid ester is 200 to 400. The adherend with a surface protection film according to any one of claims 1, 2, 5, and 6, wherein the adherend is an optical member or an electronic member. delete delete

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