TW201627441A - Surface protection film - Google Patents

Abstract

The present invention provides a surface protection film having excellent wettability and step followability even if it is bonded with an adhered object with large surface step, thereby sufficiently achieving high sealability. This invention also provides an optical member and electronic member adhered with the surface protection film. The surface protection film of this invention contains an adhesive layer which comprises a urethane-based adhesive containing polyurethane-based resin as the main component, such that the adhesive layer, which is self-adhered to the central line, may possess a sealability of 80% or greater simply because of the surface of the adhered object having an average roughness Ra of 0.2 to 2 micron.

Description

Surface protection film

The present invention relates to a surface protective film. The surface protective film of the present invention contains an adhesive layer as a surface protective film of the outermost layer, and the adhesive layer contains a urethane-based adhesive containing a polyurethane resin as a main component. The surface protective film of the present invention is preferably used, for example, for surface protection of an optical member or an electronic member.

In order to prevent surface damage during processing, assembly, inspection, transportation, and the like, the optical member or the electronic member is usually bonded to the exposed surface side. Such a surface protective film is peeled off from an optical member or an electronic member at a point of time when surface protection is not required.

Such a surface protective film is subjected to an assembly step, an inspection step, a transport step, and the like from the manufacturing steps of the optical member or the electronic member until the final release, and the same surface protective film is continuously used in most cases. In this case, such a surface protective film is attached, peeled, and reattached in many cases by manual operation.

When the surface protective film is attached by hand or when a surface protective film is attached to a large adherend, air bubbles may be trapped between the adherend and the surface protective film. Therefore, there have been reports of techniques for improving the wettability of the surface protective film in order to prevent air bubbles from being attached. For example, it is known that an organic tantalum resin having a high wetting rate is used for a surface protective film of an adhesive layer (for example, refer to Patent Document 1).

However, when an organic tantalum resin is used for the adhesive layer, the adhesive component tends to contaminate the adherend, and when used as a surface protective film for protecting the surface of a member requiring particularly low contamination such as an optical member or an electronic member. There is a big problem.

A surface protective film using an acrylic resin for the adhesive layer is known as a surface protective film having less contamination from the adhesive component (see, for example, Patent Document 2). However, the acrylic resin is used for the surface protective film of the adhesive layer, and since it is inferior in wettability, it is sometimes between the adherend and the surface protective film when the surface protective film is attached by hand. Air bubbles will be trapped. In addition, when the acrylic resin is used for the adhesive layer, there is a problem that the residual glue is likely to be generated at the time of peeling, and the surface protective film is used as a surface for protecting a member such as an optical member or an electronic member which is particularly undesirable from being mixed with foreign matter. There is a problem when using it.

In addition, when the surface protective film is attached to the adherend, it is required to have excellent wettability such as initial wettability as described above, and to require light peelability. The reason for this is that the adherend is not damaged at the time of peeling, or is attached to the adherend after peeling again and used as a surface protective film. Even if the wettability is good, if it is peeled off, the adherend will be destroyed when the adherend is thin and fragile, or the surface protective film will be deformed when the surface protective film is peeled off, and it cannot be used as a surface protection again. Membrane use. In order to avoid such a problem, the surface protective film for an optical member or an electronic member is strongly required to have a so-called reworkability in which air bubbles are not trapped, adhesion can be performed several times, and light peeling can be performed without deformation.

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

However, the surface protective film having the adhesive layer containing the urethane-based adhesive has a poor step followability when it is bonded to the adherend having a large surface step, and the high adhesion rate cannot be sufficiently achieved. The problem.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2006-152266

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2004-051825

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2014-111701

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2004-111702

An object of the present invention is to provide a surface protective film which is excellent in wettability and excellent in step followability even when it is bonded to an adherend having a large surface step, so that high adhesion can be sufficiently achieved. rate. Further, an optical member and an electronic member to which such a surface protective film is attached are provided.

The surface protective film of the present invention contains a surface protective film of an adhesive layer containing a urethane-based adhesive containing a polyurethane resin as a main component, and the adhesive layer side is only The adhesion ratio when the surface roughness of the adherend is 0.2 μm to 2 μm by the self-weight is 80% or more.

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

In a preferred embodiment, the polyol (A) has a number average molecular weight Mn of from 400 to 20,000.

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

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

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

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

In a preferred embodiment, the fatty acid ester has a number average molecular weight Mn of from 200 to 400.

The optical member of the present invention is attached with a member of the surface protective film of the present invention.

The electronic component of the present invention is attached with a member of the surface protective film of the present invention.

According to the present invention, it is possible to provide a surface protective film which is excellent in wettability and excellent in step followability even when it is attached to an adherend having a large surface step, so that high adhesion can be sufficiently achieved. rate. Further, an optical member and an electronic member to which such a surface protective film is attached are provided.

1‧‧‧ substrate layer

2‧‧‧Adhesive layer

10‧‧‧Surface protection film

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic cross-sectional view showing a surface protective film according to a preferred embodiment of the present invention.

The surface protective film of the present invention contains an adhesive layer. A release liner having a release property can be attached to the adhesive side of the adhesive layer.

The surface protective film of the present invention is preferably an adhesive layer or an adhesive layer having a releasing release liner attached to the adhesive surface side at the outermost layer.

The surface protective film of the present invention preferably has a substrate layer and an adhesive layer. The base material layer may be only one layer or two or more layers. The surface protective film of the present invention may have any other suitable layer in addition to the base material layer and the pressure-sensitive adhesive layer, without departing from the effects of the present invention.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic cross-sectional view showing a surface protective film in a preferred embodiment of the present invention. The surface protection film 10 is provided with the base material layer 1 and the adhesive layer 2. The surface protective film of the present invention may further have any other suitable layer (not shown) as needed.

The surface of the base material layer 1 to which the pressure-sensitive adhesive layer 2 is not attached may be subjected to mold release treatment by, for example, adding a fatty amide, a polyethyleneimine, a long-chain alkyl-based additive, or the like to the base material layer, or may be provided with organic A coating layer of any suitable release agent such as an oxime system, a long-chain alkyl group or a fluorine-based compound to form a wound body which is easily wound back.

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

The surface protective film of the present invention has an adhesion ratio of 80% or more when the adhesive layer side is bonded to the surface of the adherend having a center line average roughness Ra of 0.2 μm to 2 μm by its own weight. When the adhesive layer side is adhered to the surface of the adherend having a center line average roughness Ra of 0.2 μm to 2 μm by its own weight, the adhesion ratio is 80% or more, and it is possible to provide even a large step difference with the surface. When the adhesive is bonded to the adhesive, the wettability is still excellent, and the step followability is also excellent, so that the surface protective film having a high density can be sufficiently obtained.

In the surface protective film of the present invention, the adhesive layer side is bonded to the surface of the adherend having a center line average roughness Ra of 0.2 μm to 2 μm by self-weight only from the viewpoint of further exhibiting the effect of the present invention. The adhesion ratio is 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%.

With respect to the surface protective film of the present invention, it is possible to further exhibit the effect of the present invention, and the adhesive layer side is adhered only to the surface of the adherend having a center line average roughness Ra of 0.2 μm by its own weight. The rate of occurrence is preferably 80% or more, more preferably 85% or more, still more preferably 88% or more, particularly preferably 90% or more, and most preferably 92% or more. The upper limit of the adhesion ratio is preferably 100%.

With respect to the surface protective film of the present invention, from the viewpoint of further exhibiting the effects of the present invention, the adhesive layer side is bonded to the center line average roughness Ra only by its own weight. The adhesion ratio at the time of the surface of the adherend of 0.3 μm is preferably 80% or more, more preferably 83% or more, still more preferably 86% or more, particularly preferably 88% or more, and most preferably 90% or more. The upper limit of the adhesion ratio is preferably 100%.

With respect to the surface protective film of the present invention, the adhesive layer side can be bonded only to the surface of the adherend having a center line average roughness Ra of 0.8 μm by its own weight. The rate of occurrence is preferably 80% or more, more preferably 82% or more, further 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%.

With respect to the surface protective film of the present invention, it is possible to further exhibit the effect of the present invention, and the adhesive layer side is adhered only to the surface of the adherend having a center line average roughness Ra of 1.1 μm by its own weight. The rate of occurrence is preferably 80% or more, more preferably 82% or more, still more preferably 84% or more, particularly preferably 86% or more, and most preferably 87% or more. The upper limit of the adhesion ratio is preferably 100%.

Adhesive Layer

The adhesive layer contains a urethane-based adhesive containing a polyurethane resin as a main component. The content of the urethane-based adhesive in the adhesive layer is preferably from 50% by weight to 100% by weight, more preferably from 60% by weight to 100% by weight, still more preferably from 70% by weight to 100% by weight, It is particularly preferably from 80% by weight to 100% by weight, most preferably from 90% by weight to 100% by weight. By adjusting the content ratio of the urethane-based adhesive in the adhesive layer to the above range, the surface protective film of the present invention is wetted even when it is bonded to the adherend having a large surface step. The sex is also more excellent, and the step followability is also better, and the high density can be more fully achieved.

As the thickness of the adhesive layer, any appropriate thickness can be employed depending on the application. The thickness of the adhesive layer is preferably from 1 μm to 100 μm, more preferably from 3 μm to 50 μm, even more preferably from 5 μm to 30 μm, from the viewpoint of further exhibiting the effects of the present invention. The surface of the present invention is adjusted by adjusting the thickness of the adhesive layer within the above range When the protective film is bonded to the adherend having a large surface step, the wettability is more excellent, and the step followability is also more excellent, and the high density can be more fully achieved.

The adhesive layer can be made by any suitable manufacturing method. As such a production method, for example, a method in which a composition as a material for forming an adhesive layer is applied onto a base material layer to form an adhesive layer on the base material layer is exemplified. Examples of such a 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 adhesive layer may contain any appropriate other components insofar as it does not impair the effects of the present invention, in addition to the urethane-based adhesive. Examples of such other components include a resin component other than the polyurethane resin, a tackifier, an inorganic filler, an organic filler, a metal powder, a pigment, a foil, a softener, an anti-aging agent, and the like. Conductive agent, ultraviolet absorber, antioxidant, light stabilizer, surface lubricant, leveling agent, preservative, heat stabilizer, polymerization inhibitor, lubricant, solvent, catalyst, and the like.

The content of the polyurethane resin in the urethane-based adhesive is preferably from 50% by weight to 100% by weight, more preferably from 70% by weight to 100% by weight, still more preferably 90% by weight. ~100% by weight, particularly preferably 95% by weight to 100% by weight, most preferably 98% by weight to 100% by weight. By adjusting the content ratio of the polyurethane resin in the urethane-based adhesive within the above range, the surface protective film of the present invention can be bonded to the adherend having a large surface step. In addition, the wettability is also more excellent, and the step followability is also more excellent, so that the high density can be more fully achieved.

The urethane-based adhesive may contain any suitable other components insofar as it does not impair the effects of the present invention, in addition to the polyurethane-based resin. Examples of such other components include a resin component other than the polyurethane resin, a tackifier, an inorganic filler, an organic filler, a metal powder, a pigment, a foil, a softener, an anti-aging agent, and the like. Conductive agent, ultraviolet absorber, antioxidant, light stabilizer, surface lubricant, leveling agent, preservative, heat stabilizer, polymerization inhibitor, lubricant, solvent, catalyst Wait.

The urethane-based adhesive may contain a fatty acid ester. The fatty acid ester may be used alone or in combination of two or more.

The number average molecular weight Mn of the fatty acid ester is preferably from 200 to 400, more preferably from 210 to 395, still more preferably from 230 to 380, particularly preferably from 240 to 360, most preferably from 250 to 350. By adjusting the number average molecular weight Mn of the fatty acid ester within the above range, the wetting speed can be further increased. When the number average molecular weight Mn of the fatty acid ester is too small, the amount of addition is large, and the wetting rate is not improved. When the number average molecular weight Mn of the fatty acid ester is too large, the hardenability of the adhesive deteriorates during drying, which not only adversely affects the wetting property, but also adversely affects the adhesive properties.

As the fatty acid ester, any appropriate fatty acid ester can be employed within the range not impairing the effects of the present invention. Examples of such a fatty acid ester include polyoxyethylene bisphenol A laurate, butyl stearate, 2-ethylhexyl palmitate, 2-ethylhexyl stearate, and behenic acid monoglycerol. Ester, cetyl 2-ethylhexanoate, isopropyl myristate, isopropyl palmitate, cholesteryl isostearate, lauryl methacrylate, coconut fatty acid methyl ester, methyl laurate, Methyl oleate, methyl stearate, myristyl myristate, octyldodecyl myristate, pentaerythritol monooleate, pentaerythritol monostearate, pentaerythritol tetrapalmitate, stearic acid Stearyl ester, isotridecyl stearate, triglyceride 2-ethylhexanoate, butyl laurate, octyl oleate, and the like.

The proportion of the fatty acid ester in the preparation of the urethane-based adhesive is, for example, preferably from 5% by weight to 50% by weight, more preferably from 7% by weight to 45% by weight, based on the polyol (A). It is preferably from 8% by weight to 40% by weight, particularly preferably from 9% by weight to 35% by weight, most preferably from 10% by weight to 30% by weight.

The urethane-based adhesive may contain an ionic liquid containing a fluoroorganic anion. By allowing the urethane-based pressure-sensitive adhesive to contain an ionic liquid containing a fluorine organic anion, it is possible to provide a urethane-based pressure-sensitive adhesive which is excellent in antistatic property. Ionic liquids can only One type may be used in two or more types.

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

As the ionic liquid, any suitable ionic liquid can be employed as long as it is an ionic liquid containing a fluorine organic anion within a range not impairing the effects of the present invention. As such an ionic liquid, an ionic liquid composed of a fluorine organic anion and a phosphonium cation is preferable. By using an ionic liquid composed of a fluorine organic anion and a phosphonium cation as an ionic liquid, it is possible to provide a urethane-based pressure-sensitive adhesive which is excellent in antistatic property.

As the phosphonium cation which can constitute an ionic liquid, any suitable phosphonium cation can be employed within a range not impairing the effects of the present invention. The phosphonium cation is preferably at least one selected from the group consisting of a nitrogen-containing phosphonium cation, a sulfur-containing phosphonium cation, and a phosphorus-containing phosphonium cation. By selecting these phosphonium cations, it is possible to provide a urethane-based adhesive which is excellent in antistatic property.

The phosphonium cation which can constitute an ionic liquid is preferably at least one selected from the group consisting of cations having a structure represented by the general formulae (1) to (5).

In the formula (1), Ra represents a hydrocarbon group having 4 to 20 carbon atoms and may contain a hetero atom, and Rb and Rc are the same or different and represent hydrogen or a hydrocarbon group having 1 to 16 carbon atoms, and may contain a hetero atom. Wherein, in the case where the nitrogen atom has a double bond, Rc is not contained.

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

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

In the formula (4), Z represents a nitrogen atom, a sulfur atom or a phosphorus atom, and R1, Rm, Rn and Ro are the same or different and each represents a hydrocarbon group having 1 to 20 carbon atoms and may contain a hetero atom. Wherein, when Z is a sulfur atom, it does not contain Ro.

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

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

Specific examples of the cation represented by the formula (1) include 1-ethylpyridinium cation, 1-butylpyridinium cation, 1-hexylpyridinium cation, and 1-ethyl-3-methylpyridine. Ruthenium cation, 1-butyl-3-methylpyridinium cation, 1-hexyl-3-methylpyridinium cation, 1-butyl-4-methylpyridinium cation, 1-octyl-4-methyl a pyridinium cation, a 1-butyl-3,4-dimethylpyridinium cation, a pyridinium cation such as a 1,1-dimethylpyrrolidinium cation; a 1-ethyl-1-methylpyrrolidinium cation; 1-methyl-1-propylpyrrolidinium cation, 1-methyl-1-butylpyrrolidinium cation, 1-methyl-1-pentylpyrrolidinium cation, 1-methyl-1-hexyl Pyrrolidinium cation, 1-methyl-1-heptylpyrrolidinium cation, 1-ethyl-1-propylpyrrolidinium cation, 1-ethyl-1-butylpyrrolidinium cation, 1-B a -1-pentylpyrrolidinium cation, a 1-ethyl-1-hexylpyrrolidinium cation, a 1-ethyl-1-heptylpyrrolidinium cation, a 1,1-dipropylpyrrolidinium cation, 1-propyl-1-butylpyrrolidinium cation, 1,1-dibutylpyrrolidine Pyridinium cation; 1-propyl acridine cation, 1-pentyl acridine cation, 1-methyl-1-ethyl acridine cation, 1-methyl-1-propyl acridine Ruthenium cation, 1-methyl-1-butylacridinium cation, 1-methyl-1-pentylacridinium cation, 1-methyl-1-hexylacridinium cation, 1-methyl-1 a heptyl acridine cation, a 1-ethyl-1-propyl acridine cation, a 1-ethyl-1-butyl acridine cation, a 1-ethyl-1-pentyl acridine cation, 1-ethyl-1-hexylacridinium cation, 1-ethyl-1-heptylacridinium cation, 1-propyl-1-butylacridine Acridine cations such as phosphonium cation, 1,1-dimethyl acridine cation, 1,1-dipropyl acridine cation, 1,1-dibutyl acridine cation; 2-methyl-1 - pyrroline cation; 1-ethyl-2-phenylindole cation; 1,2-dimethylhydrazine cation; 1-ethylcarbazole cation, and the like.

Among these, in terms of further expressing the effects of the present invention, preferred are 1-ethylpyridinium cations, 1-butylpyridinium cations, 1-hexylpyridinium cations, 1-B. 3-methylpyridinium cation, 1-butyl-3-methylpyridinium cation, 1-hexyl-3-methylpyridinium cation, 1-butyl-4-methylpyridinium cation, 1- Pyridinium cation such as octyl-4-methylpyridinium cation; 1-ethyl-1-methylpyrrolidinium cation, 1-methyl-1-propylpyrrolidinium cation, 1-methyl-1- Butylpyrrolidinium cation, 1-methyl-1-pentylpyrrolidinium cation, 1-methyl-1-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-hexylpyrrolidine a pyrrolidinium cation such as a phosphonium cation or a 1-ethyl-1-heptylpyrrolidinium cation; a 1-methyl-1-ethylacridinium cation, a 1-methyl-1-propyl acridine cation; 1-methyl-1-butylacridinium cation, 1-methyl-1-pentyl Acridine cation, 1-methyl-1-hexylacridinium cation, 1-methyl-1-heptylacridinium cation, 1-ethyl-1-propyl acridine cation, 1-ethyl -1-butyl acridine cation, 1-ethyl-1-pentylacridinium cation, 1-ethyl-1-hexylacridinium cation, 1-ethyl-1-heptylacridinium cation And an acridinium cation such as a 1-propyl-1-butylacridinium cation, etc., more preferably a 1-hexylpyridinium cation, a 1-ethyl-3-methylpyridinium cation, or a 1-butyl- 3-methylpyridinium cation, 1-octyl-4-methylpyridinium cation, 1-methyl-1-propylpyrrolidinium cation, 1-methyl-1-propyl acridine cation.

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

Specific examples of the cation represented by the formula (2) include, for example, 1,3-dimethylimidazole. Ruthenium 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-mercapto-3-methylimidazolium cation, 1-dodecyl-3-methylimidazolium cation, 1-tetradecyl- 3-methylimidazolium cation, 1,2-dimethyl-3-propylimidazolium cation, 1-ethyl-2,3-dimethylimidazolium cation, 1-butyl-2,3-di Imidazolium cations such as methylimidazolium cations, 1-hexyl-2,3-dimethylimidazolium cations; 1,3-dimethyl-1,4,5,6-tetrahydropyrimidinium cations, 1,2 , 3-trimethyl-1,4,5,6-tetrahydropyrimidinium cation, 1,2,3,4-tetramethyl-1,4,5,6-tetrahydropyrimidinium cation, 1,2 a tetrahydropyrimidinium cation such as a 3,5-tetramethyl-1,4,5,6-tetrahydropyrimidinium cation; a 1,3-dimethyl-1,4-dihydropyrimidinium cation, 1,3 - dimethyl-1,6-dihydropyrimidinium cation, 1,2,3-trimethyl-1,4-dihydropyrimidinium cation, 1,2,3-trimethyl-1,6-di Hydroquinone cation, 1,2,3,4-tetramethyl-1,4-dihydropyrimidinium cation, 1,2,3,4-tetra A dihydropyrimidinium cation such as a keto-1,6-dihydropyrimidinium cation or the like.

Among these, 1,3-dimethylimidazolium cation, 1,3-diethylimidazolium cation, 1-ethyl-3 are preferred in terms of the effect of the present invention. -methylimidazolium cation, 1-butyl-3-methylimidazolium cation, 1-hexyl-3-methylimidazolium cation, 1-octyl-3-methylimidazolium cation, 1-mercapto- An imidazolium cation such as a 3-methylimidazolium cation, a 1-dodecyl-3-methylimidazolium cation or a 1-tetradecyl-3-methylimidazolium cation, more preferably 1-ethyl- 3-methylimidazolium cation, 1-hexyl-3-methylimidazolium cation.

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

Specific examples of the cation represented by the formula (3) include 1-methylpyrazolium cation, 3-methylpyrazolium cation, and 1-ethyl-2-methylpyrazolinium cation. 1-ethyl-2,3,5-trimethylpyrazolium cation, 1-propyl-2,3,5-trimethylpyrazolium cation, 1-butyl-2,3,5-three Pyrazolium cations such as methylpyrazole cations; 1-ethyl-2,3,5-three Pyrazoles such as methylpyrazolium cation, 1-propyl-2,3,5-trimethylpyrazolinium cation, 1-butyl-2,3,5-trimethylpyrazolinium cation A porphyrin cation or the like.

Examples of the cation represented by the formula (4) include a tetraalkylammonium cation, a trialkylsulfonium cation, a tetraalkylphosphonium cation, or a part of the above alkyl group via an alkenyl group or an alkoxy group, and further an epoxy group. Substituted cations, etc.

Specific examples of the cation represented by the formula (4) include a tetramethylammonium cation, a tetraethylammonium cation, a tetrabutylammonium cation, a tetraamylammonium cation, a tetrahexylammonium cation, and a tetraheptyl ammonium. Cationic, triethylmethylammonium cation, tributylethylammonium cation, trimethylpropylammonium cation, trimethylsulfonium ammonium cation, N,N-diethyl-N-methyl-N-( 2-methoxyethyl)ammonium cation, glycidyl trimethylammonium cation, trimethylsulfonium cation, triethylsulfonium cation, tributylphosphonium cation, trihexylphosphonium cation, diethylmethylphosphonium cation , dibutylethyl phosphonium cation, dimethyl decyl sulfonium cation, tetramethyl phosphonium cation, tetraethyl phosphonium cation, tetrabutyl phosphonium cation, tetrahexyl phosphonium cation, tetraoctyl phosphonium cation, triethyl methyl a ruthenium cation, a tributylethyl phosphonium cation, a trimethylsulfonium cation, a diallyldimethylammonium cation, or the like.

Among these, among the aspects which can further exhibit the effects of the present invention, preferred are triethylmethylammonium cation, tributylethylammonium cation, trimethylsulfonium ammonium cation, and diethyl Asymmetric four such as methyl sulfonium cation, dibutyl ethyl sulfonium cation, dimethyl decyl sulfonium cation, triethylmethyl phosphonium cation, tributyl ethyl phosphonium cation, trimethyl fluorenyl ruthenium cation Alkyl ammonium cation, trialkyl phosphonium cation, tetraalkyl phosphonium cation, or N,N-diethyl-N-methyl-N-(2-methoxyethyl) ammonium cation, glycidyl trimethyl Alkyl ammonium cation, diallyldimethylammonium cation, N,N-dimethyl-N-ethyl-N-propyl ammonium cation, N,N-dimethyl-N-ethyl-N-butyl Alkyl ammonium cation, N,N-dimethyl-N-ethyl-N-pentyl ammonium cation, N,N-dimethyl-N-ethyl-N-hexyl ammonium cation, N,N-dimethyl -N-ethyl-N-heptyl ammonium cation, N,N-dimethyl-N-ethyl-N-decyl ammonium cation, N,N-dimethyl-N,N-dipropyl ammonium cation ,N,N-Diethyl-N-propyl-N- Butyl ammonium cation, N,N-dimethyl-N-propyl-N-amyl ammonium cation, N,N-dimethyl-N-propyl-N-hexylammonium cation, N,N-dimethyl --N-propyl-N-heptyl ammonium cation, N,N-dimethyl-N-butyl-N-hexylammonium cation, N,N-diethyl-N-butyl-N-heptyl Ammonium cation, N,N-dimethyl-N-pentyl-N-hexylammonium cation, N,N-dimethyl-N,N-dihexyl ammonium cation, trimethylheptyl ammonium cation, N,N -Diethyl-N-methyl-N-propylammonium cation, N,N-diethyl-N-methyl-N-amylammonium cation, N,N-diethyl-N-methyl- N-heptyl ammonium cation, N,N-diethyl-N-propyl-N-pentyl ammonium cation, triethyl propyl ammonium cation, triethyl amyl ammonium cation, triethylheptyl ammonium cation , N,N-dipropyl-N-methyl-N-ethylammonium cation, N,N-dipropyl-N-methyl-N-amylammonium cation, N,N-dipropyl-N -butyl-N-hexylammonium cation, N,N-dipropyl-N,N-dihexyl ammonium cation, N,N-dibutyl-N-methyl-N-amyl ammonium cation, N,N -dibutyl-N-methyl-N-hexylammonium cation, trioctylmethylammonium cation, N-methyl-N-ethyl-N-propyl-N-amyl ammonium cation, etc. Best propyl trimethyl ammonium cation.

As the fluoroorganic anion capable of constituting the ionic liquid, any appropriate fluorine organic anion can be employed within the range not impairing the effects of the present invention. Such fluoroorganic anions may be fully fluorinated (perfluorinated) or partially fluorinated.

Examples of such a fluorine organic anion include a fluorinated aryl sulfonate, a perfluoroalkanesulfonate, bis(fluorosulfonyl) quinone imide, and bis(perfluoroalkanesulfonyl) fluorene imine. , cyano perfluoroalkanesulfonamide, bis(cyano)perfluoroalkanesulfonium methoxide, cyano-bis-(perfluoroalkanesulfonyl)methide, tris(perfluoroalkanesulfonyl) A methide, a trifluoroacetate, a perfluoroalkylate, a tris(perfluoroalkanesulfonyl)methide, or a (perfluoroalkanesulfonyl)trifluoroacetamide.

Among these fluorine organic anions, more preferred are perfluoroalkyl sulfonate, bis(fluorosulfonyl) ruthenium, bis(perfluoroalkanesulfonyl) quinone imine, and more specifically, for example, Is trifluoromethanesulfonate, pentafluoroethanesulfonate, heptafluoropropanesulfonate, nonafluorobutanesulfonate, bis(fluorosulfonyl)indolide, bis(trifluoromethanesulfonyl)anthracene Imine.

Specific examples of the ionic liquid can be appropriately selected from the combination of the above cationic component and the above anionic component. Specific examples of such an ionic liquid include 1-hexylpyridinium bis(fluorosulfonyl) quinone imine, 1-ethyl-3-methylpyridinium trifluoromethanesulfonate, and 1- Ethyl-3-methylpyridinium pentafluoroethanesulfonate, 1-ethyl-3-methylpyridinium heptafluoropropanesulfonate, 1-ethyl-3-methylpyridinium nonafluorobutanesulfonic acid Salt, 1-butyl-3-methylpyridinium trifluoromethanesulfonate, 1-butyl-3-methylpyridinium bis(trifluoromethanesulfonyl) quinone imine, 1-butyl-3 -methylpyridinium bis(pentafluoroethanesulfonyl) quinone imine, 1-octyl-4-methylpyridinium bis(fluorosulfonyl) quinone imine, 1,1-dimethylpyrrolidinium Bis(trifluoromethanesulfonyl) quinone imine, 1-methyl-1-ethylpyrrolidinium bis(trifluoromethanesulfonyl) quinone imine, 1-methyl-1-propylpyrrolidinium Bis(trifluoromethanesulfonyl) quinone imine, 1-methyl-1-propylpyrrolidinium bis(fluorosulfonyl) quinone imine, 1-methyl-1-butylpyrrolidinium bis ( Trifluoromethanesulfonyl) quinone imine, 1-methyl-1-pentylpyrrolidinium bis(trifluoromethanesulfonyl) quinone imine, 1-methyl-1-hexylpyrrolidinium bis (three Fluoromethanesulfonyl) quinone imine, 1-methyl-1-heptylpyrrolidinium bis(trifluoromethyl) Indenylamine, 1-ethyl-1-propylpyrrolidinium bis(trifluoromethanesulfonyl) quinone imine, 1-ethyl-1-butylpyrrolidinium bis(trifluoromethanesulfonate Indole, fluorene imine, 1-ethyl-1-pentylpyrrolidinium bis(trifluoromethanesulfonyl) quinone imine, 1-ethyl-1-hexylpyrrolidinium bis(trifluoromethanesulfonate) Iridium imine, 1-ethyl-1-heptylpyrrolidinium bis(trifluoromethanesulfonyl) quinone imine, 1,1-dipropylpyrrolidinium bis(trifluoromethanesulfonyl) Yttrium imine, 1-propyl-1-butylpyrrolidinium bis(trifluoromethanesulfonyl) quinone imine, 1,1-dibutylpyrrolidinium bis(trifluoromethanesulfonyl)pyrene Amine, 1-propyl acridine bis(trifluoromethanesulfonyl) quinone imine, 1-pentyl acridine bis(trifluoromethanesulfonyl) quinone imine, 1,1-dimethylhydrazine Pyridinium bis(trifluoromethanesulfonyl) quinone imine, 1-methyl-1-ethylacridinium bis(trifluoromethanesulfonyl) quinone imine, 1-methyl-1-propyl hydrazine Pyridinium bis(trifluoromethanesulfonyl) quinone imine, 1-methyl-1-propyl acridine bis(fluorosulfonyl) quinone imine, 1-methyl-1-butylpyridinium Bis(trifluoromethanesulfonyl) quinone imine, 1-methyl-1-pentylacridinium bis(trifluoromethanesulfonyl) quinone imine, 1-methyl-1-hexyl Acridine bis(trifluoromethanesulfonyl) quinone imine, 1-methyl-1-heptylacridinium bis(trifluoromethanesulfonyl) quinone imine, 1-ethyl-1-propyl Acridine (Trifluoromethanesulfonyl) quinone imine, 1-ethyl-1-butyl acridine bis(trifluoromethanesulfonyl) quinone imine, 1-ethyl-1-pentyl acridine fluorene (Trifluoromethanesulfonyl) quinone imine, 1-ethyl-1-hexylacridinium bis(trifluoromethanesulfonyl) quinone imine, 1-ethyl-1-heptylpyridinium bis ( Trifluoromethanesulfonyl) quinone imine, 1,1-dipropyl acridine bis(trifluoromethanesulfonyl) quinone imine, 1-propyl-1-butyl acridine bis(trifluoro Methanesulfonyl) quinone imine, 1,1-dibutyl acridine bis(trifluoromethanesulfonyl) quinone imine, 1,1-dimethylpyrrolidinium bis(pentafluoroethanesulfonyl)醯imino, 1-methyl-1-ethylpyrrolidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-methyl-1-propylpyrrolidinium bis(pentafluoroethanesulfonyl)醯imino, 1-methyl-1-butylpyrrolidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-methyl-1-pentylpyrrolidinium bis(pentafluoroethanesulfonyl)醯imino, 1-methyl-1-hexylpyrrolidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-methyl-1-heptylpyrrolidinium bis(pentafluoroethanesulfonyl) Yttrium imine, 1-ethyl-1-propylpyrrolidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-ethyl-1-butylpyrrolidinium bis(pentafluoro Sulfhydryl) quinone imine, 1-ethyl-1-pentylpyrrolidinium bis(pentafluoroethanesulfonyl) quinone imine, 1-ethyl-1-hexylpyrrolidinium bis(pentafluoroethanesulfonate Indenylamine, 1-ethyl-1-heptylpyrrolidinium bis(pentafluoroethanesulfonyl) quinone imine, 1,1-dipropylpyrrolidinium bis(pentafluoroethanesulfonyl)醯imino, 1-propyl-1-butylpyrrolidinium bis(pentafluoroethanesulfonyl) quinone imine, 1,1-dibutylpyrrolidinium bis(pentafluoroethanesulfonyl)anthracene Imine, 1-propyl acridine bis(pentafluoroethanesulfonyl) quinone imine, 1-pentyl acridine bis(pentafluoroethanesulfonyl) quinone imine, 1,1-dimethyl Acridine bis(pentafluoroethanesulfonyl) quinone imine, 1-methyl-1-ethyl acridine bis(pentafluoroethanesulfonyl) quinone imine, 1-methyl-1-propyl Acridine bis(pentafluoroethanesulfonyl) quinone imine, 1-methyl-1-butyl acridine bis(pentafluoroethanesulfonyl) quinone imine, 1-methyl-1-pentyl Acridine bis(pentafluoroethanesulfonyl) quinone imine, 1-methyl-1-hexylacridinium bis(pentafluoroethanesulfonyl) quinone imine, 1-methyl-1-heptyl hydrazine Pyridinium bis(pentafluoroethanesulfonyl) quinone imine, 1-ethyl-1-propyl acridine bis(pentafluoroethanesulfonyl) quinone imine, 1-ethyl-1- Acridine bis(pentafluoroethanesulfonyl) quinone imine, 1-ethyl-1-pentyl acridine bis(pentafluoroethanesulfonyl) quinone imine, 1-ethyl-1-hexyl Acridine bis(pentafluoroethanesulfonyl) quinone imine, 1-ethyl-1-heptyl acridine bis(pentafluoroethanesulfonyl) quinone imine, 1,1-dipropyl acridine Bis(pentafluoroethanesulfonyl) quinone imine, 1-propyl-1-butyl acridine bis(pentafluoroethanesulfonyl) quinone imine, 1,1-dibutyl acridine quinone (pentafluoroethanesulfonyl) quinone imine, 1-ethyl-3-methylimidazolium trifluoroacetate, 1-ethyl-3-methylimidazolium heptafluorobutyrate, 1-ethyl- 3-methylimidazolium trifluoromethanesulfonate, 1-ethyl-3-methylimidazolium heptafluoropropanesulfonate, 1-ethyl-3-methylimidazolium nonafluorobutanesulfonate, 1 -ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl) quinone imine, 1-ethyl-3-methylimidazolium bis(fluorosulfonyl) quinone imine, 1-ethyl- 3-methylimidazolium bis(pentafluoroethanesulfonyl) quinone imine, 1-ethyl-3-methylimidazolium tris(trifluoromethanesulfonyl)methide, 1-butyl-3- Methylimidazolium trifluoroacetate, 1-butyl-3-methylimidazolium heptafluorobutyrate, 1-butyl-3-methylimidazolium trifluoromethanesulfonate, 1-butyl-3 -methylimidazolium perfluorobutanesulfonate, 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl) quinone imine, 1-hexyl-3-methylimidazolium trifluoromethanesulfonate Acid salt, 1-hexyl-3-methylimidazolium bis(fluorosulfonyl) quinone imine, 1,2-dimethyl-3-propylimidazole Bis(trifluoromethanesulfonyl) quinone imine, 1-ethyl-2,3,5-trimethylpyrazolium bis(trifluoromethanesulfonyl) quinone imine, 1-propyl-2, 3,5-trimethylpyrazolium bis(trifluoromethanesulfonyl) quinone imine, 1-butyl-2,3,5-trimethylpyrazolium bis(trifluoromethanesulfonyl)anthracene Imine, 1-ethyl-2,3,5-trimethylpyrazolium bis(pentafluoroethanesulfonyl) quinone imine, 1-propyl-2,3,5-trimethylpyrazolium Bis(pentafluoroethanesulfonyl) quinone imine, 1-butyl-2,3,5-trimethylpyrazolium bis(pentafluoroethanesulfonyl) quinone imine, 1-ethyl-2, 3,5-trimethylpyrazolium (trifluoromethanesulfonyl) trifluoroacetamide, 1-propyl-2,3,5-trimethylpyrazolium (trifluoromethanesulfonyl) Fluoroacetamide, 1-butyl-2,3,5-trimethylpyrazolium (trifluoromethanesulfonyl)trifluoroacetamide, trimethylpropylammonium bis(trifluoromethanesulfonyl)醯imino, N,N-dimethyl-N-ethyl-N-propylammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-dimethyl-N-ethyl-N -butylammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-dimethyl-N-ethyl-N-pentyl ammonium bis(trifluoromethanesulfonyl) quinone imine, N, N-Dimethyl-N-ethyl-N-hexyl ammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-dimethyl -N-ethyl-N-heptyl ammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-dimethyl-N-ethyl-N-decyl ammonium bis(trifluoromethanesulfonyl)醯imino, N,N-dimethyl-N,N-dipropylammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-dimethyl-N-propyl-N-butyl Alkyl ammonium double (three Fluoromethanesulfonyl) quinone imine, N,N-dimethyl-N-propyl-N-pentyl ammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-dimethyl-N -propyl-N-hexyl ammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-dimethyl-N-propyl-N-heptyl ammonium bis(trifluoromethanesulfonyl) fluorene Amine, N,N-dimethyl-N-butyl-N-hexylammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-dimethyl-N-butyl-N-heptyl ammonium Bis(trifluoromethanesulfonyl) quinone imine, N,N-dimethyl-N-pentyl-N-hexyl ammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-dimethyl -N,N-dihexyl ammonium bis(trifluoromethanesulfonyl) quinone imine, trimethylheptyl ammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-diethyl-N- Methyl-N-propylammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-diethyl-N-methyl-N-pentyl ammonium bis(trifluoromethanesulfonyl) fluorene Amine, N,N-diethyl-N-methyl-N,N-heptyl ammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-diethyl-N-propyl-N- Amyl ammonium bis(trifluoromethanesulfonyl) quinone imine, triethyl propyl ammonium bis(trifluoromethanesulfonyl) quinone imine, triethyl amyl ammonium bis(trifluoromethanesulfonyl) Yttrium, triethylheptyl ammonium bis(trifluoromethanesulfonyl) quinone imine, N, N -dipropyl-N-methyl-N-ethylammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-dipropyl-N-methyl-N-pentyl ammonium bis(trifluoro Methanesulfonyl) quinone imine, N,N-dipropyl-N-butyl-N-hexyl ammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-dipropyl-N,N - Dihexyl ammonium bis(trifluoromethanesulfonyl) sulfinium imine, N,N-dibutyl-N-methyl-N-pentyl ammonium bis(trifluoromethanesulfonyl) quinone imine, N, N-dibutyl-N-methyl-N-hexyl ammonium bis(trifluoromethanesulfonyl) quinone imine, trioctylmethylammonium bis(trifluoromethanesulfonyl) quinone imine, N-A --N-ethyl-N-propyl-N-pentyl ammonium bis(trifluoromethanesulfonyl) quinone imine, 1-butylpyridinium (trifluoromethanesulfonyl) trifluoroacetamide, 1-butyl-3-methylpyridinium (trifluoromethanesulfonyl) trifluoroacetamide, 1-ethyl-3-methylimidazolium (trifluoromethanesulfonyl) trifluoroacetamide, Tetrahexylammonium bis(trifluoromethanesulfonyl) quinone imine, diallyldimethylammonium trifluoromethanesulfonate, diallyldimethylammonium bis(trifluoromethanesulfonyl)pyrene Amine, diallyldimethylammonium bis(pentafluoroethanesulfonyl) quinone imine, N,N-diethyl-N-methyl-N-(2-methoxyethyl) ammonium trifluoride Methanesulfonate, N, N- Ethyl-N-methyl-N-(2-methoxyethyl)ammonium bis(trifluoromethanesulfonyl) quinone imine, N,N-diethyl-N-methyl-N-(2 -Methoxyethyl)ammonium bis(pentafluoroethanesulfonyl) quinone imine, glycidyl trimethylammonium triflate, shrinkage Glyceryl trimethylammonium bis(trifluoromethanesulfonyl) quinone imine, glycidyl trimethylammonium bis(pentafluoroethanesulfonyl) quinone imine, diallyldimethylammonium double (three Fluoromethanesulfonyl) quinone imine, diallyldimethyl bis(pentafluoroethanesulfonyl) quinone imine, lithium bis(trifluoromethanesulfonyl) phthalimide, bis(fluorosulfonyl) Lithium imide and the like.

Among the ionic liquids, more preferred is 1-hexylpyridinium bis(fluorosulfonyl) quinone imine, 1-ethyl-3-methylpyridinium trifluoromethanesulfonate, 1-ethyl- 3-methylpyridinium pentafluoroethanesulfonate, 1-ethyl-3-methylpyridinium heptafluoropropane sulfonate, 1-ethyl-3-methylpyridinium nonafluorobutanesulfonate, 1 -butyl-3-methylpyridinium trifluoromethanesulfonate, 1-butyl-3-methylpyridinium bis(trifluoromethanesulfonyl) quinone imine, 1-octyl-4-methyl Pyridinium bis(fluorosulfonyl) quinone imine, 1-methyl-1-propylpyrrolidinium bis(trifluoromethanesulfonyl) quinone imine, 1-methyl-1-propylpyrrolidinium Bis(fluorosulfonyl) quinone imine, 1-methyl-1-propyl acridine bis(trifluoromethanesulfonyl) quinone imine, 1-methyl-1-propyl acridine bis ( Fluorosulfonyl) quinone imine, 1-ethyl-3-methylimidazolium trifluoromethanesulfonate, 1-ethyl-3-methylimidazolium heptafluoropropane sulfonate, 1-ethyl- 3-methylimidazolium bis(trifluoromethanesulfonyl) quinone imine, 1-ethyl-3-methylimidazolium bis(fluorosulfonyl) quinone imine, 1-hexyl-3-methylimidazole Bis(fluorosulfonyl) quinone imine, trimethylpropylammonium bis(trifluoromethanesulfonyl) quinone imine, double Acyl-fluoro-methanesulfonamide) (PEI), lithium bis (fluorosulfonyl acyl) acyl imide.

As the ionic liquid, a commercially available ionic liquid can be used, and it can also be synthesized as follows. The method for synthesizing the ionic liquid is not particularly limited as long as the target ionic liquid can be obtained, and the halogenated product described in the literature "Iron Liquid - Development of the Forefront and Future -" (issued by CMC Publishing Co., Ltd.) is generally used. The physical method, the hydroxide method, the acid ester method, the mismatch formation method, the neutralization method, and the like.

In the following, for the halide method, the hydroxide method, the acid ester method, the mismatch formation method and the neutralization method, the synthesis method of the nitrogen-containing cerium salt is exemplified, and other sulphur-containing cerium salts, phosphorus-containing cerium salts and the like are described. The ionic liquid can also be obtained by the same method.

The halide method is a method which is carried out by a reaction represented by the reaction formulas (1) to (3). First of all, The tertiary amine is reacted with a halogenated hydrocarbon to obtain a halide (reaction formula (1), and as a halogen, chlorine, bromine or iodine can be used).

The obtained halide is reacted with an acid (HA) or a salt (a cation which forms a salt with a target anion such as MA, M-based ammonium, lithium, sodium or potassium) having an anionic structure (A ^- ) having a target ionic liquid. an objective ionic liquid (R ₄ NA).

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

The hydroxide method is a method carried out by a reaction represented by the reaction formulas (4) to (8). First, the halide (R ₄ NX) is subjected to ion exchange membrane electrolysis (reaction formula (4)), OH type ion exchange resin method (reaction formula (5)) or reaction with silver oxide (Ag ₂ O) (reaction) The hydroxide (R ₄ NOH) is obtained by the formula (6)) (as a halogen, chlorine, bromine or iodine can be used).

With respect to the obtained hydroxide, the target ionic liquid (R ₄ NA) is obtained by the reaction of the reaction formulas (7) to (8) in the same manner as the above halogenation method.

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

The acid ester method is a method carried out by a reaction represented by the reaction formulas (9) to (11). First, a tertiary amine (R ₃ N) is reacted with an acid ester to obtain an acid ester (reaction formula (9). As an acid ester, an ester of a mineral acid such as sulfuric acid, sulfurous acid, phosphoric acid, phosphorous acid, or carbonic acid may be used or An ester of an organic acid such as methanesulfonic acid, methylphosphonic acid or formic acid, etc.).

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

The neutralization method is a method carried out by a reaction represented by the reaction formula (12). 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 And get.

[Formula _{5] (12) R 2 N} + HZ → R 3 HN + Z - [HZ: CF 3 COOH, CF 3 SO 3 H, (CF 3 SO 2) 2 NH, (CF 3 SO 2) 3 CH, (c ₂ F ₅ SO ₂ ) ₂ NH and other organic acids]

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

The amount of the ionic liquid to be added varies depending on the compatibility of the polymer to be used and the ionic liquid, and therefore it cannot be generalized, and is usually preferably 0.001 by weight based on 100 parts by weight of the polyurethane resin. The portion is preferably 50 parts by weight to 40 parts by weight, more preferably 0.01 parts by weight to 30 parts by weight, still more preferably 0.01 parts by weight to 20 parts by weight, most preferably 0.01 parts by weight to 10 parts by weight. Share. By adjusting the blending amount of the ionic liquid within the above range, it is possible to provide a urethane-based adhesive which is excellent in antistatic property. If the above-mentioned amount of the ionic liquid is less than 0.01 part by weight, sufficient antistatic properties cannot be obtained. If the above formula of ionic liquid exceeds 50 weight In this case, there is a tendency to increase the contamination of the adherend.

The urethane-based adhesive may contain a modified eucalyptus oil. The effect of the present invention can be more effectively exhibited by the urethane-based adhesive containing a modified eucalyptus oil.

When the urethane-based adhesive contains a modified eucalyptus oil, the content thereof is preferably 0.001 part by weight to 50 parts by weight, more preferably 0.01% by weight based on 100 parts by weight of the urethane-based resin. The portion is preferably 40 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. By adjusting the content ratio of the modified eucalyptus oil within the above range, the effects of the present invention can be more effectively exhibited.

As the modified eucalyptus oil, any suitable modified eucalyptus oil can be employed within the range not impairing the effects of the present invention. As such a modified eucalyptus oil, for example, a modified eucalyptus oil which can be purchased by the Chemical Industry Co., Ltd. can be mentioned.

As the modified eucalyptus oil, a polyether modified eucalyptus oil is preferred. The effect of the present invention can be more effectively exhibited by using a polyether modified eucalyptus oil.

Examples of the polyether-modified eucalyptus oil include a side chain type polyether modified eucalyptus oil and a two-end type polyether modified eucalyptus oil. Among these, a polyether-modified emu oil of a two-end type is preferable in terms of being able to sufficiently and more effectively express the effects of the present invention.

As the polyurethane resin, any appropriate polyurethane resin can be used as long as the effects of the present invention are not impaired. The polyurethane resin is preferably a polyurethane resin obtained from a composition containing a polyol (A) and a polyfunctional isocyanate compound (B), or a urethane-containing resin. A polyurethane resin obtained from a composition of the prepolymer (C) and the polyfunctional isocyanate compound (B). By using the polyurethane resin as described above as the polyurethane resin, the surface protective film of the present invention can be applied even when it is bonded to an adherend having a large surface step. The wetness is also more excellent, and the step followability is also more excellent, so that the high density can be sufficiently achieved.

For the polyurethane resin, within the range not impairing the effects of the present invention, It may contain any suitable other ingredients. Examples of such other components include a resin component other than the polyurethane resin, a tackifier, an inorganic filler, an organic filler, a metal powder, a pigment, a foil, a softener, an anti-aging agent, and the like. Conductive agent, ultraviolet absorber, antioxidant, light stabilizer, surface lubricant, leveling agent, preservative, heat stabilizer, polymerization inhibitor, lubricant, solvent, catalyst, and the like.

The polyurethane resin preferably contains a deterioration preventing agent such as an antioxidant, an ultraviolet absorber, or a light stabilizer. When the urethane-based resin contains a deterioration preventing agent, even if it is stored in a heated state after being bonded to the adherend, it is not easy to cause residual glue or the like on the adherend, and the residual adhesive resistance is excellent. Therefore, in the surface protective film of the present invention, contamination of the adherend can be further reduced. The deterioration preventing agent may be used alone or in combination of two or more. As the deterioration preventing agent, an antioxidant is particularly preferable.

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

Examples of the radical chain inhibitor include a phenolic antioxidant and an amine antioxidant.

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

Examples of the phenolic antioxidant include monophenolic antioxidants, bisphenol antioxidants, and polymeric phenol antioxidants.

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

Examples of the bisphenol-based antioxidant include 2,2'-methylenebis(4-methyl-6-tert-butylphenol) and 2,2'-methylenebis(4-ethyl-6). -T-butylphenol), 4,4'-thiobis(3-methyl-6-tert-butylphenol), 4,4'-butylene bis(3-methyl-6-tributyl) Phenol), 3,9-bis[1,1-dimethyl-2-[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propenyloxy]B Base] 2,4,8,10-tetraoxaspiro[5,5]undecane and the like.

Examples of the polymer phenol-based antioxidant include 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane and 1,3,5-trimethyl. -2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, tetra-[methylene-3-(3',5'-di-t-butyl -4'-hydroxyphenyl)propionate]methane, bis[3,3'-bis-(4'-hydroxy-3'-t-butylphenyl)butanoic acid] ethylene glycol ester, 1,3 , 5-tris(3',5'-di-t-butyl-4'-hydroxybenzyl)-s-triazine-2,4,6-(1H, 3H, 5H)trione, tocopherol, and the like.

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

Examples of the phosphorus-based antioxidant include triphenyl phosphite, diphenylisodecyl phosphite, and phenyl diisononyl phosphite.

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, and a cyanoacrylate. An ester-based ultraviolet absorber, a triazine-based ultraviolet absorber, or the like.

Examples of the benzophenone-based ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, and 2-hydroxy-4-octyloxybenzophenone. Ketone, 2-hydroxy-4-dodecyloxybenzophenone, 2,2'-dihydroxy-4-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'- Dimethoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone, bis(2-methoxy-4-hydroxy-5-benzylidenephenyl)methane Wait.

Examples of the benzotriazole-based ultraviolet absorber include 2-(2'-hydroxy-5'-methylphenyl)benzotriazole and 2-(2'-hydroxy-5'-tert-butylbenzene. Benzotriazole, 2-(2'-hydroxy-3',5'-di-t-butylphenyl)benzotriazole, 2-(2'-hydroxy-3'-tert-butyl -5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-t-butylphenyl) 5-chlorobenzotriazole, 2 -(2'-hydroxy-3',5'-di-third-pentylphenyl)benzotriazole, 2-(2'-hydroxy-4'-octyloxyphenyl)benzotriazole, 2 -[2'-hydroxy-3'-(3",4",5",6"-tetrahydrophthalene imine methyl)- 5'-Methylphenyl]benzotriazole, 2,2'-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazole -2-yl)phenol], [2(2'-hydroxy-5'-methacryloxyphenyl)-2H-benzotriazole, and the like.

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

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

Examples of the light stabilizer include a hindered amine light stabilizer, an ultraviolet stabilizer, and the like.

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

Examples of the ultraviolet stabilizer include bis(octylphenyl)sulfide nickel, [2,2'-thiobis(4-trioctylphenol)]-n-butylamine nickel, and 3,5-di- Tributyl-4-hydroxybenzyl-phosphate monoethyl acetate, nickel dibutyldithiocarbamate, quencher of benzoate type, nickel dibutyldithiocarbamate, and the like.

<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 preferably a polyol (A) and a polyfunctional isocyanate compound (B). The polyurethane resin obtained by curing the composition.

The polyol (A) may be used alone or in combination of two or more.

The polyfunctional isocyanate compound (B) may be used alone or in combination of two or more.

The polyhydric alcohol (A) is preferably, for example, a polyester polyol, a polyether polyol, a polycaprolactone polyol, a polycarbonate polyol, or a castor oil-based polyol. As the polyol (A), a polyether polyol is more preferable.

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

Examples of the polyol component include ethylene glycol, diethylene glycol, 1,3-butylene glycol, 1,4-butanediol, neopentyl glycol, and 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-nonanediol, octadecanediol, glycerin, trimethylolpropane, Pentaerythritol, hexanetriol, polypropylene glycol, and the like. Examples of the acid component include succinic acid, methyl succinic acid, adipic acid, pimelic acid, sebacic 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-naphthalene dicarboxylic acid, 4,4'-diphenyl phthalic acid, such acid anhydrides, and the like.

Examples of the polyether polyol include water, a low molecular polyol (propylene glycol, ethylene glycol, glycerin, trimethylolpropane, pentaerythritol, etc.), a bisphenol (bisphenol A, etc.), and dihydroxybenzene (o. A polyether polyol obtained by addition polymerization of an alkylene oxide such as ethylene oxide, propylene oxide or butylene oxide as a starting agent such as benzenediol, resorcin, or hydroquinone. Specific examples thereof include polyethylene glycol, polypropylene glycol, and polybutylene glycol.

The polycaprolactone polyol may, for example, be a caprolactone-based polyester diol obtained by ring-opening polymerization of a cyclic ester monomer such as ε-caprolactone or σ-valerolactone.

Examples of the polycarbonate polyol include a polycarbonate polyol obtained by subjecting the above polyol component to carbon trichloride to undergo polycondensation reaction; and the above polyol component and dimethyl carbonate, diethyl carbonate, and dipropylene carbonate. Polycarbonate obtained by transesterification condensation of carbonic acid diesters such as ester, diisopropyl carbonate, dibutyl carbonate, ethyl butyl carbonate, ethylene carbonate, propylene carbonate, diphenyl carbonate and dibenzyl carbonate a polyhydric alcohol; a copolymerized polycarbonate polyol obtained by using two or more of the above polyol components in combination; a polycarbonate polyol obtained by esterifying a plurality of the above polycarbonate polyols with a carboxyl group-containing compound; a polycarbonate polyol obtained by subjecting various polycarbonate polyols to a hydroxyl group-containing compound by etherification reaction; a polycarbonate polyol obtained by transesterifying a plurality of the above polycarbonate polyols with an ester compound; a polycarbonate polyol obtained by transesterifying a polycarbonate polyol with a hydroxyl group-containing compound, and a polyester polycarbonate obtained by subjecting the above various polycarbonate polyols to a polycondensation reaction with a dicarboxylic acid compound Polyol; a copolymerized polyether-based polycarbonate polyol obtained by copolymerizing the above various polycarbonate polyols with an alkylene oxide.

The castor oil-based polyol is, for example, a castor oil-based polyol obtained by reacting a castor oil fatty acid with the above-described polyol component. Specifically, for example, a castor oil-based polyol obtained by reacting a castor oil fatty acid with polypropylene glycol can be mentioned.

The number average molecular weight Mn of the polyol (A) is preferably from 400 to 20,000, more preferably from 500 to 17,000, still more preferably from 600 to 15,000, still more preferably from 800 to 12,000. By adjusting the number average molecular weight Mn of the polyol (A) within the above range, the surface protective film of the present invention is more excellent in wettability even when it is bonded to an adherend having a large surface step difference, and Since the step followability is also excellent, the high density can be sufficiently achieved.

The polyol (A) preferably contains a polyol (A1) having a number average molecular weight Mn of 8,000 to 20,000 having three OH groups. The polyol (A1) may be used alone or in combination of two or more.

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, still more preferably 70% by weight to 90% by weight. By adjusting the content ratio of the polyol (A1) in the polyol (A) within the above range, the surface protective film of the present invention has wettability even when it is bonded to an adherend having a large surface step. It is also more excellent, and the step followability is also superior, so that the high density can be more fully achieved.

The number average molecular weight Mn of the polyol (A1) is preferably from 8,000 to 20,000, more preferably from 8,000 to 18,000, still more preferably from 8500 to 17,000, and still more preferably from 9000 to 16,000. It is particularly preferably 9500 to 15500, and most preferably 10,000 to 15,000. By adjusting the number average molecular weight Mn of the polyol (A1) within the above range, the surface protective film of the present invention is more excellent in wettability even when it is bonded to an adherend having a large surface step difference, and The step followability is also superior, so that the high density can be more fully achieved.

The polyol (A) may contain a polyol (A2) having a number average molecular weight Mn of 5,000 or less having three or more OH groups. The polyol (A2) may be used alone or in combination of two or more. The number average molecular weight Mn of the polyol (A2) is preferably from 500 to 5,000, more preferably from 800 to 4,500, still more preferably from 1,000 to 4,000, still more preferably from 1,000 to 3,500, most preferably from 1,000 to 3,000. When the number average molecular weight Mn of the polyol (A2) deviates from the above range, there is a possibility that the adhesion with time is increased, and excellent reworkability cannot be exhibited. The polyhydric alcohol (A2) is preferably a polyol having three OH groups (triol), a polyol having four OH groups (tetraol), and a polyol having five OH groups (five) A polyol (hexaol) having 6 OH groups.

As the polyol (A2), a polyol having four OH groups (tetraol), a polyol having five OH groups (pentahydric alcohol), and at least a polyol having six OH groups (hexahydric alcohol) The total amount of one kind is preferably 10% by weight or less, more preferably 7% by weight or less, still more preferably 6% by weight or less, and particularly preferably 5% by weight based on the content of the polyol (A). the following. By the polyol (A), a polyol having four OH groups (tetraol) as a polyol (A2), a polyol having five OH groups (pentahydric alcohol), and having 6 OH groups At least one of the polyhydric alcohols (hexahydric alcohol) is adjusted within the above range, and a urethane-based adhesive which is more excellent in transparency can be provided.

The content of the polyol (A2) in the polyol (A) is preferably 30% by weight or less, more preferably 0% by weight to 30% by weight. By adjusting the content ratio of the polyol (A2) in the polyol (A) within the above range, the surface protective film of the present invention has wettability even when it is bonded to an adherend having a large surface step. It is also more excellent, and the step followability is also superior, so that the high density can be more fully achieved.

The content ratio of the polyol having a number average molecular weight Mn of 5,000 or less in the polyol (A2) having a quaternary or higher Mn group of 5,000 or less is preferably less than 10% by weight, more preferably 8% based on the total amount of the polyol (A). The weight% or less is further preferably 7% by weight or less, particularly preferably 6% by weight or less, and most preferably 5% by weight or less. When the content ratio of the polyol having a number average molecular weight Mn of 5,000 or less in the polyol (A2) is 5,000 or less, the urethane is caused to be 10% by weight or more based on the total amount of the polyol (A). The adhesive is easily whitened to reduce the transparency.

The polyfunctional isocyanate compound (B) may be used alone or in combination of two or more.

As the polyfunctional isocyanate compound (B), any appropriate polyfunctional isocyanate compound which can be used for the urethanization reaction can be used. Examples of such a polyfunctional isocyanate compound (B) include a polyfunctional aliphatic isocyanate compound, a polyfunctional alicyclic isocyanate, and a polyfunctional aromatic isocyanate compound.

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

Examples of the polyfunctional alicyclic isocyanate compound include 1,3-cyclopentene diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, and isophorone diisocyanate. Hydrogenated diphenylmethane diisocyanate, hydrogenated xylene diisocyanate, hydrogenated toluene diisocyanate, hydrogenated tetramethyl xylene diisocyanate, and the like.

Examples of the polyfunctional aromatic diisocyanate compound include phenyl diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 2,2'-diphenylmethane diisocyanate, and 4,4'-di. Benzene diisocyanate, 4,4'-toluidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, xylene diisocyanate, etc. .

As the polyfunctional isocyanate compound (B), various polyfunctionalities as described above may also be mentioned. A trimethylolpropane adduct of a cyanate compound, a biuret obtained by reacting with water, a terpolymer having an isocyanurate ring, and the like. Moreover, these can also be used in combination.

The equivalent ratio of the NCO group to the OH group in the polyol (A) and the polyfunctional isocyanate compound (B) is preferably from 0.3 to 1.0, more preferably from 0.3 to 0.9, still more preferably from 0.3 to 0.8, based on the NCO group/OH group. It is particularly preferably 0.3 to 0.7, and most preferably 0.3 to 0.6. By adjusting the equivalent ratio of the NCO group/OH group within the above range, the surface protective film of the present invention is more excellent in wettability even when it is bonded to an adherend having a large surface step difference, and the step difference is obtained. The followability is also better, so the high density can be achieved more fully.

The content ratio of the polyfunctional isocyanate compound (B) is preferably from 2.7% by weight to 8.8% by weight, more preferably from 2.7% by weight to 8.0% by weight, based on the polyol (A). It is preferably from 2.7% by weight to 7.1% by weight, particularly preferably from 2.7% by weight to 6.2% by weight, most preferably from 2.7% by weight to 5.3% by weight. By adjusting the content ratio of the polyfunctional isocyanate compound (B) within the above range, the surface protective film of the present invention is more excellent in wettability even when it is bonded to an adherend having a large surface step difference, and The step followability is also superior, so that the high density can be more fully achieved.

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

As a method of obtaining a polyurethane resin by curing a composition containing the polyol (A) and the polyfunctional isocyanate compound (B), urethane formation using bulk polymerization or solution polymerization can be employed. The reaction method or the like employs any appropriate method within the range not impairing the effects of the present invention.

In order to harden the composition containing the polyol (A) and the polyfunctional isocyanate compound (B), it is preferred to use a catalyst. Examples of such a catalyst include an organometallic compound, a tertiary amine compound, and the like.

Examples of the organometallic compound include an iron compound, a tin compound, a titanium compound, a zirconium compound, a lead compound, a cobalt compound, and a zinc compound. Things and so on. Among these, an iron-based compound or a tin-based compound is preferred in terms of the reaction rate and the effective life of the adhesive layer.

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

Examples of the tin-based compound include dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin maleate, dibutyltin dilaurate, dibutyltin diacetate, and dibutyl. Tin sulphide, tributyltin methoxide, tributyltin acetate, ethoxylated triethyltin, tributyltin ethoxylate, dioctyltin oxide, dioctyltin dilaurate, tributyltin chloride, trichloroacetic acid Butyltin, tin 2-ethylhexanoate, and the like.

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

Examples of the zirconium compound include zirconium naphthenate and zirconium acetonate.

Examples of the lead-based 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, 1,8-diazabicyclo-(5,4,0)-undecene-7 and the like.

The catalyst may be used alone or in combination of two or more. Further, a catalyst, a crosslinking retarder or the like may be used in combination. The amount of the catalyst is preferably 0.02% by weight to 0.10% by weight, more preferably 0.02% by weight to 0.08% by weight, still more preferably 0.02% by weight to 0.06% by weight, particularly preferably 0.02% by weight based on the polyol (A). %~0.05% by weight. By adjusting the amount of the catalyst within the above range, the surface protective film of the present invention is more excellent in wettability and superior in step followability even when it is bonded to an adherend having a large surface step. Therefore, the high density can be more fully achieved.

The composition containing the polyol (A) and the polyfunctional isocyanate compound (B) may contain any appropriate other components within the range not impairing the effects of the present invention. As such Examples of the other component include a resin component other than the polyurethane resin, a tackifier, an inorganic filler, an organic filler, a metal powder, a pigment, a foil, a softener, an anti-aging agent, and a conductive agent. Ultraviolet absorbers, antioxidants, light stabilizers, surface lubricants, leveling agents, preservatives, heat stabilizers, polymerization inhibitors, lubricants, solvents, catalysts, and the like.

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

The polyurethane resin obtained from the composition containing the urethane prepolymer (C) and the polyfunctional isocyanate compound (B) is a so-called "urethane prepolymer". As the raw material obtained as a raw material, any suitable polyurethane resin can be used.

The polyurethane-based resin obtained from the composition containing the urethane prepolymer (C) and the polyfunctional isocyanate compound (B), for example, may be exemplified by containing as a urethane prepolymer ( A polyurethane-based resin obtained by the combination of the polyurethane polyol of C) and the polyfunctional isocyanate compound (B). The urethane prepolymer (C) may be used alone or in combination of two or more. The polyfunctional isocyanate compound (B) may be used alone or in combination of two or more.

As the polyurethane urethane polyol of the urethane prepolymer (C), it is preferred to use the polyester polyol (a1) and the polyether polyol (a2) in the presence or absence of a catalyst. It is obtained by reacting with an organic polyisocyanate compound (a3).

As the polyester polyol (a1), any appropriate polyester polyol can be used. The polyester polyol (a1) is, for example, a polyester polyol obtained by reacting an acid component with a diol component. Examples of the acid component include terephthalic acid, adipic acid, sebacic acid, sebacic acid, phthalic anhydride, isophthalic acid, and trimellitic acid. Examples of the diol component include ethylene glycol, propylene glycol, diethylene glycol, butylene glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, and 3,3'-di. Hydroxymethylheptane, polyoxyethylene glycol, polyoxypropylene glycol, 1,4-butanediol, neopentyl glycol, butyl ethyl pentanediol; as a polyol component, glycerin, Trimethylolpropane, pentaerythritol, and the like. Examples of the polyester polyol (a1) include ring-opening polymerization of lactones such as polycaprolactone, poly(β-methyl-γ-valerolactone), and polyvalerolactone. Polyester polyols, etc.

As the molecular weight of the polyester polyol (a1), it can be used from a low molecular weight to a high molecular weight. As the molecular weight of the polyester polyol (a1), the number average molecular weight is preferably from 500 to 5,000. The number average molecular weight is less than 500, and the reactivity becomes high and gelation is easy. When the number average molecular weight exceeds 5,000, the reactivity becomes low, and the cohesive force of the polyurethane polyether itself becomes small. The amount of the polyester polyol (a1) to be used is preferably from 10 to 90 mol% in the polyol constituting the polyurethane polyalcohol.

As the polyether polyol (a2), any appropriate polyether polyol can be used. Examples of the polyether polyol (a2) include low molecular weight polyols such as water, propylene glycol, ethylene glycol, glycerin, and trimethylolpropane, which are used as initiators to form ethylene oxide and propylene oxide. A polyether polyol obtained by polymerizing an alkylene oxide compound such as butylene oxide or tetrahydrofuran. Specific examples of the polyether polyol (a2) include polyether polyols having a functional group number of 2 or more, such as polypropylene glycol, polyethylene glycol, and polytetramethylene glycol.

As the molecular weight of the polyether polyol (a2), it can be used from a low molecular weight to a high molecular weight. As the molecular weight of the polyether polyol (a2), the number average molecular weight is preferably from 1,000 to 5,000. When the number average molecular weight is less than 1,000, the reactivity becomes high and gelation is liable to occur. When the number average molecular weight exceeds 5,000, the reactivity becomes low, and the cohesive force of the polyurethane polyether itself becomes small. The amount of the polyether polyol (a2) used is preferably from 20 mol% to 80 mol% in the polyol constituting the polyurethane polyalcohol.

As the polyether polyol (a2), a part thereof may be replaced with ethylene glycol, 1,4-butanediol, neopentyl glycol, butylethylpentanediol, glycerin or trimethylolpropane, as needed. A glycol such as pentaerythritol; or a polyamine such as ethylenediamine, N-amine ethylethanolamine, isophoronediamine or xylenediamine may be used in combination.

As the polyether polyol (a2), only a difunctional polyether polyol can be used. A polyether polyol having a number average molecular weight of 1,000 to 5,000 and having at least 3 or more hydroxyl groups in one molecule is used in part or in whole. When a polyether polyol having an average molecular weight of 1,000 to 5,000 and at least three or more hydroxyl groups per molecule is used as the polyether polyol (a2), the balance between the adhesion and the removability is good. In such a polyether polyol, when the number average molecular weight is less than 1,000, the reactivity becomes high and gelation is liable to occur. In addition, when the number average molecular weight exceeds 5,000, the reactivity of the polyether polyol decreases, and the cohesive force of the polyurethane polyether itself decreases. The number average molecular weight of the polyether polyol is preferably from 2,500 to 3,500.

As the organic polyisocyanate compound (a3), any appropriate organic polyisocyanate compound can be used. Examples of such an organic polyisocyanate compound (a3) include an aromatic polyisocyanate, an aliphatic polyisocyanate, an aromatic aliphatic polyisocyanate, and an alicyclic polyisocyanate.

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

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

Examples of the aromatic aliphatic polyisocyanate include ω,ω'-diisocyanate-1,3-dimethylbenzene, ω,ω'-diisocyanate-1,4-dimethylbenzene, ω,ω'-two. Isocyanate-1,4-diethylbenzene, 1,4-tetramethylxylene diisocyanate, 1,3-tetramethylxylene diisocyanate, and the like.

Examples of the alicyclic polyisocyanate include 3-isocyanate methyl-3,5,5-trimethyl. Cyclohexyl isocyanate, 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, methyl-2,4-cyclohexane diisocyanate, methyl -2,6-cyclohexane diisocyanate, 4,4'-methylenebis(cyclohexyl isocyanate), 1,4-bis(isocyanatemethyl)cyclohexane, 1,4-bis(isocyanate methyl) Cyclohexane and the like.

As the organic polyisocyanate compound (a3), a trimethylolpropane adduct, a biuret obtained by reacting with water, a terpolymer having an isocyanurate ring, or the like may be used in combination.

As the catalyst which can be used when obtaining a polyurethane polyacrylate, any appropriate catalyst can be used. Examples of such a catalyst include a tertiary amine compound and an organometallic compound.

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

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

Examples of the tin-based compound include dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin dimaleate, dibutyltin dilaurate (DBTDL), and dibutyltin diacetate. , Dibutyltin sulfide, Tributyltin sulfide, Tributyltin oxide, Tributyltin acetate, Triethyltin oxide, Tributyltin oxide, Dioctyltin oxide, Tributyltin chloride, Trichloro Tributyltin acetate, tin 2-ethylhexanoate, and the like.

Examples of the non-tin-based compound include titanium compounds such as dibutyl titanium dichloride, tetrabutyl titanate, and butoxy titanium trichloride; lead oleate, lead 2-ethylhexanoate, and lead benzoate. And lead compounds such as lead naphthenate; iron compounds such as iron 2-ethylhexanoate and iron acetonitrile; cobalt compounds such as cobalt benzoate and cobalt 2-ethylhexanoate; zinc naphthenate, 2- A zinc-based compound such as zinc ethylhexanoate or a zirconium compound such as zirconium alkanoate.

In the case where a catalyst is used in the case of obtaining a polyurethane polyalcohol, in a system in which two polyols of a polyester polyol and a polyether polyol are present, since the reactivity is different, it is easy to produce using a separate catalyst system. Gelation or turbidity of the reaction solution. because Thus, since two kinds of catalysts are used in the case of obtaining a polyurethane polyacrylate, the reaction rate, the selectivity of the catalyst, and the like can be easily controlled, and these problems can be solved. Examples of the combination of the two kinds of catalysts include a tertiary amine/organometallic system, a tin-based/non-tin-based, and a tin-based/tin-based system, preferably a tin-based/tin-based system, and more preferably a dibutyltin dilaurate. In combination with tin 2-ethylhexanoate. The ratio of the compounding ratio of tin 2-ethylhexanoate/dibutyltin dilaurate is preferably less than 1, more preferably 0.2 to 0.6. When the compounding ratio is 1 or more, gelation tends to occur due to a balance of catalyst activity.

In the case where a catalyst is used in obtaining a polyurethane polyalcohol, the amount of the catalyst used is relative to the total amount of the polyester polyol (a1), the polyether polyol (a2), and the organic polyisocyanate compound (a3). It is preferably 0.01 to 1.0% by weight.

In the case where a catalyst is used in obtaining a polyurethane polyacrylate, the reaction temperature is preferably less than 100 ° C, more preferably 85 ° C to 95 ° C. When the temperature is higher than 100 ° C, the reaction rate and the control of the crosslinked structure become difficult, and it is difficult to obtain a ruthenium polyol having a specific molecular weight.

When a polyurethane polyalcohol is obtained, a catalyst may not be used. In this case, the reaction temperature is preferably 100 ° C or higher, more preferably 110 ° C or higher. Further, when the polyurethane urethane is obtained in the absence of a catalyst, it is preferably reacted for 3 hours or more.

As a method of obtaining a polyurethane polyacrylate, for example, 1) a method of charging a polyester polyol, a polyether polyol, a catalyst, and an organic polyisocyanate into a flask; 2) a polyester polyol The polyether polyol and the catalyst are charged into a flask, and an organic polyisocyanate is added dropwise thereto for addition. As a method of obtaining a polyurethane polyester, in terms of controlling the reaction, the method 2) is preferred.

When a polyurethane urethane is obtained, any suitable solvent can be used. Examples of such a solvent include methyl ethyl ketone, ethyl acetate, toluene, xylene, and acetone. Among these solvents, toluene is preferred.

As the polyfunctional isocyanate compound (B), the above polyfunctional isocyanic acid can be used. Ester compound.

The composition containing the urethane prepolymer (C) and the polyfunctional isocyanate compound (B) may contain any appropriate other components within the range not impairing the effects of the present invention. Examples of such other components include a resin component other than the polyurethane resin, a tackifier, an inorganic filler, an organic filler, a metal powder, a pigment, a foil, a softener, an anti-aging agent, and the like. Conductive agent, ultraviolet absorber, antioxidant, light stabilizer, surface lubricant, leveling agent, preservative, heat stabilizer, polymerization inhibitor, lubricant, solvent, catalyst, and the like.

As a method of producing a polyurethane resin obtained from a composition containing a urethane prepolymer (C) and a polyfunctional isocyanate compound (B), as long as a so-called "urethane" is used As the method for producing the polyurethane resin as a raw material, any appropriate production method can be employed.

The number average molecular weight Mn of the urethane prepolymer (C) is preferably from 1,000 to 100,000.

The equivalent ratio of the NCO group to the OH group in the urethane prepolymer (C) and the polyfunctional isocyanate compound (B) is preferably from 0.3 to 1.0, more preferably from 0.3 to 0.7 based on the NCO group/OH group. 0.9, further preferably 0.3 to 0.8, particularly preferably 0.3 to 0.7, most preferably 0.3 to 0.6. By adjusting the equivalent ratio of the NCO group/OH group within the above range, the surface protective film of the present invention is more excellent in wettability even when it is bonded to an adherend having a large surface step difference, and the step difference is obtained. The followability is also better, so the high density can be achieved more fully.

The content ratio of the polyfunctional isocyanate compound (B) is preferably from 1.1% by weight to 3.6% by weight, more preferably 1.1% by weight, based on the urethane prepolymer (C). 3.2% by weight, further preferably 1.1% by weight to 2.9% by weight, particularly preferably 1.1% by weight to 2.5% by weight, most preferably 1.1% by weight to 2.1% by weight. By adjusting the content ratio of the polyfunctional isocyanate compound (B) within the above range, the surface protective film of the present invention has wettability even when it is bonded to an adherend having a large surface step. It is more excellent, and the step followability is also superior, so that the high density can be more fully achieved.

Substrate layer

As the thickness of the base material layer, any appropriate thickness can be employed depending on the application. The thickness of the substrate layer is preferably from 5 μm to 300 μm, more preferably from 10 μm to 250 μm, still more preferably from 15 μm to 200 μm, still more preferably from 20 μm to 150 μm.

The base material layer may be a single layer or a laminate of two or more layers. The substrate layer may also be an extended substrate layer.

As the material of the substrate layer, any appropriate material can be used depending on the application. For example, plastic, paper, a metal film, a nonwoven fabric, etc. are mentioned. It is preferably plastic. The base material layer may be composed of one material or may be composed of two or more materials. For example, it may be composed of two or more kinds of plastics.

Examples of the plastic material include a polyester resin, a polyamide resin, and a polyolefin resin. Examples of the polyester resin include polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate. Examples of the polyolefin-based resin include a homopolymer of an olefin monomer, a copolymer of an olefin monomer, and the like. Specific examples of the polyolefin-based resin include a homopolypropylene; a propylene-based copolymer such as a block system, a random system, or a graft system in which an ethylene component is used as a copolymerization component; Reactor-TPO (reactor directly prepared) Thermoplastic polyolefin); ethylene-based polymer of low density, high density, linear low density, ultra low density, etc.; ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ethylene-methyl acrylate copolymer, ethylene-acrylic acid An ethylene-based copolymer, an ethylene-butyl acrylate copolymer, an ethylene-methacrylic acid copolymer, or an ethylene-methyl methacrylate copolymer or the like.

The substrate layer may contain any appropriate additives as needed. Examples of the additive which can be contained in the base layer include an antioxidant, an ultraviolet absorber, a light stabilizer, an antistatic agent, a filler, a pigment, and the like. The type and number of additives that can be contained in the substrate layer. The amount can be appropriately set according to the purpose. In particular, when the material of the base material layer is a plastic, it is preferable to contain several of the above additives for the purpose of preventing deterioration or the like. From the viewpoint of improving weather resistance and the like, an antioxidant, an ultraviolet absorber, a light stabilizer, and a filler are particularly preferable as the additive.

As the antioxidant, any appropriate antioxidant can be employed. Examples of such an antioxidant include a phenol-based antioxidant, a phosphorus-based processing heat stabilizer, a lactone-based processing heat stabilizer, a sulfur-based heat-resistant stabilizer, and a phenol-phosphorus-based antioxidant. The content ratio of the antioxidant is preferably 1% by weight or less, more preferably 0.5% by weight or less based on the base resin of the base material layer (when the base material layer is a blend, the blend is a base resin). Further, it is preferably from 0.01% by weight to 0.2% by weight.

As the ultraviolet absorber, any appropriate ultraviolet absorber can be used. Examples of such an ultraviolet absorber include a benzotriazole-based ultraviolet absorber, a triazine-based ultraviolet absorber, and a benzophenone-based ultraviolet absorber. The content of the ultraviolet absorber is preferably 2% by weight or less, more preferably 1% by weight based on the base resin forming the base material layer (when the base material layer is a blend, the blend is a base resin). % or less, further preferably 0.01% by weight to 0.5% by weight.

As the light stabilizer, any appropriate light stabilizer can be employed. Examples of such a light stabilizer include a hindered amine light stabilizer and a benzoate light stabilizer. The content ratio of the light stabilizer is preferably 2% by weight or less, more preferably 1% by weight based on the base resin forming the base material layer (when the base material layer is a blend, the blend is a base resin). % or less, further preferably 0.01% by weight to 0.5% by weight.

As the filler, any appropriate 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 ratio of the filler is preferably 20% by weight or less, more preferably 10% by weight, based on the base resin forming the base material layer (when the base material layer is a blend, the blend is a base resin). Hereinafter, it is further preferably 0.01% by weight to 10% weight%.

In addition, as an additive, for the purpose of imparting antistatic properties, an inorganic, low molecular weight, and high molecular weight antistatic agent such as a surfactant, an inorganic salt, a polyhydric alcohol, a metal compound, or carbon is preferable. In particular, from the viewpoint of contamination and maintaining adhesion, a high molecular weight antistatic agent or carbon is preferred.

"Method for manufacturing surface protective film"

The surface protective film of the present invention can be produced by any appropriate method. As such a production method, for example, it can be carried out according to any of the following suitable production methods: (1) a method of applying a solution or a hot melt of a material for forming an adhesive layer on a substrate layer; (2) based on this, a method of transferring a pressure-sensitive adhesive layer formed into a separator into a substrate layer; (3) extruding a material for forming an adhesive layer onto a substrate layer to form a coating method; and (4) a substrate layer And a method of extruding the adhesive layer in two or more layers; (5) a method of laminating a single layer of the adhesive layer on the substrate layer or a method of laminating the adhesive layer together with the laminate layer (6) A method of laminating two or more layers of a material for forming a base material layer such as an adhesive layer and a film or a laminate layer.

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

"Use of Surface Protective Film"

The surface protective film of the present invention can be used for any suitable purpose. It is preferable that the surface protective film of the present invention has very little contamination to the adherend, and is excellent in wettability or reworkability, and therefore, it is preferably used for surface protection of, for example, an optical member or an electronic member. Examples of the optical member include an LCD, a touch panel using an LCD, and the like, and a color filter for the LCD. Light sheet, polarizing plate, etc.

The member to which the surface protective film of the present invention is attached, for example, an optical member or an electronic member, can be bonded and peeled off a plurality of times by the manual operation of the surface protective film to be bonded.

That is, the optical member of the present invention is attached to the member of the surface protective film of the present invention. Further, the electronic component of the present invention is attached with a member of the surface protective film of the present invention.

[Examples]

Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to the examples. Among them, the test and evaluation methods in the examples and the like are as follows. In the case of "parts", unless otherwise specified, means "parts by weight"; in the case of "%", unless otherwise specified, means "% by weight".

<Measurement of adhesion>

The surface protective film with a separator was cut into a width of 25 mm and a length of 80 mm. After peeling off the separator, it was 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. sample. After lamination, respectively, (1) placed in an environment of 23 ° C × 50% RH for 30 minutes, (2) placed in an environment of 50 ° C for 1 week, (3) in an environment of 60 ° C × 90% RH After being placed for one week and (4) after being placed in an environment of 85 ° C for one week, each of the cases was used, and a universal extension tester (manufactured by Minebea Co., Ltd., product name: TCM-1kNB) was used, and the peeling speed was 300 mm/min. Peeling was performed at a peeling angle of 180°, and the adhesive force at this time was measured. The measurement was carried out in an environment of 23 ° C × 50% RH.

<Measurement of Wetting Speed>

The surface protective film with a separator was cut into a size of 25 mm in width and 100 mm in length as an evaluation sample. As the adherend, an AGS1 polarizing plate (manufactured by Nitto Denko Corporation, width 70 mm, length 100 mm) was used, and the separator of the evaluation sample was peeled off, and one of the end portions on the width side was fixed to the end portion on the width side of the adherend. The end portion of the unfixed width side was picked up, and the time from the release of the hand to the wetting extension of 100 mm (unit: s / 2.5 cm × 10 cm) was measured. The speed was calculated from this time, and the case where the speed was 5 cm ² /s or more was evaluated as ○, and the case where the speed was less than 5 cm ² /s was evaluated as ×.

<Measurement of peeling tape voltage>

The surface protective film with a separator was cut into a size of 70 mm in width and 130 mm in length, and after peeling off the separator, the sheet was crimped one by one with a 2 kg roller, and the acrylic plate (thickness 1 mm, width 70 mm) which was previously subjected to static elimination was superimposed and overlapped. A 1001 long AGS polarizer (manufactured by Nitto Denko Co., Ltd., 70 mm wide and 100 mm long). At this time, the surface protective film was exposed to the extent of 30 mm from the glass. After leaving it in an environment of 23 ° C × 50% RH for one day, one end portion exposed from the glass of 30 mm was fixed to an automatic winding machine, and peeling was performed under the conditions of a peeling angle of 150 degrees and a peeling speed of 10 m/min. Then, the peeling tape voltage was measured by a voltage measuring device (KSD-0103, manufactured by Kasuga Electric Co., Ltd.) fixed at a position 10 cm away from the surface protective film. The measurement was carried out in an environment of 23 ° C × 50% RH.

<Measurement of the average roughness Ra of the center line>

The AGS1 polarizing plate (manufactured by Nitto Denko Co., Ltd.), an aluminum plate, and an aluminum plate rubbed with a sandpaper of a specific particle size were placed on a console of ZYGO New View 7300 (manufactured by Canon Marketing Japan Co., Ltd.) to measure the center line average roughness. Ra. Among them, the grain size of the sandpaper used for the friction aluminum plate is (1) 320, (2) 100.

<Measurement of adhesion rate only by self-weight bonding>

An AGS1 polarizing plate (manufactured by Nitto Denko Co., Ltd., width 70 mm, length 100 mm) and an aluminum plate subjected to roughness measurement using ZYGO New View 7300 (manufactured by Canon Marketing Japan Co., Ltd.) were prepared, and the strip was cut into the same size as the same. The separator of the surface protective film with the separator is fixed to one of the ends of the width side, and the end portion of the unfixed width side is picked up, and the hand is released so that it is adhered only by the self-weight of the film. Intimate. Thereafter, the adhesion area was calculated by VHX-100F (Keyence Co., Ltd.), and the adhesion ratio was calculated by the adhesion ratio (%) = (close area/total area).

[Example 1]

As a polyol, a PREMINOL S3011 (manufactured by Asahi Glass Co., Ltd., Mn = 10000) as a polyol having three OH groups: 85 parts by weight, SANNIX GP-3000 as a polyol having three OH groups (Sanyo Chemicals Co., Ltd.) was used. Manufactured by the company, Mn = 3000): 13 parts by weight of SANNIX GP-1000 (manufactured by Sanyo Chemical Co., Ltd., Mn = 1000) as a polyol having three OH groups: 2 parts by weight, formulated as a polyfunctional isocyanate CORONATE HX (Japan Polyurethane Industry Co., Ltd.) of a polyfunctional alicyclic isocyanate compound of the compound: 2.7 parts by weight, a catalyst (manufactured by Nippon Chemical Industry Co., Ltd., trade name: N CEM second iron): 0.04 parts by weight, Irganox 1010 (manufactured by BASF): 0.50 parts by weight, Elexcel AS110 (ionic liquid, manufactured by Dai-Il Pharmaceutical Co., Ltd.): 1.50 parts by weight, KF6004 (polyether modified organic hydrazine) (manufactured by Shin-Etsu Chemical Co., Ltd.): 0.01 parts by weight of ethyl acetate: 241 parts by weight as a diluent solvent, and stirred with a disperser to obtain a urethane-based pressure-sensitive adhesive composition.

The obtained urethane-based pressure-sensitive adhesive composition was applied onto a base material "Lumirror S10" (thickness: 38 μm, manufactured by TORAY INDUSTRIES Co., Ltd.) containing a polyester resin by a fountain roll to have a thickness after drying. It reached 10 μm, and was solidified and dried under the conditions of a drying temperature of 130 ° C and a drying time of 30 seconds. In this manner, an adhesive layer containing the urethane-based adhesive (1) was formed on the substrate.

Then, an organic tantalum-treated surface of a separator containing a polyester resin having a thickness of 25 μm which was subjected to an organic tantalum treatment on the surface of the adhesive layer was bonded to obtain a surface protective film (1) with a separator.

The results are shown in Table 1.

[Examples 2 to 8]

In the same manner as in Example 1, except that the blending amount of CORONATE HX (Japan Polyurethane Industrial Co., Ltd.) of the polyfunctional alicyclic isocyanate compound as the polyfunctional isocyanate compound was changed as shown in Table 1. , obtain the surface protective film with diaphragm (2) ~ (8).

The results are shown in Table 1.

[Examples 9 to 11]

The blending amount of CORONATE HX (Japan Polyurethane Industrial Co., Ltd.) which is a polyfunctional alicyclic isocyanate compound of a polyfunctional isocyanate compound was changed as shown in Table 2, and, as shown in Table 2, it was formulated as a fatty acid ester. A surface protective film with a separator was obtained in the same manner as in Example 1 except that isopropyl myristate (manufactured by Kao Co., Ltd., trade name: EXEPARL IPM, Mn = 270): 10 parts by weight. (9)~(11).

The results are shown in Table 2.

[Examples 12 to 14]

The blending amount of CORONATE HX (Japan Polyurethane Industrial Co., Ltd.) which is a polyfunctional alicyclic isocyanate compound of a polyfunctional isocyanate compound was changed as shown in Table 2, and, as shown in Table 2, it was formulated as a fatty acid ester. A surface protective film with a separator was obtained in the same manner as in Example 1 except that isopropyl myristate (manufactured by Kao Co., Ltd., trade name: EXEPARL IPM, Mn = 270): 30 parts by weight. (12)~(14).

The results are shown in Table 2.

[Examples 15 to 17]

The blending amount of CORONATE HX (Japan Polyurethane Industrial Co., Ltd.) which is a polyfunctional alicyclic isocyanate compound of a polyfunctional isocyanate compound was changed as shown in Table 3, and, as shown in Table 3, it was formulated as a fatty acid ester. In the same manner as in Example 1, except that the ethyl cetyl 2-ethylhexanoate (manufactured by Nisshin Oilli O Group Co., Ltd., trade name: Salacos 816T, Mn = 368): 10 parts by weight, was obtained in the same manner as in Example 1. The surface protective film of the diaphragm (15)~(17).

The results are shown in Table 3.

[Examples 18 to 20]

The blending amount of CORONATE HX (Japan Polyurethane Industrial Co., Ltd.) which is a polyfunctional alicyclic isocyanate compound of a polyfunctional isocyanate compound was changed as shown in Table 3, and, as shown in Table 3, it was formulated as a fatty acid ester. In the same manner as in Example 1, except that the ethyl cetyl 2-ethylhexanoate (manufactured by Nisshin Oilli O Group Co., Ltd., trade name: Salacos 816T, Mn = 368): 30 parts by weight, was obtained in the same manner as in Example 1. The surface protection film of the diaphragm (18)~(20).

The results are shown in Table 3.

[Example 21]

100 parts by weight of a CYABINE SH-109H (solid content: 54%, containing a fatty acid ester, manufactured by Toyo Ink) as a urethane prepolymer, and a polyfunctional alicyclic isocyanate compound as a polyfunctional isocyanate compound CORONATE HX (Japan Polyurethane Industry Co., Ltd.): 1.4 parts by weight, Elexcel AS110 (ionic liquid, manufactured by Daiichi Kogyo Co., Ltd.): 1.50 parts by weight, KF6004 (polyether modified organic hydrazine, Shin-Etsu Chemical Co., Ltd. (manufactured by Ltd.): 0.01 parts by weight of toluene as a diluent solvent: 208 parts by weight, and stirred by a disperser to obtain a urethane-based pressure-sensitive adhesive composition.

The obtained urethane-based pressure-sensitive adhesive composition was applied onto a substrate "Lumirror S10" (thickness: 38 μm, manufactured by TORAY INDUSTRIES Co., Ltd.) containing a polyester resin by a dipping roller to have a thickness of 10 μm after drying. Curing and drying under the conditions of a drying temperature of 130 ° C and a drying time of 30 seconds. In this manner, an adhesive layer containing an urethane-based adhesive (21) was formed on a substrate.

Then, an organic tantalum-treated surface of a separator containing a polyester resin having a thickness of 25 μm which was subjected to an organic tantalum treatment on the surface of the adhesive layer was bonded to obtain a surface protective film (21) with a separator.

The results are shown in Table 4.

[Examples 22 to 25]

In the same manner as in Example 21, except that the blending amount of CORONATE HX (Japan Polyurethane Industrial Co., Ltd.) of the polyfunctional alicyclic isocyanate compound as the polyfunctional isocyanate compound was changed as shown in Table 4. , obtain the surface protective film (22) ~ (25) with a diaphragm.

The results are shown in Table 4.

[Comparative Examples 1 to 3]

In the same manner as in Example 1, except that the blending amount of CORONATE HX (Japan Polyurethane Industrial Co., Ltd.) which is a polyfunctional alicyclic isocyanate compound of a polyfunctional isocyanate compound was changed as shown in Table 5. , obtain the surface protective film (C1) ~ (C3) with a diaphragm.

The results are shown in Table 5.

[Comparative Example 4]

In the same manner as in Example 21, except that the blending amount of CORONATE HX (Japan Polyurethane Industrial Co., Ltd.) of the polyfunctional alicyclic isocyanate compound as the polyfunctional isocyanate compound was changed as shown in Table 5. A surface protective film (C4) with a separator was obtained.

The results are shown in Table 5.

[Example 26]

The separator of the surface protective film with a separator obtained in Example 1 was peeled off and attached to a polarizing plate (manufactured by Nitto Denko Corporation, trade name "TEG1465DUHC") as an optical member to obtain an optical film to which a surface protective film was attached. member.

[Example 27]

The separator of the surface protective film with a separator obtained in Example 9 was peeled off and attached to a polarizing plate (manufactured by Nitto Denko Corporation, trade name "TEG1465DUHC") as an optical member to obtain an optical film to which a surface protective film was attached. member.

[Example 28]

The separator of the surface protective film with a separator obtained in Example 15 was peeled off and attached to a polarizing plate (manufactured by Nitto Denko Corporation, trade name "TEG1465DUHC") as an optical member to obtain an optical film to which a surface protective film was attached. member.

[Example 29]

The separator of the surface protective film with a separator obtained in Example 21 was peeled off and attached to a polarizing plate (manufactured by Nitto Denko Corporation, trade name "TEG1465DUHC") as an optical member to obtain an optical film to which a surface protective film was attached. member.

[Example 30]

The separator of the surface protective film with a separator obtained in Example 1 was peeled off and attached to a conductive film (manufactured by Nitto Denko Corporation, trade name "ELECRYSTA V270L-TFMP") as an electronic member to obtain a surface to which the surface was attached. The electronic component of the protective film.

[Example 31]

The separator of the surface protective film with a separator obtained in Example 9 was peeled off and attached to a conductive film (manufactured by Nitto Denko Corporation, trade name "ELECRYSTA V270L-TFMP") as an electronic member, and a surface was attached thereto. The electronic component of the protective film.

[Example 32]

The separator of the surface protective film with a separator obtained in Example 15 was peeled off and attached to a conductive film (manufactured by Nitto Denko Corporation, trade name "ELECRYSTA V270L-TFMP") as an electronic member to obtain a surface to which the surface was attached. The electronic component of the protective film.

[Example 33]

The separator of the surface protective film with a separator obtained in Example 21 was peeled off and attached to a conductive film (manufactured by Nitto Denko Co., Ltd., trade name "ELECRYSTA V270L-TFMP") as an electronic member, and a surface was attached thereto. The electronic component of the protective film.

[Industrial availability]

The surface protective film of the present invention can be used for any suitable purpose. Preferably, the surface protective film of the present invention is preferably used for surface protection of optical members or electronic members.

1‧‧‧ substrate layer

2‧‧‧Adhesive layer

10‧‧‧Surface protection film

Claims (10)

A surface protective film comprising an adhesive layer comprising a urethane-based adhesive containing a polyurethane resin as a main component, such that the adhesive layer side only by its own weight The adhesion ratio when bonded to the surface of the adherend having an average roughness Ra of the center line of 0.2 μm to 2 μm is 80% or more. The surface protective film of claim 1, wherein the polyurethane resin is a polyurethane resin obtained from a composition containing a polyol (A) and a polyfunctional isocyanate compound (B). The surface protective film of claim 2, wherein the polyol (A) has a number average molecular weight Mn of from 400 to 20,000. The surface protective film of claim 2, wherein the equivalent ratio of the NCO group to the OH group in the above polyol (A) and the polyfunctional isocyanate compound (B) is from 0.3 to 1.0 in terms of NCO group/OH group. The surface protective film of claim 1, wherein the above-mentioned polyurethane resin is a polyamine group obtained from a composition containing a urethane prepolymer (C) and a polyfunctional isocyanate compound (B). Acid ester resin. The surface protective film of claim 5, wherein the equivalent ratio of the NCO group to the OH group in the above urethane prepolymer (C) and the polyfunctional isocyanate compound (B) is 0.3 based on the NCO group/OH group. ~1.0. The surface protective film of claim 1, wherein the urethane-based adhesive contains a fatty acid ester. The surface protective film of claim 7, wherein the fatty acid ester has a number average molecular weight Mn of from 200 to 400. An optical member to which surface protection as claimed in any one of claims 1 to 8 is attached membrane. An electronic component to which a surface protective film according to any one of claims 1 to 8 is attached.