TWI661020B - Urethane-based pressure-sensitive adhesive and surface protective film using the pressure-sensitive adhesive - Google Patents

Abstract

The present invention provides a urethane-based adhesive that is very excellent in antistatic properties and excellent in paste residue resistance or secondary processability. In addition, the present invention provides a surface protective film, which uses such a urethane-based adhesive for an adhesive layer, and has very good antistatic properties, and excellent paste residue resistance or secondary processability. The present invention also provides an optical member or an electronic member to which such a surface protective film is attached. The urethane-based adhesive of the present invention is an urethane-based adhesive containing a urethane-based resin, and the urethane-based resin will contain a polyol (A) and a polyfunctional isocyanate compound (B Urethane resin obtained by curing the composition; the equivalent ratio of NCO group to OH group in the polyol (A) and the polyfunctional isocyanate compound (B) is more than 1.0 in terms of NCO group / OH group It is 5.0 or less; the urethane-based adhesive contains an ionic liquid containing a fluorine organic anion.

Description

Urethane adhesive and surface protective film using the same

The present invention relates to a urethane-based adhesive. Although the urethane-based adhesive of the present invention is an urethane-based adhesive generally known as a paste-sustaining agent, it is excellent in paste-resistance. The present invention also relates to a surface protection film using such a urethane-based adhesive. The surface protection film of the present invention has a base material layer and an adhesive layer, and is preferably used, for example, for attaching a surface of an optical member or an electronic member to protect the surface.

LCD (liquid crystal display, liquid crystal display), organic EL (Electro-Luminescence) display, the use of such touch panels, camera lens parts, electronic components such as electronic devices or electronic components, in order to prevent processing, For surface damage during assembly, inspection, and transportation, a surface protective film is usually attached to the exposed surface. At the point when no surface protection is required, such a surface protection film is peeled from the optical member or the electronic member.

Such surface protection films are increasingly used from the manufacturing steps of optical components or electronic components, through assembly steps, inspection steps, transportation steps, etc., until the final shipment, and the same surface protection film is continuously used. In this case, such a surface protection film is often attached, peeled off, and reattached by manual operation in each step.

When the surface protection film is attached by hand, there may be a case where air bubbles are caught between the adherend and the surface protection film. Therefore, there are some techniques reported to improve the wettability of the surface protection film so that air bubbles are not involved during the attachment. For example, it is known that the adhesive layer uses a surface protective film having a silicone resin with a faster wetting rate. However, when a silicone resin is used for the adhesive layer, the adhesive component tends to contaminate the adherend, and thus it is used as a surface protective film for protecting the surface of a member requiring particularly low pollution such as an optical member or an electronic member. There are problems.

As a surface protection film with less contamination due to an adhesive component, it is known to use an acrylic resin surface protection film for the adhesive layer. However, the surface protective film using an acrylic resin for the adhesive layer has poor wettability. Therefore, when the surface protective film is attached by hand, bubbles may be caught between the adherend and the surface protective film. Situation. In addition, when an acrylic resin is used for an adhesive layer, there is a problem that a paste residue is liable to occur during peeling, and thus it is used as a surface protection for protecting the surface of a member such as an optical member or an electronic member that is particularly resistant to the inclusion of impurities. There is a problem with the membrane.

As a surface protective film that can have both excellent wettability, low staining properties, and reduced paste residue, a surface protective film using a urethane-based adhesive as an adhesive layer has recently been reported (for example, refer to Patent Document 1).

However, conventional urethane-based adhesives are known as those which are liable to paste residue. For example, if it is stored in a heated state after being attached to an adherend, there is a problem that a paste residue is liable to be generated on the adherend.

In addition, when a surface protection film is attached to a to-be-adhered body by a manual operation, excellent wettability and light peelability are required. The reason for this is that after the surface protective film attached to the adherend is peeled off, it is reattached to the adherend and used again as the surface protective film. Even if the wettability is good, if the peeling is heavy, the surface protective film is deformed when the surface protective film is peeled, so that it cannot be used as a surface protective film again. In order to avoid such a problem, a surface protective film for an optical member or an electronic member is strongly requested for so-called reprocessing. Properties: Can be attached multiple times without being trapped in air bubbles and can be peeled off lightly without deformation. However, the surface protective film using a urethane-based adhesive for the adhesive layer reported so far has the following problems: the adhesive force of the adhesive layer is increased over time, and the state of being adhered to the adherend is sustained for a long period of time. Peeling and poor reworkability.

In addition, as described above, the surface protection film is peeled from the adherend such as an optical member or an electronic member at a point in time when no surface protection is required. At this time, the base material layer of the surface protection film, the optical member, or the electronic member contains a plastic material as a constituent material, and therefore has high electrical insulation properties, and generates static electricity during friction or peeling. Therefore, static electricity is also generated when the surface protective film is peeled off from an optical member such as a polarizing plate. If a voltage is applied to the liquid crystal in a state where such static electricity remains, the alignment of the liquid crystal molecules is lost or the panel is damaged.

[Prior technical literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2006-182795

The object of the present invention is to provide a urethane-based adhesive, which is very excellent in antistatic properties and excellent in paste residue resistance and reworkability. The object of the present invention is to provide a surface protection film whose adhesive layer uses such a urethane-based adhesive, and which has excellent antistatic properties and excellent paste residue or reworkability. An object of the present invention is to provide an optical member or an electronic member to which such a surface protective film is attached.

The urethane-based adhesive of the present invention includes a urethane-based resin, and the urethane-based resin is obtained by curing a composition containing a polyol (A) and a polyfunctional isocyanate compound (B). An urethane-based resin; the equivalent ratio of the NCO group to the OH group in the polyol (A) and the polyfunctional isocyanate compound (B) exceeds 1.0 and is 5.0 or less based on the NCO group / OH group; and This urethane-based adhesive contains an ionic liquid containing a fluorine organic anion.

In a preferred embodiment, the ionic liquid is composed of the fluorine organic anion and the onium cation.

In a preferred embodiment, the onium cation is at least one selected from the group consisting of a nitrogen-containing cation, a sulfur-containing cation, and a phosphorus-containing cation.

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

In a preferred embodiment, the content ratio of the polyfunctional isocyanate compound (B) to the polyol (A) is 5 to 60% by weight.

The surface protection film of the present invention includes a substrate layer and an adhesive layer, and the adhesive layer includes the urethane-based adhesive of the present invention.

The optical member of the present invention is one to which the surface protective film of the present invention is attached.

The electronic component of the present invention is one to which the surface protective film of the present invention is attached.

According to the present invention, it is possible to provide an urethane-based adhesive which is very excellent in antistatic properties and excellent in paste residue resistance or reworkability. In addition, according to the present invention, a surface protective film can be provided in which the urethane-based adhesive is used as the adhesive layer, and the antistatic property is very excellent, and the paste residual property or reworkability is also excellent. Furthermore, according to the present invention, it is possible to provide an optical member or an electronic member to which such a surface protection film is attached.

1‧‧‧ substrate layer

2‧‧‧ Adhesive layer

10‧‧‧ surface protective film

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

<< A. Urethane-based adhesives >> <A-1. Urethane resin>

The urethane-based adhesive of the present invention contains a urethane-based resin.

The lower limit value of the content ratio of the urethane-based resin in the urethane-based adhesive of the present invention is preferably 40% by weight or more, more preferably 50% by weight or more, and still more preferably 55% by weight or more. It is more preferably 60% by weight, particularly preferably 65% by weight, most preferably 70% by weight, and the upper limit value is preferably 99.999% by weight or less, more preferably 99.99% by weight or less, and still more preferably 99.9% by weight or less. It is further preferably 99% by weight or less, particularly preferably 95% by weight or less, and most preferably 90% by weight or less. Adjusting the content ratio of the urethane-based resin in the urethane-based adhesive of the present invention within the above-mentioned range can provide, for example, a very excellent antistatic property and excellent anti-paste residue or reworkability. Urethane-based adhesive.

The urethane-based resin is an urethane-based resin obtained by curing a composition containing a polyol (A) and a polyfunctional isocyanate compound (B).

As the polyol (A), there may be only one kind, or two or more kinds.

As the polyol (A), any polyol may be used as long as it is a polyol having two or more OH groups. Examples of such a polyol (A) include a polyol (diol) having two OH groups, a polyol (triol) having three OH groups, and a polyol (tetraol) having four OH groups. , A polyol (pentaol) having five OH groups, and a polyol (hexaol) having six OH groups.

In the present invention, as the polyol (A), a polyol (triol) having three OH groups is preferably used as an essential component. By using a polyhydric alcohol (triol) having three OH groups as an essential component as the polyhydric alcohol (A) in this way, it is possible to provide, for example, an amine having excellent antistatic properties and excellent paste residue or reworkability. Ethyl formate-based adhesive. The content ratio of the polyol (triol) having three OH groups in the polyol (A) is preferably 50% to 100% by weight, more preferably 70% to 100% by weight, and even more preferably 80% by weight. % To 100% by weight, more preferably 90% to 100% by weight, particularly preferably 95% to 100% by weight, and most preferably substantially 100% by weight.

As the polyol (A), it is preferred to include a number average molecular weight Mn of 400 to 20,000. Polyol. The content ratio of the polyol having a number average molecular weight Mn of 400 to 20,000 in the polyol (A) is preferably 50% to 100% by weight, more preferably 70% to 100% by weight, and even more preferably 90% by weight. ~ 100% by weight, particularly preferably from 95% to 100% by weight, and most preferably substantially 100% by weight. Adjusting the content ratio of the polyol with a number average molecular weight Mn of 400 to 20,000 in the polyol (A) within the above range can provide an amine having excellent antistatic properties and excellent paste residue or reworkability. Ethyl formate-based adhesive.

In the present invention, when a polyol (triol) having three OH groups is used as an essential component as the polyol (A), it is preferred to use a triol having a number average molecular weight Mn of 7,000 to 20,000 in combination. Triol having an average molecular weight Mn of 2,000 to 6000 and triol having a number average molecular weight Mn of 400 to 1900, more preferably a triol having a number average molecular weight Mn of 8000 to 15000 and a triol having a number average molecular weight Mn of 2,000 to 5,000 And triol having a number average molecular weight Mn of 500 to 1800, and further preferably a triol having a number average molecular weight Mn of 8000 to 12000, a triol having a number average molecular weight Mn of 2000 to 4000, and a number average molecular weight Mn of 500 to 1500 triol. When the three triols are used in combination, for example, a urethane-based adhesive having excellent antistatic properties and excellent paste residue or reworkability can be provided.

Examples of the polyol (A) include polyester polyol, polyether polyol, polycaprolactone polyol, polycarbonate polyol, and castor oil-based polyol.

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

Examples of the polyol component include ethylene glycol, diethylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, and 3-methyl-1,5-pentanediol. Alcohol, 2-butyl-2-ethyl-1,3-propanediol, 2,4-diethyl-1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, 1,8-decanediol, stearyl glycol, glycerol, trimethylolpropane , Pentaerythritol, hexanetriol, polypropylene glycol, etc.

Examples of the acid component include succinic acid, methylsuccinic acid, adipic acid, pimelic acid, azelaic acid, sebacic acid, 1,12-dodecanedioic acid, and 1,14-tetradecanedioic acid. Acid, dimer acid, 2-methyl-1,4-cyclohexanedicarboxylic acid, 2-ethyl-1,4-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, o-benzene Dicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, anhydrides thereof, and the like.

Examples of the polyether polyol include water, low molecular polyols (propylene glycol, ethylene glycol, glycerol, trimethylolpropane, pentaerythritol, etc.), bisphenols (bisphenol A, etc.), and dihydroxybenzene ( Catechol, resorcinol, hydroquinone, etc.) are polyether polyols obtained by addition polymerization of alkylene oxides such as ethylene oxide, propylene oxide, and butylene oxide. Specific examples include polyethylene glycol, polypropylene glycol, and polybutylene glycol.

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

Examples of the polycarbonate polyol include: a polycarbonate polyol obtained by performing a polycondensation reaction of the above-mentioned polyol component and phosgene; and a polyol component and dimethyl carbonate, diethyl carbonate, and dicarbonate It is obtained by transesterification of carbonic acid diesters such as propyl ester, diisopropyl carbonate, dibutyl carbonate, ethylbutyl carbonate, ethylene carbonate, propylene carbonate, diphenyl carbonate, and dibenzyl carbonate. Polycarbonate polyols; copolymerized polycarbonate polyols obtained by combining two or more of the above-mentioned polyol components; polycarbonate polyols obtained by esterifying the various polycarbonate polyols described above with carboxyl-containing compounds ; A polycarbonate polyol obtained by performing an etherification reaction on the above-mentioned various polycarbonate polyols and a hydroxyl-containing compound; a polycarbonate obtained by performing an ester interchange reaction on the above-mentioned various polycarbonate polyols and an ester compound Polyols; Polycarbonate polyols obtained by transesterifying the above-mentioned various polycarbonate polyols with hydroxyl-containing compounds; Polyester-based carboxylic acid compound obtained by a polycondensation reaction of a polycarbonate polyol; of the above polycarbonate polyol with an alkylene oxide obtained by the copolymerization of copolyether polycarbonate-based polyol.

Examples of the castor oil-based polyol include a castor oil-based polyol obtained by reacting a castor oil fatty acid with the above-mentioned polyol component. Specific examples include castor oil-based polyols obtained by reacting castor oil fatty acids with polypropylene glycol.

The polyfunctional isocyanate compound (B) may be only one kind, or may be two or more kinds.

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

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

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

Examples of the polyfunctional aromatic diisocyanate compound include benzene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 2,2'-diphenylmethane diisocyanate, and 4,4'- Diphenylmethane diisocyanate, 4,4'-toluidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, benzenediphenyl Methylene diisocyanate.

Examples of the polyfunctional isocyanate compound (B) include the trimethylolpropane adduct of the polyfunctional isocyanate compound described above, biuret that reacts with water, and a terpolymer having an isocyanurate ring. Wait. In addition, these may be used in combination.

The content ratio of the polyfunctional isocyanate compound (B) is preferably 5 to 60% by weight, and more preferably 8 to 60% by weight relative to the polyol (A). The amount is preferably 10% by weight to 60% by weight. By adjusting the content ratio of the polyfunctional isocyanate compound (B) within the above range, for example, it is possible to provide an urethane-based adhesive that is very excellent in antistatic properties and excellent in paste residue resistance or reworkability.

The equivalent ratio of the NCO group to the OH group in the polyol (A) and the polyfunctional isocyanate compound (B) exceeds 1.0 and is 5.0 or less in terms of the NCO group / OH group, preferably 1.1 to 5.0, and more preferably 1.2 to 4.0. , More preferably 1.5 to 3.5, and particularly preferably 1.8 to 3.0. Adjusting the equivalent ratio of the NCO group / OH group within the above range can provide, for example, an urethane-based adhesive that is very excellent in antistatic properties and excellent in paste residue resistance or reworkability.

The urethane-based resin is obtained by curing a composition containing a polyol (A) and a polyfunctional isocyanate compound (B). Such a composition may contain any appropriate other components in addition to the polyol (A) and the polyfunctional isocyanate compound (B), as long as the effect of the present invention is not impaired. Examples of such other components include catalysts, resin components other than urethane resins, tackifiers, inorganic fillers, organic fillers, metal powders, pigments, foils, softeners, and plastics. Chemical agents, anti-aging agents, conductive agents, antioxidants, ultraviolet absorbers, light stabilizers, surface lubricants, leveling agents, corrosion inhibitors, heat-resistant stabilizers, polymerization inhibitors, lubricants, solvents, etc.

The urethane-based resin preferably contains an anti-deterioration agent such as an antioxidant, an ultraviolet absorber, and a light stabilizer. Since the urethane-based resin contains an anti-deterioration agent, even if it is stored in a warmed state after being adhered to the adherend, it is difficult to cause paste residues such as paste residues to be excellent in the adherend. The anti-deterioration agent may be only one kind, or may be two or more kinds. As the deterioration preventing agent, an antioxidant is particularly preferable.

The content ratio of the anti-deterioration agent is preferably 0.01% to 20% by weight, more preferably 0.02% to 15% by weight, and still more preferably 0.03% to 10% by weight relative to the polyol (A). It is preferably 0.05% to 7% by weight, more preferably 0.1% to 5% by weight, particularly preferably 0.1% to 3% by weight, and most preferably 0.1% to 1% by weight. Adjust the content ratio of the anti-deterioration agent within the above range, even after attaching to the adherend It can be stored in a warmed state, and paste residues are not easily generated on the adherend, which can further improve paste residue resistance. If the content ratio of the anti-deterioration agent is too small, there is a possibility that the anti-paste residue property may not be sufficiently expressed. If the content ratio of the anti-deterioration agent is too large, there is a possibility that a problem that is disadvantageous in terms of cost, a problem that the adhesion characteristics cannot be maintained, or a problem that the adherend is contaminated.

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

Examples of the free radical chain inhibitor include phenol-based antioxidants and amine-based antioxidants.

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

Examples of the phenol-based antioxidant include a monophenol-based antioxidant, a bisphenol-based antioxidant, and a polymer-type phenol-based antioxidant.

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

Examples of the bisphenol-based antioxidant include 2,2'-methylenebis (4-methyl-6-third-butylphenol) and 2,2'-methylenebis (4-ethyl- 6-third butylphenol), 4,4'-thiobis (3-methyl-6-third butylphenol), 4,4'-butylenebis (3-methyl-6-third Butylphenol), 3,9-bis [1,1-dimethyl-2- [β- (3-third-butyl-4-hydroxy-5-methylphenyl) propanyloxy] ethyl ] 2,4,8,10-tetraoxaspiro [5,5] undecane and the like.

Examples of the polymer-type phenolic antioxidant include 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane and 1,3,5-trimethyl -2,4,6-tris (3,5-di-third-butyl-4-hydroxybenzyl) benzene, tetra- [methylene-3- (3 ', 5'-di-third-butyl -4'-hydroxyphenyl) propionate] methane, di [3,3'-bis- (4'-hydroxy-3'-third butylphenyl) butanoic acid] ethylene glycol ester, 1, 3,5-tris (3 ', 5'-di-tertiary-butyl-4'-hydroxybenzyl) -s-triazine-2,4,6- (1H, 3H, 5H) trione, fertility Phenol and so on.

Examples of the sulfur-based antioxidant include: 3,3'-thiodipropionate dilauryl, 3,3'-thiodipropionate dimyristyl, and 3,3'-thiodipropionate Stearyl ester, etc.

Examples of the phosphorus-based antioxidant include triphenyl phosphite, diphenyl isodecyl phosphite, and phenyl diisodecyl phosphite.

Examples of the ultraviolet absorber include a benzophenone-based ultraviolet absorber, a benzotriazole-based ultraviolet absorber, a salicylic acid-based ultraviolet absorber, a chlorhexidine-based ultraviolet absorber, and a cyanoacrylate-based ultraviolet light Absorbers, triazine-based ultraviolet absorbers, and the like.

Examples of the benzophenone-based ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, and 2-hydroxy-4-octyloxybenzophenone. Methanone, 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, etc.

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

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

Examples of the cyanoacrylic ultraviolet absorber include 2-ethylhexyl-2- Cyano-3,3'-diphenylacrylate, ethyl-2-cyano-3,3'-diphenylacrylate, 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-piperidinyl) sebacate] and bis (1,2,2,6,6 -Pentamethyl-4-piperidinyl) sebacate, 1,2,2,6,6-pentamethyl-4-piperidinylsebacate and the like.

Examples of the ultraviolet stabilizer include bis (octylphenyl) nickel sulfide, [2,2'-thiobis (4-third octylphenol)]-n-butylamine nickel, and nickel complex- 3,5-Di-tert-butyl-4-hydroxybenzyl-monoethyl phosphate, nickel dibutyldithiocarbamate, benzoate type quencher, dibutyl dithioamine Nickel formate and so on.

As the deterioration preventing agent, a deterioration preventing agent having a hindered phenol structure is preferred. In the case where an anti-degradation agent having a hindered phenol structure is included as an anti-degradation agent, the content ratio thereof is preferably 0.01% to 10% by weight, and more preferably 0.05% to 10% by weight relative to the polyol (A). It is more preferably 0.1% by weight to 10% by weight. The content ratio of the anti-deterioration agent with a hindered phenol structure is adjusted within the above range, and even if it is stored in a heated state after being adhered to the adherend, it is difficult to produce paste residues on the adherend, etc. The paste residue is further excellent. If the content of the anti-deterioration agent having a hindered phenol structure is too small, there is a possibility that the anti-paste residue property may not be sufficiently expressed. If the content ratio of the anti-deterioration agent having a hindered phenol structure is too large, there is a possibility that a problem that is disadvantageous in terms of cost, a problem that the adhesion characteristics cannot be maintained, or a problem that the adherend is contaminated.

As the anti-deterioration agent having a hindered phenol structure, for example, as long as it has at least one adjacent carbon atom of a carbon atom on an aromatic ring bonded to an OH group bonded to phenol, a third butyl group such as a sterically hindered group is blocked. A phenol-based deterioration preventing agent is sufficient, and any appropriate deterioration preventing agent can be used. Considering that the use of a specific anti-deterioration agent having such a hindered phenol structure as an anti-deterioration agent can greatly reduce the molecular weight reduction of the polyol compared to the previous one, the anti-paste residue performance can be compared with the previous one. Particularly excellent effect.

Specific examples of such a deterioration preventing agent having a hindered phenol structure include dibutyl hydroxytoluene (BHT); trade names "IRGANOX 1010" (manufactured by BASF), trade names "IRGANOX 1010FF" (manufactured by BASF), Trade name "IRGANOX 1035" (manufactured by BASF), trade name "IRGANOX 1035FF" (manufactured by BASF), trade name "IRGANOX 1076" (manufactured by BASF), trade name "IRGANOX 1076FD" (manufactured by BASF), trade name "IRGANOX 1076DWJ" (Made by BASF), trade name `` IRGANOX 1098 '' (made by BASF), trade name `` IRGANOX 1135 '' (made by BASF), trade name `` IRGANOX 1330 '' (made by BASF), trade name `` IRGANOX 1726 '' (made by BASF), product Name "IRGANOX 1425WL" (made by BASF), trade name "IRGANOX 1520L" (made by BASF), trade name "IRGANOX 245" (made by BASF), trade name "IRGANOX 245FF" (made by BASF), trade name "IRGANOX 259" ( (Made by BASF), trade name "IRGANOX 3114" (made by BASF), trade name "IRGANOX 565" (made by BASF), trade name "IRGANOX 295" (bath Hindered phenol-based antioxidants, etc .; trade name "TINUVIN P" (manufactured by BASF), trade name "TINUVIN P FL" (manufactured by BASF), trade name "TINUVIN 234" (manufactured by BASF), trade name "TINUVIN 326" ( BASF), trade name `` TINUVIN 326FL '' (manufactured by BASF), trade name `` TINUVIN 328 '' (manufactured by BASF), trade name `` TINUVIN 329 '' (manufactured by BASF), trade name `` TINUVIN 329FL '' (manufactured by BASF), etc. Triazole-based UV absorbers; liquid UV absorbers such as "TINUVIN 213" (manufactured by BASF) and "TINUVIN 571" (manufactured by BASF); triazine-based UV rays such as "TINUVIN 1577ED" (manufactured by BASF) Absorbents; benzoate-based UV absorbers such as the brand name "TINUVIN 120" (manufactured by BASF); hindered amine-based light stabilizers such as the brand name "TINUVIN 144" (manufactured by BASF).

The urethane-based resin preferably contains a fatty acid ester. When the urethane-based resin contains a fatty acid ester, the wetting rate can be increased. The fatty acid ester may be only one or may be More than two.

The content ratio of the fatty acid ester relative to the polyol (A) is preferably 5% to 50% by weight, more preferably 7% to 40% by weight, and still more preferably 8% to 35% by weight, and is particularly preferable. It is preferably 9% to 30% by weight, and most preferably 10% to 20% by weight. Adjusting the content ratio of the fatty acid ester within the above range can further increase the wetting rate. If the content ratio of the fatty acid ester is too small, there is a possibility that the wetting rate cannot be sufficiently increased. If the content ratio of the fatty acid ester is too large, there may be a problem that it is disadvantageous in terms of cost, a problem that the adhesion characteristics cannot be maintained, or a problem that the adherend is contaminated.

The number average molecular weight Mn of the fatty acid ester is preferably 200 to 400, more preferably 210 to 395, still more preferably 230 to 380, particularly preferably 240 to 360, and most preferably 270 to 340. By adjusting the number average molecular weight Mn of the fatty acid ester within the above range, the wetting rate can be further increased. If the number average molecular weight Mn of the fatty acid ester is too small, there is a possibility that the wetting rate will not increase even if the number of added components is large. If the number average molecular weight Mn of the fatty acid ester is too large, the hardenability of the adhesive during drying may be deteriorated, which may adversely affect not only the wetting characteristics but also other adhesive characteristics.

As long as the effect of the present invention is not impaired, any appropriate fatty acid ester can be used as the fatty acid ester. Examples of such fatty acid esters include polyoxyethylene bisphenol A laurate, butyl stearate, 2-ethylhexyl palmitate, 2-ethylhexyl stearate, and behenane Acid monoglyceride, cetyl 2-ethylhexanoate, isopropyl myristate, isopropyl palmitate, cholesteryl isostearate, lauryl methacrylate, methyl cocoate, Methyl laurate, methyl oleate, methyl stearate, myristyl myristate, octyl dodecyl myristate, pentaerythritol monooleate, pentaerythritol monostearate, pentaerythritol tetrapalmitate Esters, stearyl stearate, isotridecyl stearate, 2-ethylhexanoate triglyceride, butyl laurate, octyl oleate, and the like.

The urethane-based resin preferably contains a leveling agent. By including a leveling agent in the urethane-based resin, uneven appearance due to orange peel can be prevented. Leveling agent can be only one, or It can be two or more.

The content ratio of the leveling agent is preferably 0.001% by weight to 1% by weight, more preferably 0.002% by weight to 0.5% by weight, and further preferably 0.003% by weight to 0.1% by weight relative to the polyol (A). It is preferably 0.004% to 0.05% by weight, and most preferably 0.005% to 0.01% by weight. By adjusting the content ratio of the leveling agent within the above range, it is possible to further prevent the appearance unevenness caused by the orange peel. If the content ratio of the leveling agent is too small, the appearance unevenness caused by the orange peel may not be prevented. If the content ratio of the leveling agent is too large, there may be a problem that it is disadvantageous in terms of cost, a problem that the adhesive properties cannot be maintained, or a problem that the adherend is contaminated.

As the leveling agent, any appropriate leveling agent can be used as long as the effect of the present invention is not impaired. Examples of such a leveling agent include an acrylic leveling agent, a fluorine leveling agent, and a silicon leveling agent. Examples of the acrylic leveling agent include POLYFLOW No. 36, POLYFLOW No. 56, POLYFLOW No. 85HF, and POLYFLOW No. 99C (all manufactured by Kyoeisha Chemical Co., Ltd.). Examples of the fluorine-based leveling agent include MEGAFACE F470N, MEGAFACE F556 (both manufactured by DIC Corporation), and the like. Examples of the silicon-based leveling agent include GRANDIC PC4100 (manufactured by DIC Corporation).

As a method for obtaining a urethane-based resin by curing a composition containing a polyol (A) and a polyfunctional isocyanate compound (B) as long as the effect of the present invention is not impaired, block polymerization or a solution can be used. Any appropriate method such as a urethane reaction method such as polymerization. However, there is a possibility that the effect of the present invention may not be exhibited in an urethane-based resin obtained through a so-called urethane prepolymer. Therefore, it is a combination of a polyol (A) and a polyfunctional isocyanate compound (B) The method for obtaining a urethane-based resin by curing the material is preferably a method other than a method for obtaining a urethane-based resin through a urethane prepolymer.

In order to harden a composition containing a polyol (A) and a polyfunctional isocyanate compound (B), it is preferable to use a catalyst. Examples of such catalysts include organometallic compounds Compounds, tertiary amine compounds, etc.

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

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

Examples of the tin-based compound include dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin maleate, dibutyltin dilaurate, dibutyltin diacetate, and dibutyltin. Tin sulfide, tributyltin methoxide, tributyltin acetate, triethylethoxytin, tributylethoxytin, dioctyltin oxide, dioctyltin dilaurate, tributyltin chloride , Tributyltin trichloroacetate, 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-based compound include zirconium naphthenate and zirconium acetoacetone.

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) undec-7-ene, and the like. ,

The catalyst may be only one type, or may be two or more types. In addition, a catalyst, a cross-linking retarder, and 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, and more preferably 0.02% by weight to 0.06% by weight relative to the polyol (A), and particularly preferably 0.02% to 0.05% by weight. When the amount of the catalyst is adjusted within the above range, for example, a urethane-based adhesive having excellent antistatic properties and excellent paste residue or reworkability can be provided.

<A-2. Ionic liquid>

The urethane-based adhesive of the present invention contains an ionic liquid containing a fluorine organic anion. Since the urethane-based adhesive of the present invention contains an ionic liquid containing a fluorine organic anion, an urethane-based adhesive having excellent antistatic properties can be provided. The urethane-based adhesive of the present invention may contain only one ionic liquid or two or more ionic liquids.

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

As long as the effect of the present invention is not impaired, any appropriate ionic liquid may be used as long as the ionic liquid is a liquid containing a fluorine organic anion. As such an ionic liquid, for example, an ionic liquid composed of a fluorine organic anion and an onium cation is preferable. As an ionic liquid, by using an ionic liquid composed of a fluorine organic anion and an onium cation, an urethane-based adhesive having extremely excellent antistatic properties can be provided.

As the onium cation that can constitute an ionic liquid, any appropriate onium cation can be used as long as the effect of the present invention is not impaired. Such an onium cation is preferably at least one selected from the group consisting of a nitrogen-containing cation, a sulfur-containing cation, and a phosphorus-containing cation. By selecting these onium cations, it is possible to provide an urethane-based adhesive with extremely excellent antistatic properties.

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

In the general formula (1), Ra represents a hydrocarbon group having 4 to 20 carbon atoms and may include 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 include a hetero atom. However, when the nitrogen atom contains a double bond, Rc does not exist.

In the general formula (2), Rd represents a hydrocarbon group having 2 to 20 carbon atoms and may include heteroatoms, 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 include heteroatoms.

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

In the general formula (4), Z represents a nitrogen atom, a sulfur atom, or a phosphorus atom, R1, Rm, Rn, and Ro are the same or different, and represent a hydrocarbon group having 1 to 20 carbon atoms, which may include a hetero atom. However, when Z is a sulfur atom, Ro does not exist.

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

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

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

Among them, in terms of further exhibiting the effects of the present invention, preferred examples include 1-ethylpyridinium cation, 1-butylpyridinium cation, 1-hexylpyridinium cation, and 1-ethyl 3-methylpyridinium cation, 1-butyl-3-methylpyridinium cation, 1-hexyl-3-methylpyridinium cation, 1-butyl-4-methylpyridinium cation, 1- Pyridinium cations 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 Pyrrolidinium cations such as onium cations, 1-ethyl-1-heptylpyrrolidinium cations; 1-methyl-1-ethylpiperidinium cations, 1-methyl-1-propylpiperidinium cations, 1-methyl-1-butylpiperidinium cation, 1-methyl-1-pentylpiper Pyridinium cation, 1-methyl-1-hexylpiperidinium cation, 1-methyl-1-heptylpiperidinium cation, 1-ethyl-1-propylpiperidinium cation, 1-ethyl- 1-butylpiperidinium cation, 1-ethyl-1-pentylpiperidinium cation, 1-ethyl-1-hexylpiperidinium cation, 1-ethyl-1-heptylpiperium Piperidinium cations such as a pyridinium cation, 1-propyl-1-butylpiperidinium cation, etc .; more preferably 1-hexylpyridinium cation, 1-ethyl-3-methylpyridinium cation, 1-butane 3-methylpyridinium cation, 1-octyl-4-methylpyridinium cation, 1-methyl-1-propylpyrrolidinium cation, 1-methyl-1-propylpiperidinium cation .

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

Specific examples of the cation represented by the general formula (2) include, for example, 1,3-dimethylimidazolium cation, 1,3-diethylimidazolium cation, and 1-ethyl-3-methylimidazolium. Cation, 1-butyl-3-methylimidazolium cation, 1-hexyl-3-methylimidazolium cation, 1-octyl-3-methylimidazolium cation, 1-decyl-3-methylimidazolium Onium cation, 1-dodecyl-3-methylimidazolium cation, 1-tetradecyl-3-methylimidazolium cation, 1,2-dimethyl-3-propylimidazolium cation, 1 -Ethyl-2,3-dimethylimidazolium cation, 1-butyl-2,3-dimethylimidazolium cation, 1-hexyl-2,3-dimethylimidazolium cation, and other imidazolium cations; 1,3-dimethyl-1,4,5,6-tetrahydropyrimidinium cation, 1,2,3-trimethyl-1,4,5,6-tetrahydropyrimidinium cation, 1,2, Tetrahydrogen such as 3,4-tetramethyl-1,4,5,6-tetrahydropyrimidinium cation, 1,2,3,5-tetramethyl-1,4,5,6-tetrahydropyrimidinium cation Pyrimidinium cations; 1,3-dimethyl-1,4-dihydropyrimidinium cations, 1,3-dimethyl-1,6-dihydropyrimidinium cations, 1,2,3-trimethyl- 1,4-dihydropyrimidinium cation, 1,2,3-trimethyl-1,6-di Dihydrogen such as pyrimidinium cation, 1,2,3,4-tetramethyl-1,4-dihydropyrimidinium cation, 1,2,3,4-tetramethyl-1,6-dihydropyrimidinium cation Pyrimidinium cations and the like.

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

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

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

Examples of the cation represented by the general formula (4) include a tetraalkylammonium cation, a trialkylphosphonium cation, a tetraalkylphosphonium cation, or an alkyl group substituted with an alkenyl group or an alkoxy group and then an epoxy group. Finished and so on.

Specific examples of the cation represented by the general formula (4) include a tetramethylammonium cation, a tetraethylammonium cation, a tetrabutylammonium cation, a tetrapentylammonium cation, a tetrahexylammonium cation, and a tetraheptylammonium cation. Cation, triethylmethylammonium cation, tributylethylammonium cation, trimethylpropylammonium cation, trimethyldecylammonium cation, N, N-diethyl-N-methyl-N- ( 2-methoxyethyl) ammonium cation, glycidyl trimethylammonium cation, trimethylphosphonium cation, triethylphosphonium cation, tributylphosphonium cation, trihexylphosphonium cation, diethylmethylphosphonium cation , Dibutylethylphosphonium cation, dimethyldecylphosphonium cation, tetramethylphosphonium cation, tetraethylphosphonium cation, tetrabutylphosphonium cation, tetrahexylphosphonium cation, tetraoctylphosphonium cation, triethylformyl Methyl sulfonium cation, tributylethylsulfonium cation, trimethyldecylsulfonium cation, diallyldimethylammonium cation, and the like.

Among these, in terms of further exhibiting the effects of the present invention, preferred examples include triethylmethylammonium cation, tributylethylammonium cation, trimethyldecylammonium cation, and diethyl Methylmethylsulfonium cation, dibutylethylsulfonium cation, dimethyldecylsulfonium cation, triethylmethylsulfonium cation, tributylethylsulfonium cation, trimethyldecylsulfonium Asymmetric tetraalkylammonium cation, trialkylphosphonium cation, tetraalkylphosphonium cation; or N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium cation, Glycidyltrimethylammonium cation, diallyldimethylammonium cation, N, N-dimethyl-N-ethyl-N-propylammonium cation, N, N-dimethyl-N-ethyl -N-butylammonium cation, N, N-dimethyl-N-ethyl-N-pentylammonium cation, N, N-dimethyl-N-ethyl-N-hexylammonium cation, N, N-dimethyl-N-ethyl-N-heptylammonium cation, N, N-dimethyl-N-ethyl-N-nonylammonium cation, N, N-dimethyl-N, N- Dipropylammonium cation, N, N-diethyl-N-propyl-N-butylammonium cation, N, N-dimethyl-N-propyl-N-pentylammonium cation, N, N- Dimethyl-N-propyl-N-hexylammonium cation, N, N-dimethyl-N-propyl-N-heptylammonium cation, N, N-dimethyl-N-butyl-N- Hexyl ammonium cation, N, N-diethyl-N-butyl-N-heptylammonium cation, N, N-dimethyl-N-pentyl-N-hexylammonium cation, N, N-dimethyl -N, N-dihexylammonium cation, trimethylheptylammonium cation, N, N-diethyl-N-methyl-N-propylammonium cation, N, N-diethyl -N-methyl-N-pentylammonium cation, N, N-diethyl-N-methyl-N-heptylammonium cation, N, N-diethyl-N-propyl-N-pentyl Ammonium cation, triethylpropylammonium cation, triethylpentylammonium cation, triethylheptylammonium cation, N, N-dipropyl-N-methyl-N-ethylammonium cation, N, N -Dipropyl-N-methyl-N-pentylammonium cation, N, N-dipropyl-N-butyl-N-hexylammonium cation, N, N-dipropyl-N, N-dihexyl Ammonium cation, N, N-dibutyl-N-methyl-N-pentylammonium cation, N, N-dibutyl-N-methyl-N-hexylammonium cation, trioctylmethylammonium cation, N-methyl-N-ethyl-N-propyl-N-pentylammonium cation and the like, more preferably trimethylpropylammonium cation.

As a fluorine organic anion which can constitute an ionic liquid, any appropriate fluorine organic anion can be used as long as the effect of the present invention is not impaired. Such fluoroorganic anions may be fully fluorinated (perfluorinated) or may be partially fluorinated.

Examples of such fluoroorganic anions include fluorinated arylsulfonates, perfluoroalkanesulfonates, bis (fluorosulfonyl) fluorenimines, and bis (perfluoroalkanesulfonyl) fluorenes. Amines, cyanoperfluoroalkanesulfonamides, bis (cyano) perfluoroalkanesulfonamidomethylates, cyano- Bis (perfluoroalkanesulfonyl) methylate, tris (perfluoroalkanesulfonyl) methylate, trifluoroacetate, perfluoroalkylate, tris (perfluoroalkanesulfonyl) methylate , (Perfluoroalkanesulfonyl) trifluoroacetamide and the like.

Among the fluoroorganic anions, more preferred are perfluoroalkylsulfonate, bis (fluorosulfofluorenyl) fluorenimide, and bis (perfluoroalkanesulfonyl) fluorenimide, and more specifically, for example, tris Fluoromethanesulfonate, pentafluoroethylsulfonate, heptafluoropropylsulfonate, nonafluorobutylsulfonate, bis (fluorosulfonyl) fluorenimide, bis (trifluoromethylsulfonium) Amidyl) imine.

Specific examples of the ionic liquid contained in the urethane-based adhesive of the present invention can be appropriately selected and used from the combination of the above-mentioned cationic component and the above-mentioned anionic component. Specific examples of such an ionic liquid include 1-hexylpyridinium bis (fluorosulfonyl) fluorenimine, 1-ethyl-3-methylpyridinium trifluoromethanesulfonate, 1 -Ethyl-3-methylpyridinium pentafluoroethylsulfonate, 1-ethyl-3-methylpyridinium heptafluoropropylsulfonate, 1-ethyl-3-methylpyridinium nonafluoro Butylsulfonate, 1-butyl-3-methylpyridinium trifluoromethanesulfonate, 1-butyl-3-methylpyridinium bis (trifluoromethylsulfonyl) fluorenimine, 1-butyl-3-methylpyridinium bis (pentafluoroethylsulfonyl) fluorenimide, 1-octyl-4-methylpyridinium bis (fluorosulfonyl) fluorenimide, 1,1 -Dimethylpyrrolidinium bis (trifluoromethylsulfonyl) fluorenimine, 1-methyl-1-ethylpyrrolidinium bis (trifluoromethylsulfonyl) fluorenimine, 1-methyl Propyl-1-propylpyrrolidinium bis (trifluoromethylsulfonyl) fluorenimide, 1-methyl-1-propylpyrrolidinium bis (fluorosulfonyl) fluorenimine, 1-methyl 1-Butylpyrrolidinium bis (trifluoromethylsulfonyl) fluorenimine, 1-methyl-1-pentylpyrrolidinium bis (trifluoromethylsulfonyl) fluorenimine, 1- Methyl-1-hexylpyrrolidinium bis (trifluoromethylsulfonyl) fluorenimine, 1-methyl 1-heptylpyrrolidinium bis (trifluoromethylsulfonyl) fluorenimine, 1-ethyl-1-propylpyrrolidinium bis (trifluoromethylsulfonyl) fluorenimine, 1 -Ethyl-1-butylpyrrolidinium bis (trifluoromethylsulfonyl) fluorenimine, 1-ethyl-1-pentylpyrrolidinium bis (trifluoromethylsulfonyl) fluorenimine , 1-ethyl-1-hexylpyrrolidinium bis (trifluoromethylsulfonyl) fluorenimine, 1-ethyl-1-heptylpyrrolidinium bis (trifluoromethylsulfonyl) fluorene Amine, 1,1-dipropylpyrrolidinium bis (trifluoromethylsulfonyl) fluorenimine, 1-propyl-1-butyl Pyrrolidinium bis (trifluoromethylsulfonyl) fluorenimide, 1,1-dibutylpyrrolidinium bis (trifluoromethylsulfonyl) phosphonium imine, 1-propylpiperidinium bis ( Trifluoromethylsulfonyl) fluorenimide, 1-pentylpiperidinium bis (trifluoromethylsulfonyl) fluorenimide, 1,1-dimethylpiperidinium bis (trifluoromethylsulfonium) (Fluorenyl) fluorenimine, 1-methyl-1-ethylpiperidinium bis (trifluoromethylsulfonyl) fluorenimide, 1-methyl-1-propylpiperidinium bis (trifluoromethyl) Sulfofluorenyl) fluorenimine, 1-methyl-1-propylpiperidinium bis (fluorosulfonyl) fluorenimine, 1-methyl-1-butylpiperidinium bis (trifluoromethyl) Sulfonyl) fluorenimine, 1-methyl-1-pentylpiperidinium bis (trifluoromethylsulfonyl) fluorenimide, 1-methyl-1-hexylpiperidinium bis (trifluoromethyl) Sulfofluorenyl) fluorenimine, 1-methyl-1-heptylpiperidinium bis (trifluoromethylsulfonyl) fluorenimide, 1-ethyl-1-propylpiperidinium bis (tri Fluoromethylsulfonyl) fluorenimine, 1-ethyl-1-butylpiperidinium bis (trifluoromethylsulfonyl) fluorenimide, 1-ethyl-1-pentylpiperidinium bis (Trifluoromethylsulfonyl) fluorenimine, 1-ethyl-1-hexylpiperidinium bis (trifluoromethylsulfonyl) fluorenimide, 1-ethyl-1-heptylpiperyl Onium bis (trifluoromethylsulfonyl) fluorenimide, 1,1-dipropylpiperidinium bis (trifluoromethylsulfonyl) fluorenimide, 1-propyl-1-butylpiperidine Onium bis (trifluoromethylsulfonyl) fluorenimide, 1,1-dibutylpiperidinium bis (trifluoromethylsulfonyl) fluorenimide, 1,1-dimethylpyrrolidinium bis (Pentafluoroethylsulfonyl) fluorenimine, 1-methyl-1-ethylpyrrolidinium bis (pentafluoroethylsulfonyl) fluorenimine, 1-methyl-1-propylpyrrolidine Onium bis (pentafluoroethylsulfonyl) fluorenimide, 1-methyl-1-butylpyrrolidinium bis (pentafluoroethylsulfonyl) fluorenimine, 1-methyl-1-pentyl Pyrrolidinium bis (pentafluoroethylsulfonyl) fluorenimide, 1-methyl-1-hexylpyrrolidinium bis (pentafluoroethylsulfonyl) fluorenimide, 1-methyl-1-heptanium Pyrrolidinium bis (pentafluoroethylsulfonyl) fluorenimide, 1-ethyl-1-propylpyrrolidinium bis (pentafluoroethylsulfonyl) fluorenimide, 1-ethyl-1 -Butylpyrrolidinium bis (pentafluoroethylsulfonyl) fluorenimide, 1-ethyl-1-pentylpyrrolidinium bis (pentafluoroethylsulfonyl) fluorenimide, 1-ethyl 1-hexylpyrrolidinium bis (pentafluoroethylsulfonyl) fluorenimine, 1-ethyl-1-heptylpyrrolidinium bis (pentafluoro Sulfofluorenyl) fluorenimine, 1,1-dipropylpyrrolidinium bis (pentafluoroethylsulfonyl) fluorenimine, 1-propyl-1-butylpyrrolidinium bis (pentafluoroethyl) Sulfofluorenyl) fluorenimine, 1,1-dibutylpyrrolidinium bis (pentafluoroethylsulfonyl) fluorenimide, 1-propylpiperidinium bis (pentafluoroethylsulfonate) (Fluorenyl) fluorenimine, 1-pentylpiperidinium bis (pentafluoroethylsulfonyl) fluorenimide, 1,1-dimethylpiperidinium bis (pentafluoroethylsulfonyl) fluorenimide Amine, 1-methyl-1-ethylpiperidinium bis (pentafluoroethylsulfonyl) fluorenimide, 1-methyl-1-propylpiperidinium bis (pentafluoroethylsulfonyl) Fluorenimine, 1-methyl-1-butylpiperidinium bis (pentafluoroethylsulfonyl) fluorenimide, 1-methyl-1-pentylpiperidinium bis (pentafluoroethylsulfonium) Sulfonyl) imine, 1-methyl-1-hexylpiperidinium bis (pentafluoroethylsulfonyl) fluorenimide, 1-methyl-1-heptylpiperidinium bis (pentafluoroethylsulfonate) Fluorenyl) fluorenimine, 1-ethyl-1-propylpiperidinium bis (pentafluoroethylsulfonyl) fluorenimide, 1-ethyl-1-butylpiperidinium bis (pentafluoroethyl) Sulfofluorenyl) fluorenimine, 1-ethyl-1-pentylpiperidinium bis (pentafluoroethylsulfonyl) fluorenimide, 1-ethyl-1-hexylpiperidinium bis (pentafluoro Ethylsulfonyl) fluorenimine, 1-ethyl-1-heptylpiperidinium bis (pentafluoroethylsulfonyl) fluorenimide, 1,1-dipropylpiperidinium bis (pentafluoro) Ethylsulfonyl) fluorenimine, 1-propyl-1-butylpiperidinium bis (pentafluoroethylsulfonyl) fluorenimide, 1,1-dibutylpiperidinium bis (pentafluoro) Ethyl Sulfonyl) fluorenimine, 1-ethyl-3-methylimidazolium trifluoroacetate, 1-ethyl-3-methylimidazolium heptafluorobutyrate, 1-ethyl-3-methyl Imidazolium trifluoromethanesulfonate, 1-ethyl-3-methylimidazolium heptafluoropropylsulfonate, 1-ethyl-3-methylimidazolium nonafluorobutylsulfonate, 1- Ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) fluorenimide, 1-ethyl-3-methylimidazolium bis (fluorosulfonyl) fluorenimide, 1-ethyl- 3-methylimidazolium bis (pentafluoroethylsulfonyl) fluorenimide, 1-ethyl-3-methylimidazolium tris (trifluoromethylsulfonyl) methylate, 1-butyl- 3-methylimidazolium trifluoroacetate, 1-butyl-3-methylimidazolium heptafluorobutyrate, 1-butyl-3-methylimidazolium trifluoromethanesulfonate, 1-butane 3-methylimidazolium perfluorobutylsulfonate, 1-butyl-3-methylimidazolium bis (trifluoromethylsulfonyl) fluorenimine, 1-hexyl-3-methylimidazole Onium trifluoromethanesulfonate, 1-hexyl-3-methylimidazolium bis (fluorosulfonyl) fluorenimine, 1,2-dimethyl-3-propylimidazolium bis (trifluoromethyl) Sulfonyl) fluorenimine, 1-ethyl-2,3,5-trimethylpyrazolium bis (trifluoromethylsulfonyl) fluorene Amine, 1-propyl-2,3,5-trimethylpyrazolium bis (trifluoromethylsulfonyl) fluorenimine, 1-butyl-2,3,5-trimethylpyrazolium Bis (trifluoromethylsulfonyl) fluorenimide, 1-ethyl-2,3,5-trimethylpyrazolium bis (pentafluoroethylsulfonyl) fluorenimide, 1-propyl- 2,3,5- Trimethylpyrazolium bis (pentafluoroethylsulfonyl) fluorenimide, 1-butyl-2,3,5-trimethylpyrazolium bis (pentafluoroethylsulfonyl) fluorenimide 1-ethyl-2,3,5-trimethylpyrazolium (trifluoromethylsulfonyl) trifluoroacetamide, 1-propyl-2,3,5-trimethylpyrazolium (Trifluoromethylsulfonyl) trifluoroacetamidamine, 1-butyl-2,3,5-trimethylpyrazolium (trifluoromethylsulfonyl) trifluoroacetamidamine, trimethyl Propylammonium bis (trifluoromethylsulfonyl) fluorenimide, N, N-dimethyl-N-ethyl-N-propylammonium bis (trifluoromethylsulfonyl) fluorenimide, N , N-dimethyl-N-ethyl-N-butylammonium bis (trifluoromethylsulfonyl) fluorenimine, N, N-dimethyl-N-ethyl-N-pentylammonium bis (Trifluoromethylsulfonamido) fluorenimine, N, N-dimethyl-N-ethyl-N-hexylammonium bis (trifluoromethylsulfonamido) fluorenimine, N, N-dimethyl -N-ethyl-N-heptylammonium bis (trifluoromethylsulfonyl) fluorenimine, N, N-dimethyl-N-ethyl-N-nonylammonium bis (trifluoromethyl) Sulfonyl) fluorenimine, N, N-dimethyl-N, N-dipropylammonium bis (trifluoromethylsulfonyl) fluorenimine, N, N-dimethyl-N-propyl -N-butylammonium bis (trifluoromethylsulfonyl) fluorenimine, N, N-dimethyl-N-propyl- N-pentylammonium bis (trifluoromethylsulfonyl) fluorenimine, N, N-dimethyl-N-propyl-N-hexylammonium bis (trifluoromethylsulfonyl) fluorenimine, N, N-dimethyl-N-propyl-N-heptylammonium bis (trifluoromethylsulfonyl) fluorenimine, N, N-dimethyl-N-butyl-N-hexylammonium bis (Trifluoromethylsulfonyl) fluorenimine, N, N-dimethyl-N-butyl-N-heptylammonium bis (trifluoromethylsulfonyl) fluorenimine, N, N-di Methyl-N-pentyl-N-hexylammonium bis (trifluoromethylsulfonyl) fluorenimine, N, N-dimethyl-N, N-dihexylammonium bis (trifluoromethylsulfonylsulfonyl) ) Iminoimide, trimethylheptylammonium bis (trifluoromethylsulfonyl) imino, N, N-diethyl-N-methyl-N-propylammonium bis (trifluoromethylsulfonate) (Fluorenyl) fluorenimine, N, N-diethyl-N-methyl-N-pentylammonium bis (trifluoromethylsulfonyl) fluorenimine, N, N-diethyl-N-formyl -N, N-heptylammonium bis (trifluoromethylsulfonyl) fluorenimine, N, N-diethyl-N-propyl-N-pentylammonium bis (trifluoromethylsulfonyl) ) Fluorenimine, triethylpropylammonium bis (trifluoromethylsulfonyl) fluorenimide, triethylpentylammonium bis (trifluoromethylsulfonyl) fluorenimine, triethylheptyl Ammonium bis (trifluoromethylsulfonyl) phosphonium imine, N, N-di -N-methyl-N-ethylammonium bis (trifluoromethylsulfonyl) fluorenimine, N, N-dipropyl-N-methyl-N-pentylammonium bis (trifluoromethyl Sulfonyl) fluorenimine, N, N-dipropyl-N-butyl-N-hexylammonium bis (trifluoromethylsulfonyl) Fluorenimine, N, N-dipropyl-N, N-dihexylammonium bis (trifluoromethylsulfonyl) fluorenimine, N, N-dibutyl-N-methyl-N-pentyl Ammonium bis (trifluoromethylsulfonyl) fluorenimide, N, N-dibutyl-N-methyl-N-hexylammonium bis (trifluoromethylsulfonyl) fluorenimide, trioctylmethyl Ammonium bis (trifluoromethylsulfonyl) fluorenimide, N-methyl-N-ethyl-N-propyl-N-pentylammonium bis (trifluoromethylsulfonyl) fluorenimide, 1-butylpyridinium (trifluoromethylsulfonyl) trifluoroacetamide, 1-butyl-3-methylpyridinium (trifluoromethylsulfonyl) trifluoroacetamide, 1-ethyl 3-methylimidazolium (trifluoromethylsulfonyl) trifluoroacetamidine, tetrahexylammonium bis (trifluoromethylsulfonyl) fluorenimide, diallyldimethylammonium trifluoro Methanesulfonate, diallyldimethylammonium bis (trifluoromethylsulfonyl) fluorenimide, diallyldimethylammonium bis (pentafluoroethylsulfonyl) sulfonium imine, N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium trifluoromethanesulfonate, N, N-diethyl-N-methyl-N- (2 -Methoxyethyl) ammonium bis (trifluoromethylsulfonyl) phosphonium imine, N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium bis (penta (Fluoroethylsulfonyl) Imine, glycidyl trimethylammonium trifluoromethanesulfonate, glycidyl trimethylammonium bis (trifluoromethylsulfonyl) sulfonium imine, glycidyl trimethylammonium bis (pentafluoro Ethylsulfonyl) fluorenimide, diallyldimethylammonium bis (trifluoromethylsulfonyl) fluorenimide, diallyldimethylbis (pentafluoroethylsulfonyl) fluorene Imines, lithium bis (trifluoromethylsulfonyl) fluorenimide, lithium bis (fluorosulfonyl) fluorenimide, and the like.

Among the ionic liquids, 1-hexylpyridinium bis (fluorosulfonyl) fluorenimine, 1-ethyl-3-methylpyridinium trifluoromethanesulfonate, and 1-ethyl- 3-methylpyridinium pentafluoroethylsulfonate, 1-ethyl-3-methylpyridinium heptafluoropropylsulfonate, 1-ethyl-3-methylpyridinium nonafluorobutylsulfonic acid Salt, 1-butyl-3-methylpyridinium trifluoromethanesulfonate, 1-butyl-3-methylpyridinium bis (trifluoromethylsulfonyl) fluorenimine, 1-octyl 4-methylpyridinium bis (fluorosulfonyl) fluorenimide, 1-methyl-1-propylpyrrolidinium bis (trifluoromethylsulfonyl) fluorenimine, 1-methyl-1 -Propylpyrrolidinium bis (fluorosulfonyl) fluorenimine, 1-methyl-1-propylpiperidinium bis (trifluoromethylsulfonyl) fluorenimine, 1-methyl-1- Propylpiperidinium bis (fluorosulfonyl) fluorenimine, 1-ethyl-3-methylimidazolium trifluoromethanesulfonate, 1-ethyl-3-methylimidazole Onium heptafluoropropylsulfonate, 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) fluorenimide, 1-ethyl-3-methylimidazolium bis (fluorosulfonium) Stilbene) imine, 1-hexyl-3-methylimidazolium bis (fluorosulfonyl) fluorenimide, trimethylpropylammonium bis (trifluoromethylsulfonyl) fluorenimide, bis (tris Lithium fluoromethylsulfonyl) fluorenimide, lithium bis (fluorosulfonyl) fluorenimide.

Commercially available ionic liquids can be used, but they can also be synthesized as follows. The method of synthesizing the ionic liquid is not particularly limited as long as the target ionic liquid is obtained, but the halogenation described in the document "Ionic Liquids-Frontline and Future of Development" (published and issued by CMC Corporation) is usually used. Physical method, hydroxide method, ester method, error method, and neutralization method.

Regarding the following halide method, hydroxide method, ester method, error method, and neutralization method, the nitrogen-containing onium salt is taken as an example to describe the synthesis method, but other sulfonium-containing salts, phosphonium-containing salts, etc. It can also be obtained by the same method as other ionic liquids.

The halide method is a method performed by a reaction represented by the reaction formulae (1) to (3). First, a tertiary amine is reacted with a halogenated alkyl group to obtain a halide (Reaction formula (1) using chlorine, bromine, and iodine as a halogen).

Halide obtained by making the structure of the target anion having an ionic liquids (A ^-) acid (HA), or of a salt (MA, M represents an ammonium, lithium, sodium and potassium salts of the target anion cation) Reaction The target ionic liquid (R ₄ NA) was obtained.

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

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

The obtained hydroxide was obtained in the same manner as in the above-mentioned halogenation method, using the reactions of reaction formulae (7) to (8), thereby obtaining the target ionic liquid (R ₄ NA).

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

The acid ester method is a method in which a reaction shown in reaction formulae (9) to (11) is performed. First, a tertiary amine (R ₃ N) is reacted with an acid ester to obtain an acid ester (Reaction formula (9), as the acid ester, an ester of an inorganic acid such as sulfuric acid, sulfurous acid, phosphoric acid, phosphorous acid, or carbonic acid, or Esters of organic acids such as methanesulfonic acid, methylphosphonic acid, formic acid, etc.).

With respect to the obtained acid ester, the reaction of the reaction formulae (10) to (11) was used in the same manner as the above-mentioned halide to obtain a target ionic liquid (R ₄ NA). In addition, an ionic liquid can also be directly obtained by using methyl trifluoromethanesulfonate, methyl trifluoroacetate, or the like as an acid ester.

The neutralization method is a method performed by a reaction represented by the reaction formula (12). The tertiary amine can be reacted with organic acids such as CF ₃ COOH, CF ₃ SO ₃ H, (CF ₃ SO ₂ ) ₂ NH, (CF ₃ SO ₂ ) ₃ CH, (C ₂ F ₅ SO ₂ ) ₂ NH, etc. And get.

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

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

The formulation amount of the ionic liquid varies depending on the compatibility between the polymer used and the ionic liquid, and cannot be defined in general. However, it is generally preferably 0.001 to 100 parts by weight of the urethane resin. Part by weight to 50 parts by weight, more preferably 0.01 to 40 parts by weight, still more preferably 0.01 to 30 parts by weight, particularly preferably 0.01 to 20 parts by weight, and most preferably 0.01 to 10 parts by weight Parts by weight. By adjusting the blending amount of the ionic liquid within the above range, a urethane-based adhesive having excellent antistatic properties can be provided. If the blending amount of the ionic liquid is less than 0.01 part by weight, there is a possibility that sufficient antistatic properties may not be obtained. If the amount of the ionic liquid to be formulated exceeds 50 parts by weight, contamination of the adherend tends to increase.

<A-3. Other ingredients>

As long as the effect of the present invention is not impaired, the urethane-based adhesive of the present invention may contain any appropriate other components in addition to the urethane-based resin and the ionic liquid as described above. Examples of such other components include resin components other than urethane resins, tackifiers, inorganic fillers, organic fillers, metal powders, pigments, foils, softeners, plasticizers, Anti-aging agent, conductive agent, ultraviolet absorber, antioxidant, light stabilizer, surface lubricant, leveling agent, anti-corrosive agent, heat resistance Stabilizers, polymerization inhibitors, lubricants, solvents, etc.

The urethane-based adhesive of the present invention may include a modified silicone oil. When the urethane-based adhesive of the present invention contains a modified silicone oil, the effect of the present invention can be further effectively expressed.

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

As long as the effect of the present invention is not impaired, as the modified silicone oil, any appropriate modified silicone oil can be used. As such a modified silicone oil, for example, a modified silicone oil that can be obtained from Shinsei Yue Chemical Industry Co., Ltd. is mentioned.

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

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

<A-4. Characteristics>

The urethane-based adhesive of the present invention has excellent antistatic properties, and the absolute value of the peeling charging voltage with respect to the glass plate is preferably less than 4.0 kV, more preferably 3.5 kV or less, and further preferably 3.0 kV. Hereinafter, it is more preferably 2.5 kV or less, still more preferably 2.0 kV or less, still more preferably 1.5 kV or less, still more preferably 1.0 kV or less, particularly preferably 0.5 kV or less, and most preferably 0.3 kV or less. When the peeling charging voltage is within the above range, the urethane-based adhesive of the present invention is very excellent in antistatic properties.

The adhesive force of the urethane-based adhesive of the present invention to a glass plate is just adhered to The initial adhesion meter after the glass plate is preferably 0.5N / 25mm or less, more preferably 0.005N / 25mm ~ 0.5N / 25mm, even more preferably 0.005N / 25mm ~ 0.4N / 25mm, and particularly preferably 0.005 N / 25mm ~ 0.3N / 25mm, preferably 0.01N / 25mm ~ 0.2N / 25mm. With the above-mentioned initial adhesive force being within the above range, the urethane-based adhesive of the present invention has a moderate initial adhesiveness and can exhibit further excellent reworkability.

In addition, the measurement of the above-mentioned initial adhesive force can be performed by cutting a surface protective film having an adhesive layer containing the urethane-based adhesive of the present invention into a width of 25 mm and a length of 150 mm as an evaluation test. In a sample at a temperature of 23 ° C and a humidity of 50% RH, the 2.0 kg roll was reciprocated once, and the adhesive layer of the sample for evaluation was attached to a glass plate (Matsulang Glass Industrial Co., Ltd., trade name: Micro Slide Glass S), cured in an atmosphere at a temperature of 23 ° C. and a humidity of 50% RH for 30 minutes. Thereafter, a general-purpose tensile tester (manufactured by Minebea Corporation, product name: TCM-1kNB) was used to peel off The peeling was performed at an angle of 180 ° and a tensile speed of 300 mm / min, and the adhesive force was measured.

The adhesion of the urethane-based adhesive of the present invention to a glass plate is preferably 0.5N / 25mm or less, more preferably 0.005N after being attached to the glass plate and at 50 ° C × 50% RH × 7 days. /25mm~0.5N/25mm, more preferably 0.005N / 25mm ~ 0.4N / 25mm, particularly preferably 0.005N / 25mm ~ 0.3N / 25mm, and most preferably 0.01N / 25mm ~ 0.2N / 25mm. When the above-mentioned adhesive force is within the above range, the urethane-based adhesive of the present invention can exhibit further excellent reworkability.

In addition, the measurement of the above-mentioned adhesion can be performed by preparing a sample for evaluation by the same method as the initial adhesion to the glass plate, and measuring the temperature at 50 ° C. by the same method as the initial adhesion. Adhesion after storage for 7 days at 50% RH.

The adhesion force of the urethane-based adhesive of the present invention to a glass plate is preferably 0.5N / 25mm or less, more preferably 0.005N after being attached to the glass plate and 60 ° C × 90% RH × 7 days. /25mm~0.5N/25mm, more preferably 0.005N / 25mm ~ 0.4N / 25 mm, particularly preferably 0.005N / 25mm ~ 0.3N / 25mm, and most preferably 0.01N / 25mm ~ 0.2N / 25mm. When the above-mentioned adhesive force is within the above range, the urethane-based adhesive of the present invention can exhibit further excellent reworkability.

In addition, the measurement of the above-mentioned adhesive force can be performed by the following methods: preparing the sample for evaluation by the same method as the initial adhesion to the glass plate; and measuring the temperature at 60 ° C. by the same method as the initial adhesion. Adhesion after storage for 7 days at 90% RH.

The adhesion force of the urethane-based adhesive of the present invention to a glass plate is preferably 0.5N / 25mm or less, more preferably 0.005N / after being attached to the glass plate and 85 ° C × 50% RH × 7 days. 25mm ~ 0.5N / 25mm, more preferably 0.005N / 25mm ~ 0.4N / 25mm, particularly preferably 0.005N / 25mm ~ 0.3N / 25mm, and most preferably 0.01N / 25mm ~ 0.2N / 25mm. When the above-mentioned adhesive force is within the above range, the urethane-based adhesive of the present invention can exhibit further excellent reworkability.

In addition, the measurement of the above-mentioned adhesive force can be performed as follows: a sample for evaluation is prepared by the same method as the initial adhesion to the glass plate; and the temperature is measured at 85 ° C. by the same method as the initial adhesion. Adhesion after storage for 7 days at 50% RH.

The adhesive force of the urethane-based adhesive of the present invention to the glass plate is immediately after being attached to the glass plate, and then attached to the glass plate at 50 ° C × 50% RH × 7 days, at 60 ° C × 90% After RH × 7 days, and after 85 ° C × 50% RH × 7 days, it is preferably 0.5N / 25mm or less, more preferably 0.005N / 25mm to 0.5N / 25mm, and still more preferably 0.005N / 25mm ~ 0.4N / 25mm, particularly preferably 0.005N / 25mm ~ 0.3N / 25mm, and most preferably 0.01N / 25mm ~ 0.2N / 25mm. When the above-mentioned adhesive force is within the above range, the urethane-based adhesive of the present invention can exhibit further excellent reworkability.

The urethane-based adhesive of the present invention preferably has high transparency. Since the urethane-based adhesive of the present invention has high transparency, it can be accurately inspected in a state of being attached to the surface of an optical member or an electronic member. The haze of the urethane-based adhesive of the present invention is preferably 5% or less, more preferably 4% or less, still more preferably 3% or less, and particularly preferably It is 2% or less, preferably 1% or less.

In addition, the above haze is measured by using a haze meter HM-150 (manufactured by Murakami Color Technology Research Institute Co., Ltd.), and according to JIS-K-7136, the haze (%) = (Td / Tt) × 100 (Td: diffuse transmittance, Tt: total light transmittance) were calculated.

<< B. Surface protective film >>

The surface protection film of the present invention is a surface protection film which is preferably used for surface protection of an optical member or an electronic member. The surface protection film of the present invention has a substrate layer and an adhesive layer, and the adhesive layer includes the urethane-based adhesive of the present invention.

FIG. 1 is a schematic cross-sectional view of a surface protective film according to a preferred embodiment of the present invention. The surface protection film 10 includes a base material layer 1 and an adhesive layer 2. The surface protective film of the present invention may have any appropriate other layer (not shown) as required.

In order to form a rolled body that can be easily rolled back on the surface of the base material layer 1 without the adhesive layer 2 attached thereto, for example, fatty base, polyethyleneimine, and long-chain alkyl-based additives can be added to the base material layer. The peeling process may be provided with a coating layer containing any appropriate release agent such as a polysiloxane-based, long-chain alkyl-based, or fluorine-based one.

The surface protective film of the present invention can be bonded to a release liner having releasability.

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 fully expressing 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 protection film of the present invention has excellent antistatic properties and the absolute value of the peeling charging voltage relative to the glass plate is preferably less than 4.0 kV, more preferably 3.5 kV or less, still more preferably 3.0 kV or less, and more preferably It is 2.5 kV or less, further preferably 2.0 kV or less, still more preferably 1.5 kV or less, still more preferably 1.0 kV or less, particularly preferably 0.5 kV or less, and most preferably 0.3 kV or less. When the peeling charging voltage is within the above range, the antistatic property of the surface protective film of the present invention is very excellent.

The adhesion of the surface protective film of the present invention to the glass plate is preferably 0.5N / 25mm or less, more preferably 0.005N / 25mm to 0.5N / 25mm, based on the initial adhesion force immediately after being attached to the glass plate, and further It is preferably 0.005N / 25mm to 0.4N / 25mm, particularly preferably 0.005N / 25mm to 0.3N / 25mm, and most preferably 0.01N / 25mm to 0.2N / 25mm. With the above-mentioned initial adhesive force being within the above range, the surface protective film of the present invention has moderate initial adhesion and can exhibit further excellent reworkability.

In addition, the measurement of the initial adhesive force can be performed by cutting the surface protective film into a width of 25 mm and a length of 150 mm to prepare a sample for evaluation, and in an atmosphere at a temperature of 23 ° C and a humidity of 50% RH, A 2.0 kg roller was reciprocated once, and the surface of the adhesive layer of the sample for evaluation was attached to a glass plate (manufactured by Songlang Glass Industry Co., Ltd., trade name: Micro Slide Glass S) at a temperature of 23 ° C and a humidity of 50% RH. It was cured in an atmosphere for 30 minutes, and then peeled using a universal tensile tester (manufactured by Minebea Corporation, product name: TCM-1kNB) at a peeling angle of 180 ° and a tensile speed of 300 mm / min Determination of adhesion.

The adhesion of the surface protective film of the present invention to a glass plate is preferably 0.5N / 25mm or less, more preferably 0.005N / 25mm ~ 0.5 after being adhered to the glass plate and 50 ° C × 50% RH × 7 days. N / 25mm, more preferably 0.005N / 25mm ~ 0.4N / 25mm, particularly preferably 0.005N / 25mm ~ 0.3N / 25mm, and most preferably 0.01N / 25mm ~ 0.2N / 25mm. With the above-mentioned adhesive force being within the above range, the surface protective film of the present invention can exhibit further excellent reworkability.

In addition, the measurement of the above-mentioned adhesive force can be performed as follows: a sample for evaluation is prepared by the same method as the initial adhesion to the glass plate; and the temperature is measured at 50 ° C. by the same method as the initial adhesion. Adhesion after 7 days storage at 50% RH.

The adhesion of the surface protective film of the present invention to a glass plate is preferably 0.5N / 25mm or less, more preferably 0.005N / 25mm ~ 0.5 after being adhered to the glass plate and 60 ° C × 90% RH × 7 days. N / 25mm, more preferably 0.005N / 25mm ~ 0.4N / 25mm, especially It is preferably 0.005N / 25mm to 0.3N / 25mm, and most preferably 0.01N / 25mm to 0.2N / 25mm. With the above-mentioned adhesive force being within the above range, the surface protective film of the present invention can exhibit further excellent reworkability.

In addition, the measurement of the above-mentioned adhesive force can be performed as follows: a sample for evaluation is prepared by the same method as the initial adhesion to the glass plate; and the temperature is measured at 60 ° C. by the same method as the initial adhesion. Adhesion after storage for 7 days at 90% RH.

The adhesion of the surface protective film of the present invention to a glass plate is preferably 0.5N / 25mm or less, more preferably 0.005N / 25mm ~ 0.5 after being attached to the glass plate and at 85 ° C × 50% RH × 7 days. N / 25mm, more preferably 0.005N / 25mm ~ 0.4N / 25mm, particularly preferably 0.005N / 25mm ~ 0.3N / 25mm, and most preferably 0.01N / 25mm ~ 0.2N / 25mm. With the above-mentioned adhesive force being within the above range, the surface protective film of the present invention can exhibit further excellent reworkability.

In addition, the measurement of the above-mentioned adhesive force can be performed as follows: a sample for evaluation is prepared by the same method as the initial adhesion to the glass plate; and the temperature is measured at 85 ° C. by the same method as the initial adhesion. Adhesion after storage for 7 days at 50% RH.

The adhesive force of the surface protective film of the present invention on the glass plate is immediately after being attached to the glass plate, and then attached to the glass plate at 50 ° C × 50% RH × 7 days, and then at 60 ° C × 90% RH × 7 After 5 days, and after 85 ° C × 50% RH × 7 days, it is preferably 0.5N / 25mm or less, more preferably 0.005N / 25mm ~ 0.5N / 25mm, and still more preferably 0.005N / 25mm ~ 0.4N / 25mm, particularly preferably 0.005N / 25mm to 0.3N / 25mm, and most preferably 0.01N / 25mm to 0.2N / 25mm. With the above-mentioned adhesive force being within the above range, the surface protective film of the present invention can exhibit further excellent reworkability.

The surface protection film of the present invention is preferably highly transparent. Since the surface protection film of the present invention has high transparency, it can be accurately inspected and the like in a state of being attached to the surface of an optical member or an electronic member. The haze of the surface protective film of the present invention is preferably 5% or less, more preferably 4% or less, further preferably 3% or less, particularly preferably 2% or less, and most preferably 1% or less. under. The measurement of the haze is the same as described above.

<B-1. Adhesive layer>

The adhesive layer contains the urethane-based adhesive of the present invention. The content ratio of the urethane-based adhesive in the adhesive layer of the present invention is preferably 50% to 100% by weight, more preferably 70% to 100% by weight, and still more preferably 90% to 100% by weight. %, Particularly preferably 95% to 100% by weight, and most preferably 98% to 100% by weight. By adjusting the content ratio of the urethane-based adhesive of the present invention in the adhesive layer within the above-mentioned range, a surface protective film having excellent paste resistance can be provided.

As the thickness of the adhesive layer, any appropriate thickness can be adopted depending on the application. The thickness of the adhesive layer is preferably 1 μm to 100 μm, more preferably 3 μm to 50 μm, and even more preferably 5 μm to 30 μm.

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

<B-2. Base material layer>

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

The substrate layer may be a single layer, or may be a laminate of two or more layers. The substrate layer may be an stretcher.

As a material of the base material layer, any appropriate material can be adopted depending on the application. Examples include plastic, paper, metal film, and non-woven fabric. More preferably, it is plastic. The base material layer may be composed of one material, or may be composed of two or more materials. For example, the above layer may be composed of two or more plastics.

Examples of the plastic include polyester resins, polyamide resins, and polyolefin resins. Examples of the polyester-based resin include polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate. Examples of the polyolefin-based resin include a homopolymer of an olefin monomer and a copolymer of an olefin monomer. Specific examples of the polyolefin-based resin include: homopolypropylene; block-based, random-based, and graft-based propylene-based copolymers using an ethylene component as a copolymerization component; and a reactor directly preparing a thermoplastic polyolefin (reactor) TPO); low density, high density, linear low density, ultra-low density and other ethylene-based polymers; ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer Products, ethylene-butyl acrylate copolymers, ethylene-methacrylic acid copolymers, ethylene-methyl methacrylate copolymers, and other ethylene-based copolymers.

The base material layer may contain any appropriate additive as needed. Examples of the additives that can be contained in the substrate layer include antioxidants, ultraviolet absorbers, light stabilizers, antistatic agents, fillers, pigments, and the like. The type, number, and amount of additives that can be contained in the substrate layer can be appropriately set according to the purpose. In particular, when the material of the base material layer is plastic, it is preferable to contain several of the aforementioned additives in order to prevent deterioration and the like. From the viewpoint of improving weather resistance, particularly preferred additives include antioxidants, ultraviolet absorbers, light stabilizers, and fillers.

As the antioxidant, any appropriate antioxidant can be used. 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 stabilizer, and a phenol-phosphorus-based antioxidant. The content of the antioxidant is preferably 1% by weight or less, and more preferably 0.5% by weight or less, relative to the base resin of the base material layer (in the case where the base material layer is a blend, the blend is a base resin). , And more preferably 0.01% by weight to 0.2% by weight.

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

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

As the filler, any appropriate filler can be used. Examples of such a filler include an inorganic filler. Specific examples of the inorganic filler include carbon black, titanium oxide, and zinc oxide. The content of the filler is preferably 20% by weight or less, and more preferably 10% by weight, relative to the base resin forming the base layer (when the base layer is a blend, the blend is a base resin). Hereinafter, it is more preferably 0.01% by weight to 10% by weight.

Further, as an additive, for the purpose of imparting antistatic properties, preferably, surfactants, inorganic salts, polyhydric alcohols, metal compounds, carbon, and other inorganic-based, low-molecular-weight, and high-molecular-weight antistatic agents are also mentioned. In particular, a high molecular weight antistatic agent or carbon is preferred from the viewpoint of contamination and maintaining adhesiveness.

<B-3. Manufacturing method of surface protective film>

The surface protective film of the present invention can be produced by any appropriate method. Such a manufacturing method can be performed, for example, according to any appropriate manufacturing method as follows: (1) A material for forming an adhesive layer (for example, a polyol (A containing a raw material of the urethane-based adhesive of the present invention (A ) And a method of applying a solution of a composition of the polyfunctional isocyanate compound (B)) or a hot melt to the substrate layer; (2) according to the method, the adhesive layer coated and formed on the separator is transferred to the substrate Wood layer Method; (3) a method of extruding the material for forming the adhesive layer on the substrate layer to form a coating; (4) a method of extruding the substrate layer and the adhesive layer into two or more layers; (5) A method of laminating a single layer of an adhesive layer on a substrate layer, or a method of laminating two layers of a laminate layer and an adhesive layer together; or (6) a method of laminating an adhesive layer with a film or a laminate layer The material layer forming method is a method of laminating two layers or a plurality of layers.

<< C. Uses >>

The urethane-based adhesive of the present invention can be used for any appropriate application. Since the urethane-based adhesive of the present invention is excellent in paste resistance, the surface protective film can be preferably used for an optical member or an electronic member by using the adhesive layer as a surface protective film. Surface protection. The optical member or electronic member to which the surface protection film of the present invention is attached can be manually attached and peeled off multiple times.

Examples

Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to these examples. In addition, the test and evaluation method in an Example etc. are as follows. In addition, as long as there is no special note, the case described as "part" means "weight part", and as long as there is no special note, the case described as "%" means "weight%".

<Measurement of peeling charging voltage with respect to glass plate>

When the surface protective film was cut to a width of 70 mm and a length of 130 mm and a separator was used, the separator was peeled off, and then a 2 kg roll was rolled on untreated glass (made by Songlang Glass Co., Ltd., dimensions 1.35 mm × 10 cm × 10cm). At this time, the surface protection film was in a state of protruding 30 cm from the glass. After being left in an environment of 23 ° C. × 50% RH for one day, one end protruding from the glass by 30 cm was fixed to an automatic winder and peeled at a peeling angle of 150 ° and a peeling speed of 10 m / min. Then, a potentiometer (Kasuga (Manufactured by Denki Co., Ltd., KSD-0103), and measured the peeling electrification voltage. This measurement was performed in an environment of 23 ° C × 50% RH.

<Measurement of adhesion to glass plate> (Initial adhesion just after being attached to the glass plate)

The surface protective film was cut into a width of 25 mm and a length of 150 mm to prepare a sample for evaluation. At a temperature of 23 ° C. and a humidity of 50% RH, the 2.0 kg roll was reciprocated once, and the adhesive layer of the sample for evaluation was attached to a glass plate (manufactured by Songlang Glass Industry Co., Ltd., trade name: Micro Slide Glass S), curing in an atmosphere at a temperature of 23 ° C. and a humidity of 50% RH for 30 minutes, and then using a universal tensile tester (manufactured by Minebea Corporation, product name: TCM-1kNB) at a peel angle of 180 ° 2. Peel at a tensile speed of 300 mm / min, and measure the adhesion.

(Adhesion after sticking to glass plate and 50 ℃ × 50% RH × 7 days)

The surface protective film was cut into a width of 25 mm and a length of 150 mm to prepare a sample for evaluation. In an atmosphere at a temperature of 23 ° C and a humidity of 50% RH, the 2.0 kg roll was reciprocated once, and the adhesive layer of the evaluation sample was attached to a glass plate (manufactured by Songlang Glass Industry Co., Ltd., trade name: Micro Slide Glass S), cured in an atmosphere with a humidity of 23 ° C and a humidity of 50% RH for 30 minutes, and then stored at a temperature of 50 ° C and a humidity of 50% RH for 7 days. Thereafter, a universal tensile tester (Minebea Corp. Co., Ltd., product name: TCM-1kNB), peeled at a peeling angle of 180 ° and a tensile speed of 300 mm / min, and measured the adhesive force.

(Adhesion after sticking to glass plate and 60 ℃ × 90% RH × 7 days)

The surface protective film was cut into a width of 25 mm and a length of 150 mm to prepare a sample for evaluation. In an atmosphere at a temperature of 23 ° C and a humidity of 50% RH, the 2.0 kg roll was reciprocated once, and the adhesive layer of the evaluation sample was attached to a glass plate (manufactured by Songlang Glass Industry Co., Ltd., trade name: Micro Slide Glass S), cured in an atmosphere at a temperature of 23 ° C and a humidity of 50% RH for 30 minutes, and then stored at a temperature of 60 ° C and a humidity of 90% RH for 7 days. Then, a universal tensile tester (manufactured by Minebea Co., Ltd., product name: TCM-1kNB) was used to perform peeling at a peeling angle of 180 ° and a tensile speed of 300 mm / min to measure the adhesive force.

(Adhesion after sticking to a glass plate and 85 ° C × 50% RH × 7 days)

The surface protective film was cut into a width of 25 mm and a length of 150 mm to prepare a sample for evaluation. In an atmosphere at a temperature of 23 ° C and a humidity of 50% RH, the 2.0 kg roll was reciprocated once, and the adhesive layer of the evaluation sample was attached to a glass plate (manufactured by Songlang Glass Industry Co., Ltd., trade name: Micro Slide Glass S), cured in an atmosphere at a temperature of 23 ° C and a humidity of 50% RH for 30 minutes, and then stored at a temperature of 85 ° C and a humidity of 50% RH for 7 days. Thereafter, a universal tensile tester (Minebea (Product name: TCM-1kNB), peeled at a peeling angle of 180 ° and a tensile speed of 300 mm / min, and the adhesive force was measured.

[Example 1]

As the polyol (A), 85 parts by weight of a polyol having three OH groups of PREMINOL S3011 (manufactured by Asahi Glass Co., Ltd., Mn = 10000) and 13 parts by weight of SANNIX GP of a polyol having three OH groups -3000 (manufactured by Sanyo Chemical Industry Co., Ltd., Mn = 3000), 2 parts by weight of SANNIX GP-1000 (manufactured by Sanyo Chemical Industry Co., Ltd., Mn = 1000), as multifunctional 18 parts by weight of polyfunctional alicyclic isocyanate compound CORONATE HX (manufactured by Japan Polyurethane Industry Co., Ltd.) of isocyanate compound (B), 0.04 parts by weight of catalyst (manufactured by Japan Chemical Industry Co., Ltd., trade name: Nacem Ferric Iron), 0.50 parts by weight of Irganox 1010 (manufactured by BASF), 30 parts by weight of fatty acid esters (isopropyl palmitate, manufactured by Kao Corporation, trade name: EXCEPARL IPP, Mn = 299), 0.01 part by weight of 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) fluorenimide (manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd., IL210), and 241 parts by weight of a diluting solvent Ethyl acetate Mixed, and then into a disperser Stirring was performed to obtain a urethane-based adhesive composition.

The obtained urethane-based adhesive composition was coated on a substrate “Lumirror S10” (thickness: 38 μm, manufactured by Toray Industries, Ltd.) containing a polyester resin with a dipping roller, and the thickness after drying was obtained. It became 12 micrometers, and it solidified and dried under the conditions of the drying temperature of 130 degreeC, and the drying time of 2 minutes. In this manner, an adhesive layer containing a urethane-based adhesive (1) on the substrate was prepared.

Then, a silicone-treated surface of a substrate containing a polyester resin with a thickness of 25 μm, which is silicone-treated on one side, is adhered to the surface of the adhesive layer to obtain a surface protective film (1).

The evaluation results are shown in Table 1.

[Example 2]

Except that the amount of 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) fluorenimide was changed to 0.1 part by weight, it was produced on the substrate in the same manner as in Example 1 and included Adhesive layer of urethane-based adhesive (2).

Then, a silicone-treated surface of a substrate containing a polyester resin with a thickness of 25 μm that was subjected to a silicone treatment on one side was bonded to the surface of the adhesive layer to obtain a surface protection film (2).

The evaluation results are shown in Table 1.

[Example 3]

Except that the amount of 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) fluorenimide was changed to 1 part by weight, it was produced on the substrate in the same manner as in Example 1 and included Adhesive layer of urethane-based adhesive (3).

Then, a silicone-treated surface of a substrate containing a polyester resin with a thickness of 25 μm, which was subjected to a silicone treatment on one side, was adhered to the surface of the adhesive layer to obtain a surface protective film (3).

The evaluation results are shown in Table 1.

[Example 4]

Except that the amount of 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) fluorenimide was changed to 10 parts by weight, it was produced on the substrate in the same manner as in Example 1 and contained on the substrate. Adhesive layer of urethane-based adhesive (4).

Then, a silicone-treated surface of a substrate containing a polyester resin with a thickness of 25 μm, which is silicone-treated on one side, is adhered to the surface of the adhesive layer to obtain a surface protection film (4).

The evaluation results are shown in Table 1.

[Example 5]

Except changing 0.01 parts by weight of 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) fluorenimide to 0.01 parts by weight of 1-ethyl-3-methylimidazolium bis (fluoro A pressure-sensitive adhesive layer containing a urethane-based pressure-sensitive adhesive (4) was prepared on the substrate in the same manner as in Example 1 except for the sulfo) imide (manufactured by Daiichi Kogyo Co., Ltd., AS210). .

Then, a silicone-treated surface of a substrate containing a polyester resin with a thickness of 25 μm, which is silicone-treated on one side, is adhered to the surface of the adhesive layer to obtain a surface protection film (4).

The evaluation results are shown in Table 1.

[Example 6]

Except that the amount of 1-ethyl-3-methylimidazolium bis (fluorosulfonyl) fluorenimide was changed to 0.1 part by weight, the same method as in Example 5 was used to prepare a substrate containing ethyl carbamate. Adhesive layer of the ester-based adhesive (6).

Then, a silicone-treated surface of a substrate containing a polyester resin with a thickness of 25 μm that was subjected to a silicone treatment on one side was bonded to the surface of the adhesive layer to obtain a surface protection film (6).

The evaluation results are shown in Table 1.

[Example 7]

Except that the amount of 1-ethyl-3-methylimidazolium bis (fluorosulfonyl) fluorenimide was changed to 1 part by weight, in the same manner as in Example 5, an ethyl carbamate was produced on the substrate. Adhesive layer of the ester-based adhesive (7).

Then, a silicone-treated surface of a substrate containing a polyester resin with a thickness of 25 μm, which is silicone-treated on one side, is adhered to the surface of the adhesive layer to obtain a surface protective film (7).

The evaluation results are shown in Table 1.

[Example 8]

Except that the amount of 1-ethyl-3-methylimidazolium bis (fluorosulfonyl) fluorenimine was changed to 10 parts by weight, in the same manner as in Example 5, ethyl carbamate was produced on the substrate. Adhesive layer of the ester-based adhesive (8).

Then, a silicone-treated surface of a substrate containing a polyester resin with a thickness of 25 μm that is subjected to a silicone treatment on one side is bonded to the surface of the adhesive layer to obtain a surface protection film (8).

The evaluation results are shown in Table 1.

[Example 9]

Except changing 0.01 parts by weight of 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) fluorenimide to 0.01 parts by weight of 1-ethyl-3-methylimidazolium heptafluoropropene An adhesive layer containing a urethane-based adhesive (9) on a substrate was prepared in the same manner as in Example 1 except for a sulfonic acid salt (manufactured by Mitsubishi Materials Electrochemical Corporation, EMI-EF31).

Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one surface was bonded to the surface of the adhesive layer to obtain a surface protection film (9).

The evaluation results are shown in Table 2.

[Example 10]

In addition to changing the amount of 1-ethyl-3-methylimidazolium heptafluoropropylsulfonate to 0.1 parts by weight Other than that, in the same manner as in Example 9, an adhesive layer containing a urethane-based adhesive (10) on a substrate was prepared.

Then, a silicone-treated surface of a substrate containing a polyester resin with a thickness of 25 μm that is subjected to a silicone treatment on one surface is adhered to the surface of the adhesive layer to obtain a surface protection film (10).

The evaluation results are shown in Table 2.

[Example 11]

Except that the amount of 1-ethyl-3-methylimidazolium heptafluoropropylsulfonate was changed to 1 part by weight, a urethane-based adhesive was produced on the substrate in the same manner as in Example 9. The adhesive layer of the agent (11).

Then, a silicone-treated surface of a substrate containing a polyester resin with a thickness of 25 μm that was subjected to a silicone treatment on one side was bonded to the surface of the adhesive layer to obtain a surface protection film (11).

The evaluation results are shown in Table 2.

[Example 12]

Except that the amount of 1-ethyl-3-methylimidazolium heptafluoropropylsulfonate was changed to 10 parts by weight, a urethane-based adhesive was produced on the substrate in the same manner as in Example 9. The adhesive layer of the agent (12).

Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one side was bonded to the surface of the adhesive layer to obtain a surface protection film (12).

The evaluation results are shown in Table 2.

[Example 13]

Except changing 0.01 parts by weight of 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) fluorenimide to 0.01 parts by weight of 1-ethyl-3-methylimidazolium trifluoromethane Except for sulfonic acid salt (manufactured by Mitsubishi Materials Electrochemical Corporation, EMI-EF11), in the same manner as in Example 1, An adhesive layer containing a urethane-based adhesive (13) on a substrate.

Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one surface was bonded to the surface of the adhesive layer to obtain a surface protection film (13).

The evaluation results are shown in Table 2.

[Example 14]

Except that the amount of 1-ethyl-3-methylimidazolium trifluoromethanesulfonate was changed to 0.1 part by weight, a urethane-based adhesive was produced on the substrate in the same manner as in Example 13 The adhesive layer of the agent (14).

Then, a silicone-treated surface of a substrate containing a polyester resin with a thickness of 25 μm, which is silicone-treated on one side, is adhered to the surface of the adhesive layer to obtain a surface protection film (14).

The evaluation results are shown in Table 2.

[Example 15]

Except that the amount of 1-ethyl-3-methylimidazolium trifluoromethanesulfonate was changed to 1 part by weight, a urethane-based adhesive was produced on the substrate in the same manner as in Example 13 The adhesive layer of the agent (15).

Then, a silicone-treated surface of a substrate containing a polyester resin with a thickness of 25 μm, which is silicone-treated on one side, is adhered to the surface of the adhesive layer to obtain a surface protection film (15).

The evaluation results are shown in Table 2.

[Example 16]

Except that the amount of 1-ethyl-3-methylimidazolium trifluoromethanesulfonate was changed to 10 parts by weight, a urethane-based adhesive was produced on the substrate in the same manner as in Example 13 The adhesive layer of the agent (16).

Next, a 25 μm-thick polyester resin containing polysiloxane will be treated on one side. The silicone-treated surface of the substrate is adhered to the surface of the adhesive layer to obtain a surface protection film (16).

The evaluation results are shown in Table 2.

[Example 17]

Except changing 0.01 parts by weight of 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) fluorenimide to 0.01 parts by weight of 1-hexyl-3-methylimidazolium bis (fluorosulfonic acid) An adhesive containing urethane-based adhesive (17) on the substrate was produced in the same manner as in Example 1 except for fluorenyl) imine (manufactured by Mitsubishi Materials Electrochemical Corporation, HMI-FSI). Floor.

Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one side was bonded to the surface of the adhesive layer to obtain a surface protection film (17).

The evaluation results are shown in Table 3.

[Example 18]

Except that the amount of 1-hexyl-3-methylimidazolium bis (fluorosulfonyl) fluorenimide was changed to 0.1 part by weight, a urethane was prepared on the substrate in the same manner as in Example 17 The adhesive layer of the adhesive (18).

Then, a silicone-treated surface of a substrate containing a polyester resin with a thickness of 25 μm that was subjected to a silicone treatment on one side was bonded to the surface of the adhesive layer to obtain a surface protection film (18).

The evaluation results are shown in Table 3.

[Example 19]

Except that the amount of 1-hexyl-3-methylimidazolium bis (fluorosulfonyl) fluorenimide was changed to 1 part by weight, a urethane was prepared on the substrate in the same manner as in Example 17 The adhesive layer of the adhesive (19).

Then, a silicone-treated surface of a substrate containing a polyester resin with a thickness of 25 μm which is subjected to a silicone treatment on one side is bonded to the surface of the adhesive layer to obtain a surface protective film. (19).

The evaluation results are shown in Table 3.

[Example 20]

Except that the amount of 1-hexyl-3-methylimidazolium bis (fluorosulfonyl) fluorenimide was changed to 10 parts by weight, a urethane was included on the substrate in the same manner as in Example 17. The adhesive layer of the adhesive (20).

Then, a silicone-treated surface of a substrate containing a polyester resin and having a thickness of 25 μm subjected to a silicone treatment on one surface was bonded to the surface of the adhesive layer to obtain a surface protection film (20).

The evaluation results are shown in Table 3.

[Example 21]

Except changing 0.01 parts by weight of 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) fluorenimine to 0.01 parts by weight of 1-ethyl-3-methylpyridinium nonafluorobutane An adhesive layer containing a urethane-based adhesive (21) on a substrate was prepared in the same manner as in Example 1 except for a sulfonic acid salt (manufactured by Mitsubishi Materials Electrochemical Corporation, EtMePy-EF41).

Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one surface was bonded to the surface of the adhesive layer to obtain a surface protection film (21).

The evaluation results are shown in Table 3.

[Example 22]

Except that the amount of 1-ethyl-3-methylpyridinium nonafluorobutyl sulfonate was changed to 0.1 parts by weight, a urethane-based adhesive was produced on the substrate in the same manner as in Example 21 The adhesive layer of the agent (22).

Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one side was bonded to the surface of the adhesive layer to obtain a surface protection film (22).

The evaluation results are shown in Table 3.

[Example 23]

Except that the amount of 1-ethyl-3-methylpyridinium nonafluorobutyl sulfonate was changed to 1 part by weight, a urethane-based adhesive was produced on the substrate in the same manner as in Example 21 The adhesive layer of the agent (23).

Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one side was bonded to the surface of the adhesive layer to obtain a surface protection film (23).

The evaluation results are shown in Table 3.

[Example 24]

Except that the amount of 1-ethyl-3-methylpyridinium nonafluorobutylsulfonate was changed to 10 parts by weight, a urethane-based adhesive was produced on the substrate in the same manner as in Example 21 The adhesive layer of the agent (24).

Then, a silicone-treated surface of a substrate containing a polyester resin with a thickness of 25 μm, which is silicone-treated on one side, is adhered to the surface of the adhesive layer to obtain a surface protection film (24).

The evaluation results are shown in Table 3.

[Example 25]

Except changing 0.01 parts by weight of 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) fluorenimine to 0.01 parts by weight of 1-ethyl-3-methylpyridinium heptafluoropropene An adhesive layer containing a urethane-based adhesive (25) on a substrate was prepared in the same manner as in Example 1 except for a sulfonic acid salt (manufactured by Mitsubishi Materials Electrochemical Corporation, EtMePy-EF31).

Then, a silicone-treated surface of a substrate containing a polyester resin and having a thickness of 25 μm, which is silicone-treated on one side, is adhered to the surface of the adhesive layer to obtain a surface protection film (25).

The evaluation results are shown in Table 4.

[Example 26]

A urethane-based adhesive was produced on the substrate in the same manner as in Example 25 except that the amount of 1-ethyl-3-methylpyridinium heptafluoropropylsulfonate was changed to 0.1 part by weight. The adhesive layer of the agent (26).

Then, a silicone-treated surface of a substrate containing a polyester resin with a thickness of 25 μm, which is silicone-treated on one side, is adhered to the surface of the adhesive layer to obtain a surface protection film (26).

The evaluation results are shown in Table 4.

[Example 27]

Except that the amount of 1-ethyl-3-methylpyridinium heptafluoropropylsulfonate was changed to 1 part by weight, a urethane-based adhesive was produced on the substrate in the same manner as in Example 25. The adhesive layer of the agent (27).

Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one side was bonded to the surface of the adhesive layer to obtain a surface protection film (27).

The evaluation results are shown in Table 4.

[Example 28]

A urethane-based adhesive was prepared on the substrate in the same manner as in Example 25 except that the amount of 1-ethyl-3-methylpyridinium heptafluoropropylsulfonate was changed to 10 parts by weight. The adhesive layer of the agent (28).

Then, a silicone-treated surface of a substrate containing a polyester resin with a thickness of 25 μm that was subjected to a silicone treatment on one side was bonded to the surface of the adhesive layer to obtain a surface protection film (28).

The evaluation results are shown in Table 4.

[Example 29]

In addition to 0.01 parts by weight of 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) fluorene Except that the amine was changed to 0.01 parts by weight of 1-ethyl-3-methylpyridinium pentafluoroethylsulfonate (manufactured by Mitsubishi Materials Electrochemical Corporation, EtMePy-EF21), in the same manner as in Example 1, An adhesive layer containing a urethane-based adhesive (29) on a substrate is prepared.

Then, a silicone-treated surface of a substrate containing a polyester resin with a thickness of 25 μm that was subjected to a silicone treatment on one side was bonded to the surface of the adhesive layer to obtain a surface protection film (29).

The evaluation results are shown in Table 4.

[Example 30]

Except that the amount of 1-ethyl-3-methylpyridinium pentafluoroethylsulfonate was changed to 0.1 part by weight, a urethane-based adhesive was produced on the substrate in the same manner as in Example 29. The adhesive layer of the agent (30).

Then, a silicone-treated surface of a substrate containing a polyester resin with a thickness of 25 μm, which is silicone-treated on one side, is adhered to the surface of the adhesive layer to obtain a surface protection film (30).

The evaluation results are shown in Table 4.

[Example 31]

Except that the amount of 1-ethyl-3-methylpyridinium pentafluoroethylsulfonate was changed to 1 part by weight, a urethane-based adhesive was produced on the substrate in the same manner as in Example 29. The adhesive layer of the agent (31).

Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one side was bonded to the surface of the adhesive layer to obtain a surface protection film (31).

The evaluation results are shown in Table 4.

[Example 32]

Except that the amount of 1-ethyl-3-methylpyridinium pentafluoroethylsulfonate was changed to 10 parts by weight, a urethane-based adhesive was prepared on the substrate in the same manner as in Example 29. Adhesive layer of the adhesive (32).

Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one side is adhered to the surface of the adhesive layer to obtain a surface protection film (32).

The evaluation results are shown in Table 4.

[Example 33]

Except changing 0.01 parts by weight of 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) fluorenimide to 0.01 parts by weight of 1-ethyl-3-methylpyridinium trifluoromethane An adhesive layer containing a urethane-based adhesive (33) on a substrate was prepared in the same manner as in Example 1 except for a sulfonic acid salt (manufactured by Mitsubishi Materials Electrochemical Corporation, EtMePy-EF11).

Then, a silicone-treated surface of a substrate containing a polyester resin and having a thickness of 25 μm, which is silicone-treated on one side, is adhered to the surface of the adhesive layer to obtain a surface protection film (33).

The evaluation results are shown in Table 5.

[Example 34]

Except that the amount of 1-ethyl-3-methylpyridinium trifluoromethanesulfonate was changed to 0.1 part by weight, a urethane-based adhesive was produced on the substrate in the same manner as in Example 33. The adhesive layer of the agent (34).

Then, a silicone-treated surface of a substrate containing a polyester resin with a thickness of 25 μm, which is silicone-treated on one side, is adhered to the surface of the adhesive layer to obtain a surface protection film (34).

The evaluation results are shown in Table 5.

[Example 35]

A urethane-based adhesive was produced on the substrate in the same manner as in Example 33 except that the amount of 1-ethyl-3-methylpyridinium trifluoromethanesulfonate was changed to 1 part by weight. The adhesive layer of the agent (35).

Then, a silicone-treated surface of a substrate containing a polyester resin with a thickness of 25 μm, which is silicone-treated on one side, is adhered to the surface of the adhesive layer to obtain a surface protection film (35).

The evaluation results are shown in Table 5.

[Example 36]

Except that the amount of 1-ethyl-3-methylpyridinium trifluoromethanesulfonate was changed to 10 parts by weight, a urethane-based adhesive was produced on the substrate in the same manner as in Example 33. The adhesive layer of the agent (36).

Then, a silicone-treated surface of a substrate containing a polyester resin with a thickness of 25 μm, which is silicone-treated on one side, is adhered to the surface of the adhesive layer to obtain a surface protection film (36).

The evaluation results are shown in Table 5.

[Example 37]

Except changing 0.01 parts by weight of 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) fluorenimide to 0.01 parts by weight of 1-butyl-3-methylpyridinium bis (tri A pressure-sensitive adhesive layer containing a urethane-based pressure-sensitive adhesive (37) on the substrate was prepared in the same manner as in Example 1 except for fluoromethylsulfonyl) fluorene imine (CIL312, manufactured by Japan Carlit).

Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one surface was bonded to the surface of the adhesive layer to obtain a surface protection film (37).

The evaluation results are shown in Table 5.

[Example 38]

A substrate was prepared in the same manner as in Example 37 except that the amount of 1-butyl-3-methylpyridinium bis (trifluoromethylsulfonyl) fluorenimide was changed to 0.1 part by weight. Adhesive layer of urethane-based adhesive (38).

Next, a 25 μm-thick polyester resin containing polysiloxane will be treated on one side. The silicone-treated surface of the substrate is adhered to the surface of the adhesive layer to obtain a surface protection film (38).

The evaluation results are shown in Table 5.

[Example 39]

A substrate was prepared in the same manner as in Example 37 except that the amount of 1-butyl-3-methylpyridinium bis (trifluoromethylsulfonyl) fluorenimide was changed to 1 part by weight. Adhesive layer of urethane-based adhesive (39).

Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one surface was bonded to the surface of the adhesive layer to obtain a surface protection film (39).

The evaluation results are shown in Table 5.

[Example 40]

Except that the amount of 1-butyl-3-methylpyridinium bis (trifluoromethylsulfonyl) fluorenimide was changed to 10 parts by weight, the same method as in Example 37 was used to prepare a substrate. Adhesive layer of urethane-based adhesive (40).

Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one surface is adhered to the surface of the adhesive layer to obtain a surface protection film (40).

The evaluation results are shown in Table 5.

[Example 41]

Except changing 0.01 parts by weight of 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) fluorenimide to 0.01 parts by weight of 1-butyl-3-methylpyridinium trifluoromethane An adhesive layer containing a urethane-based adhesive (41) on a substrate was prepared in the same manner as in Example 1 except for a sulfonic acid salt (CIL313, manufactured by Japan Carlit Corporation).

Then, a silicone-treated surface of a substrate containing a polyester resin with a thickness of 25 μm, which is silicone-treated on one side, is bonded to the surface of the adhesive layer to obtain a surface protective film. (41).

The evaluation results are shown in Table 6.

[Example 42]

Except that the amount of 1-butyl-3-methylpyridinium trifluoromethanesulfonate was changed to 0.1 part by weight, a urethane-based adhesive was produced on the substrate in the same manner as in Example 41. The adhesive layer of the agent (42).

Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one surface is adhered to the surface of the adhesive layer to obtain a surface protection film (42).

The evaluation results are shown in Table 6.

[Example 43]

A urethane-based adhesive was produced on the substrate in the same manner as in Example 41 except that the amount of 1-butyl-3-methylpyridinium trifluoromethanesulfonate was changed to 1 part by weight. The adhesive layer of the agent (43).

Then, a silicone-treated surface of a substrate containing a polyester resin and having a thickness of 25 μm, which is silicone-treated on one side, is adhered to the surface of the adhesive layer to obtain a surface protection film (43).

The evaluation results are shown in Table 6.

[Example 44]

A urethane-based adhesive was produced on the substrate in the same manner as in Example 41 except that the amount of 1-butyl-3-methylpyridinium trifluoromethanesulfonate was changed to 10 parts by weight. The adhesive layer of the agent (44).

Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one surface was bonded to the surface of the adhesive layer to obtain a surface protection film (44).

The evaluation results are shown in Table 6.

[Example 45]

Except changing 0.01 parts by weight of 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) fluorenimide to 0.01 parts by weight of 1-hexylpyridinium bis (fluorosulfonyl) fluorene Except for amines (manufactured by Mitsubishi Materials Electrochemical Corporation, HxPy-FSI), an adhesive layer containing a urethane-based adhesive (45) on a substrate was prepared in the same manner as in Example 1.

Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one surface was bonded to the surface of the adhesive layer to obtain a surface protection film (45).

The evaluation results are shown in Table 6.

[Example 46]

Except that the amount of 1-hexylpyridinium bis (fluorosulfonyl) fluorenimide was changed to 0.1 part by weight, a urethane-based adhesive (46 ) 'S adhesive layer.

Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one surface was bonded to the surface of the adhesive layer to obtain a surface protection film (46).

The evaluation results are shown in Table 6.

[Example 47]

A urethane-based adhesive (47) was prepared on the substrate in the same manner as in Example 45 except that the amount of 1-hexylpyridinium bis (fluorosulfonyl) fluorenimide was changed to 1 part by weight. ) 'S adhesive layer.

Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one surface was bonded to the surface of the adhesive layer to obtain a surface protection film (47).

The evaluation results are shown in Table 6.

[Example 48]

Except that the amount of 1-hexylpyridinium bis (fluorosulfofluorenyl) fluorenimine was changed to 10 parts by weight, a urethane-based adhesive (48 ) 'S adhesive layer.

Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one surface was bonded to the surface of the adhesive layer to obtain a surface protection film (48).

The evaluation results are shown in Table 6.

[Example 49]

Except changing 0.01 parts by weight of 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) fluorenimide to 0.01 parts by weight of 1-octyl-4-methylpyridinium bis (fluoro Sulfonyl) fluorene imine (manufactured by Daiichi Kogyo Co., Ltd., MP403) was prepared in the same manner as in Example 1, and an adhesive layer containing a urethane-based adhesive (49) on a substrate was prepared.

Then, a silicone-treated surface of a substrate containing a polyester resin with a thickness of 25 μm that was subjected to a silicone treatment on one side was bonded to the surface of the adhesive layer to obtain a surface protection film (49).

The evaluation results are shown in Table 7.

[Example 50]

Except that the amount of 1-octyl-4-methylpyridinium bis (fluorosulfonyl) fluorenimine was changed to 0.1 part by weight, the same procedure as in Example 49 was performed to include ethyl carbamate on the substrate. Adhesive layer of the ester-based adhesive (50).

Then, a silicone-treated surface of a substrate containing a polyester resin and having a thickness of 25 μm subjected to a silicone treatment on one surface was bonded to the surface of the adhesive layer to obtain a surface protection film (50).

The evaluation results are shown in Table 7.

[Example 51]

In addition to changing the amount of 1-octyl-4-methylpyridinium bis (fluorosulfonyl) fluorenimine to 1 weight Except for the components, an adhesive layer containing a urethane-based adhesive (51) on a substrate was prepared in the same manner as in Example 49.

Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one surface was bonded to the surface of the adhesive layer to obtain a surface protection film (51).

The evaluation results are shown in Table 7.

[Example 52]

Except that the amount of 1-octyl-4-methylpyridinium bis (fluorosulfonyl) fluorenimide was changed to 10 parts by weight, in the same manner as in Example 49, ethyl carbamate was produced on the substrate. Adhesive layer of the ester-based adhesive (52).

Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one surface was bonded to the surface of the adhesive layer to obtain a surface protection film (52).

The evaluation results are shown in Table 7.

[Example 53]

Except changing 0.01 parts by weight of 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) fluorenimide to 0.01 parts by weight of trimethylpropylammonium bis (trifluoromethylsulfonium) Base) fluorene imine (manufactured by Toyo Kogyo Co., Ltd., TMPA-TFSI), in the same manner as in Example 1, an adhesive layer containing a urethane-based adhesive (53) on a substrate was prepared.

Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one surface was bonded to the surface of the adhesive layer to obtain a surface protection film (53).

The evaluation results are shown in Table 7.

[Example 54]

Except that the amount of trimethylpropylammonium bis (trifluoromethylsulfonyl) fluorenimide was changed to 0.1 part by weight, a urethane system was produced on the substrate in the same manner as in Example 53. Adhesive layer of adhesive (54).

Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one surface was bonded to the surface of the adhesive layer to obtain a surface protection film (54).

The evaluation results are shown in Table 7.

[Example 55]

Except that the amount of trimethylpropylammonium bis (bistrifluoromethylsulfonyl) sulfonium imine was changed to 1 part by weight, a urethane was included on the substrate in the same manner as in Example 53. The adhesive layer of the adhesive (55).

Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one surface was bonded to the surface of the adhesive layer to obtain a surface protection film (55).

The evaluation results are shown in Table 7.

[Example 56]

Except that the amount of trimethylpropylammonium bis (bistrifluoromethylsulfonyl) fluorenimide was changed to 10 parts by weight, a urethane was prepared on the substrate in the same manner as in Example 53. The adhesive layer of the adhesive (56).

Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one surface is adhered to the surface of the adhesive layer to obtain a surface protection film (56).

The evaluation results are shown in Table 7.

[Example 57]

Except changing 0.01 parts by weight of 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) fluorenimide to 0.01 parts by weight of 1-methyl-1-propylpyrrolidinium bis ( A urethane-based adhesive (57) was produced on the substrate in the same manner as in Example 1 except for trifluoromethylsulfonyl) fluorenimine (IL220 manufactured by Daiichi Kogyo Co., Ltd.). Adhesive layer.

Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one surface was bonded to the surface of the adhesive layer to obtain a surface protection film (57).

The evaluation results are shown in Table 8.

[Example 58]

A substrate was prepared on the substrate in the same manner as in Example 57 except that the amount of 1-methyl-1-propylpyrrolidinium bis (trifluoromethylsulfonyl) fluorenimide was changed to 0.1 part by weight. An adhesive layer containing a urethane-based adhesive (58).

Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one surface was bonded to the surface of the adhesive layer to obtain a surface protection film (58).

The evaluation results are shown in Table 8.

[Example 59]

A substrate was prepared on the substrate in the same manner as in Example 57 except that the amount of 1-methyl-1-propylpyrrolidinium bis (trifluoromethylsulfonyl) fluorenimide was changed to 1 part by weight. An adhesive layer containing a urethane-based adhesive (59).

Then, a silicone-treated surface of a substrate containing a polyester resin with a thickness of 25 μm that is subjected to a silicone treatment on one side is bonded to the surface of the adhesive layer to obtain a surface protection film (59).

The evaluation results are shown in Table 8.

[Example 60]

A substrate was prepared on the substrate in the same manner as in Example 57 except that the amount of 1-methyl-1-propylpyrrolidinium bis (trifluoromethylsulfonyl) fluorenimide was changed to 10 parts by weight. An adhesive layer containing a urethane-based adhesive (60).

Then, a silicone-treated surface of a substrate containing a polyester resin with a thickness of 25 μm, which is silicone-treated on one side, is bonded to the surface of the adhesive layer to obtain a surface protective film. (60).

The evaluation results are shown in Table 8.

[Example 61]

Except changing 0.01 parts by weight of 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) fluorenimide to 0.01 parts by weight of 1-methyl-1-propylpyrrolidinium bis ( An adhesive containing a urethane-based adhesive (61) on the substrate was prepared in the same manner as in Example 1 except for fluorosulfonyl) fluorenimine (manufactured by Daiichi Kogyo Co., Ltd., AS120). Floor.

Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one surface was bonded to the surface of the adhesive layer to obtain a surface protection film (61).

The evaluation results are shown in Table 8.

[Example 62]

Except that the amount of 1-methyl-1-propylpyrrolidinium bis (fluorosulfonyl) fluorenimine was changed to 0.1 part by weight, a carbamic acid was produced on the substrate in the same manner as in Example 61. Adhesive layer of ethyl-based adhesive (62).

Next, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one surface was bonded to the surface of the adhesive layer to obtain a surface protection film (62).

The evaluation results are shown in Table 8.

[Example 63]

Except that the amount of 1-methyl-1-propylpyrrolidinium bis (fluorosulfonyl) fluorenimine was changed to 1 part by weight, carbamic acid was produced on the substrate in the same manner as in Example 61. Adhesive layer of ethyl-based adhesive (63).

Then, a silicone-treated surface of a substrate containing a polyester resin and having a thickness of 25 μm, which is silicone-treated on one side, is adhered to the surface of the adhesive layer to obtain a surface protection film (63).

The evaluation results are shown in Table 8.

[Example 64]

Except that the amount of 1-methyl-1-propylpyrrolidinium bis (fluorosulfonyl) fluorenimide was changed to 10 parts by weight, a carbamic acid was produced on the substrate in the same manner as in Example 61. Adhesive layer of ethyl-based adhesive (64).

Next, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one surface was bonded to the surface of the adhesive layer to obtain a surface protection film (64).

The evaluation results are shown in Table 8.

[Example 65]

Except changing 0.01 parts by weight of 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) fluorenimide to 0.01 parts by weight of 1-methyl-1-propylpiperidinium bis ( Except for trifluoromethylsulfonyl) fluorene imine (manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd., IL230), a urethane-based adhesive (65) was produced on the substrate in the same manner as in Example 1. Adhesive layer.

Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one surface was bonded to the surface of the adhesive layer to obtain a surface protection film (65).

The evaluation results are shown in Table 9.

[Example 66]

A substrate was prepared on the substrate in the same manner as in Example 65 except that the amount of 1-methyl-1-propylpiperidinium bis (trifluoromethylsulfonyl) fluorenimide was changed to 0.1 part by weight. An adhesive layer containing a urethane-based adhesive (66).

Then, a silicone-treated surface of a substrate containing a polyester resin with a thickness of 25 μm, which is silicone-treated on one side, is adhered to the surface of the adhesive layer to obtain a surface protection film (66).

The evaluation results are shown in Table 9.

[Example 67]

A substrate was prepared on the substrate in the same manner as in Example 65 except that the amount of 1-methyl-1-propylpiperidinium bis (trifluoromethylsulfonyl) fluorenimide was changed to 1 part by weight. An adhesive layer containing a urethane-based adhesive (67).

Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one surface was bonded to the surface of the adhesive layer to obtain a surface protection film (67).

The evaluation results are shown in Table 9.

[Example 68]

Except that the amount of 1-methyl-1-propylpiperidinium bis (trifluoromethylsulfonyl) fluorenimide was changed to 10 parts by weight, it was produced on the substrate in the same manner as in Example 65. An adhesive layer containing a urethane-based adhesive (68).

Then, a silicone-treated surface of a substrate containing a polyester resin and having a thickness of 25 μm subjected to a silicone treatment on one side was bonded to the surface of the adhesive layer to obtain a surface protection film (68).

The evaluation results are shown in Table 9.

[Example 69]

Except changing 0.01 parts by weight of 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) fluorenimide to 0.01 parts by weight of 1-methyl-1-propylpiperidinium bis ( An adhesive containing a urethane-based adhesive (69) on the substrate was prepared in the same manner as in Example 1 except for fluorosulfonyl) fluorenimine (manufactured by Daiichi Kogyo Co., Ltd., AS130). Floor.

Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one surface was bonded to the surface of the adhesive layer to obtain a surface protection film (69).

The evaluation results are shown in Table 9.

[Example 70]

Except that the amount of 1-methyl-1-propylpiperidinium bis (fluorosulfofluorenyl) fluorenimide was changed to 0.1 part by weight, carbamic acid was produced on the substrate in the same manner as in Example 69. Adhesive layer of ethyl-based adhesive (70).

Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one surface is adhered to the surface of the adhesive layer to obtain a surface protection film (70).

The evaluation results are shown in Table 9.

[Example 71]

Except that the amount of 1-methyl-1-propylpiperidinium bis (fluorosulfofluorenyl) fluorenimide was changed to 1 part by weight, carbamic acid was produced on the substrate in the same manner as in Example 69. Adhesive layer of ethyl-based adhesive (71).

Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one surface was bonded to the surface of the adhesive layer to obtain a surface protection film (71).

The evaluation results are shown in Table 9.

[Example 72]

Except that the amount of 1-methyl-1-propylpiperidinium bis (fluorosulfofluorenyl) fluorenimine was changed to 10 parts by weight, uramic acid was produced on the substrate in the same manner as in Example 69. Adhesive layer of ethyl-based adhesive (72).

Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one surface was bonded to the surface of the adhesive layer to obtain a surface protection film (72).

The evaluation results are shown in Table 9.

[Example 73]

Except changing 0.01 parts by weight of 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) fluorenimide to 0.01 parts by weight of lithium bis (trifluoromethylsulfonyl) sulfonium imine (Morita Chemical Industry Co., Ltd. Except for Li-TFSI, manufactured by Co., Ltd., in the same manner as in Example 1, an adhesive layer containing a urethane-based adhesive (73) on a substrate was prepared.

Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one surface was bonded to the surface of the adhesive layer to obtain a surface protection film (73).

The evaluation results are shown in Table 10.

[Example 74]

A urethane-based adhesive (74) was produced on the substrate in the same manner as in Example 73 except that the amount of lithium bis (trifluoromethylsulfonyl) fluorenimide was changed to 0.1 part by weight. Adhesive layer.

Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one surface is bonded to the surface of the adhesive layer to obtain a surface protection film (74).

The evaluation results are shown in Table 10.

[Example 75]

A urethane-based adhesive (75) was produced on the substrate in the same manner as in Example 73 except that the amount of lithium bis (trifluoromethylsulfonyl) fluorenimide was changed to 1 part by weight. Adhesive layer.

Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one side was bonded to the surface of the adhesive layer to obtain a surface protection film (75).

The evaluation results are shown in Table 10.

[Example 76]

A urethane-based adhesive (76) was produced on the substrate in the same manner as in Example 73 except that the amount of lithium bis (trifluoromethylsulfonyl) fluorenimide was changed to 10 parts by weight. Adhesive layer.

Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one side is adhered to the surface of the adhesive layer to obtain a surface protection film (76).

The evaluation results are shown in Table 10.

[Example 77]

In addition to changing 0.01 parts by weight of 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) fluorenimide to 0.01 parts by weight of lithium bis (fluorosulfonyl) fluorenimide (Morita Chemicals) Except for Li-TFSI (manufactured by Industrial Co., Ltd.), an adhesive layer containing a urethane-based adhesive (77) on a substrate was prepared in the same manner as in Example 1.

Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one surface was bonded to the surface of the adhesive layer to obtain a surface protective film (77).

The evaluation results are shown in Table 10.

[Example 78]

An adhesive containing a urethane-based adhesive (78) on the substrate was produced in the same manner as in Example 77 except that the amount of lithium bis (fluorosulfonyl) fluorenimide was changed to 0.1 part by weight. Floor.

Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one surface is adhered to the surface of the adhesive layer to obtain a surface protective film (78).

The evaluation results are shown in Table 10.

[Example 79]

An adhesive containing a urethane-based adhesive (79) on the substrate was produced in the same manner as in Example 77 except that the amount of lithium bis (fluorosulfonyl) fluorenimide was changed to 1 part by weight. Floor.

Next, a 25 μm-thick polyester resin containing polysiloxane will be treated on one side. The silicone-treated surface of the base material is adhered to the surface of the adhesive layer to obtain a surface protection film (79).

The evaluation results are shown in Table 10.

[Example 80]

An adhesive containing a urethane-based adhesive (80) on the substrate was produced in the same manner as in Example 77 except that the amount of lithium bis (fluorosulfonyl) fluorenimide was changed to 10 parts by weight. Floor.

Then, a silicone-treated surface of a substrate containing a polyester resin and having a thickness of 25 μm, which is silicone-treated on one side, is adhered to the surface of the adhesive layer to obtain a surface protective film (80).

The evaluation results are shown in Table 10.

[Example 81]

Except for adding 0.001 parts by weight of a two-terminal polyether-modified silicone oil (Shin-Etsu Chemical Industry Co., Ltd., KF-6004) as a formulation when manufacturing a urethane-based adhesive composition, In the same manner as in Example 5, an adhesive layer containing a urethane-based adhesive (81) on a substrate was prepared.

Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one side was bonded to the surface of the adhesive layer to obtain a surface protective film (81).

The evaluation results are shown in Table 11.

[Example 82]

Except for adding 0.001 parts by weight of a two-terminal polyether-modified silicone oil (Shin-Etsu Chemical Industry Co., Ltd., KF-6004) as a formulation for producing a urethane-based adhesive composition, the same procedure as in the examples was performed. 6 In the same manner, an adhesive layer containing a urethane-based adhesive (82) on the substrate was prepared.

Next, a 25 μm-thick polyester resin containing polysiloxane will be treated on one side. The silicone-treated surface of the substrate is adhered to the surface of the adhesive layer to obtain a surface protection film (82).

The evaluation results are shown in Table 11.

[Example 83]

Except for adding 0.001 parts by weight of a two-terminal polyether-modified silicone oil (Shin-Etsu Chemical Industry Co., Ltd., KF-6004) as a formulation when manufacturing a urethane-based adhesive composition, In the same manner as in Example 7, an adhesive layer containing a urethane-based adhesive (83) on a substrate was prepared.

Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one side was bonded to the surface of the adhesive layer to obtain a surface protection film (83).

The evaluation results are shown in Table 11.

[Example 84]

Except that 0.001 part by weight of a two-terminal polyether-modified silicone oil (Shin-Etsu Chemical Industry Co., Ltd., KF-6004) was further formulated as a formulation for producing a urethane-based adhesive composition, the same procedures as in the examples 8 In the same manner, an adhesive layer containing a urethane-based adhesive (84) on a substrate was prepared.

Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one surface was bonded to the surface of the adhesive layer to obtain a surface protection film (84).

The evaluation results are shown in Table 11.

[Example 85]

Except for adding 0.1 parts by weight of a two-terminal polyether-modified silicone oil (Shin-Etsu Chemical Industry Co., Ltd., KF-6004) as a formulation when producing a urethane-based adhesive composition, In the same manner as in Example 5, an adhesive layer containing a urethane-based adhesive (85) on a substrate was prepared.

Next, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one side was bonded to the surface of the adhesive layer to obtain a surface protection film (85).

The evaluation results are shown in Table 11.

[Example 86]

Except for adding 0.1 parts by weight of a two-terminal polyether-modified silicone oil (Shin-Etsu Chemical Industry Co., Ltd., KF-6004) as a formulation when producing a urethane-based adhesive composition, In the same manner as in Example 6, an adhesive layer containing a urethane-based adhesive (86) on a substrate was prepared.

Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one surface was bonded to the surface of the adhesive layer to obtain a surface protection film (86).

The evaluation results are shown in Table 11.

[Example 87]

Except for adding 0.1 parts by weight of a two-terminal polyether-modified silicone oil (Shin-Etsu Chemical Industry Co., Ltd., KF-6004) as a formulation when producing a urethane-based adhesive composition, In the same manner as in Example 7, an adhesive layer containing a urethane-based adhesive (87) on a substrate was prepared.

Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one surface was bonded to the surface of the adhesive layer to obtain a surface protection film (87).

The evaluation results are shown in Table 11.

[Example 88]

Except for adding 0.1 parts by weight of a two-terminal polyether-modified silicone oil (Shin-Etsu Chemical Industry Co., Ltd., KF-6004) as a formulation when producing a urethane-based adhesive composition, In the same manner as in Example 8 Adhesive layer of ethyl-based adhesive (88).

Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one surface was bonded to the surface of the adhesive layer to obtain a surface protection film (88).

The evaluation results are shown in Table 11.

[Example 89]

In addition, 1 part by weight of a two-terminal polyether-modified silicone oil (Shin-Etsu Chemical Industry Co., Ltd., KF-6004) was added as a formulation when the urethane-based adhesive composition was manufactured, in accordance with the examples. 5 In the same manner, an adhesive layer containing a urethane-based adhesive (89) on a substrate was prepared.

Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one surface was bonded to the surface of the adhesive layer to obtain a surface protection film (89).

The evaluation results are shown in Table 12.

[Example 90]

Except for the addition of 1 part by weight of a two-terminal polyether-modified silicone oil (Shin-Etsu Chemical Industry Co., Ltd., KF-6004) as a formulation when producing a urethane-based adhesive composition, In the same manner as in Example 6, an adhesive layer containing a urethane-based adhesive (90) on a substrate was prepared.

Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one surface was bonded to the surface of the adhesive layer to obtain a surface protection film (90).

The evaluation results are shown in Table 12.

[Example 91]

In addition, 1 part by weight of a two-terminal polyether-modified silicone oil (KF-6004, manufactured by Shin-Etsu Chemical Co., Ltd.) is used as a urethane-based adhesive composition. Except for the preparation, an adhesive layer containing a urethane-based adhesive (91) on the substrate was prepared in the same manner as in Example 7.

Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one surface is bonded to the surface of the adhesive layer to obtain a surface protection film (91).

The evaluation results are shown in Table 12.

[Example 92]

In addition to adding 1 part by weight of a two-terminal polyether-modified silicone oil (manufactured by Shin-Etsu Chemical Industry Co., Ltd., KF-6004), as a formulation when producing a urethane-based adhesive composition, In the same manner as in Example 8, an adhesive layer containing a urethane-based adhesive (92) on the substrate was prepared.

Then, a silicone-treated surface of a substrate containing a polyester resin with a thickness of 25 μm, which is silicone-treated on one side, is adhered to the surface of the adhesive layer to obtain a surface protection film (92).

The evaluation results are shown in Table 12.

[Example 93]

Except for adding 0.001 parts by weight of a side chain polyether-modified silicone oil (Shin-Etsu Chemical Industry Co., Ltd., KF-353) as a formulation when manufacturing a urethane-based adhesive composition, In the same manner as in Example 5, an adhesive layer containing a urethane-based adhesive (93) on a substrate was prepared.

Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one surface was bonded to the surface of the adhesive layer to obtain a surface protection film (93).

The evaluation results are shown in Table 12.

[Example 94]

In addition, 0.001 parts by weight of a side chain polyether-modified silicone oil was added (Shin-Etsu Chemical Industry Co., Ltd. Co., Ltd., KF-353) was prepared in the same manner as in Example 6 except that it was used as a formulation when producing a urethane-based adhesive composition, and a urethane-based adhesive (94 ) 'S adhesive layer.

Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one side was bonded to the surface of the adhesive layer to obtain a surface protection film (94).

The evaluation results are shown in Table 12.

[Example 95]

Except for adding 0.001 parts by weight of a side chain polyether-modified silicone oil (Shin-Etsu Chemical Industry Co., Ltd., KF-353) as a formulation when manufacturing a urethane-based adhesive composition, In the same manner as in Example 7, an adhesive layer containing a urethane-based adhesive (95) on a substrate was prepared.

Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one surface was bonded to the surface of the adhesive layer to obtain a surface protection film (95).

The evaluation results are shown in Table 12.

[Example 96]

Except for adding 0.001 parts by weight of a side chain polyether-modified silicone oil (Shin-Etsu Chemical Industry Co., Ltd., KF-353) as a formulation when manufacturing a urethane-based adhesive composition, In the same manner as in Example 8, an adhesive layer containing a urethane-based adhesive (96) on a substrate was prepared.

Then, a silicone-treated surface of a substrate containing a polyester resin and having a thickness of 25 μm, which is silicone-treated on one side, is adhered to the surface of the adhesive layer to obtain a surface protection film (96).

The evaluation results are shown in Table 12.

[Example 97]

In addition to adding 0.1 parts by weight of a side chain polyether-modified silicone oil (KF-353, manufactured by Shin-Etsu Chemical Industry Co., Ltd.) as a formulation when producing a urethane-based adhesive composition, In the same manner as in Example 5, an adhesive layer containing a urethane-based adhesive (97) on a substrate was prepared.

Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one surface was bonded to the surface of the adhesive layer to obtain a surface protection film (97).

The evaluation results are shown in Table 13.

[Example 98]

In addition to adding 0.1 parts by weight of a side chain polyether-modified silicone oil (KF-353, manufactured by Shin-Etsu Chemical Industry Co., Ltd.) as a formulation when producing a urethane-based adhesive composition, In the same manner as in Example 6, an adhesive layer containing a urethane-based adhesive (98) on a substrate was prepared.

Then, a silicone-treated surface of a substrate containing a polyester resin with a thickness of 25 μm, which is silicone-treated on one side, is adhered to the surface of the adhesive layer to obtain a surface protection film (98).

The evaluation results are shown in Table 13.

[Example 99]

In addition to adding 0.1 parts by weight of a side chain polyether-modified silicone oil (KF-353, manufactured by Shin-Etsu Chemical Industry Co., Ltd.) as a formulation when producing a urethane-based adhesive composition, In the same manner as in Example 7, an adhesive layer containing a urethane-based adhesive (99) on a substrate was prepared.

Next, a silicone-treated surface of a substrate containing a polyester resin with a thickness of 25 μm, which was subjected to a silicone treatment on one side, was adhered to the surface of the adhesive layer to obtain a surface protection film (99).

The evaluation results are shown in Table 13.

[Example 100]

In addition to adding 0.1 parts by weight of a side chain polyether-modified silicone oil (KF-353, manufactured by Shin-Etsu Chemical Industry Co., Ltd.) as a formulation when producing a urethane-based adhesive composition, In the same manner as in Example 8, an adhesive layer containing a urethane-based adhesive (100) on a substrate was prepared.

Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one surface was bonded to the surface of the adhesive layer to obtain a surface protection film (100).

The evaluation results are shown in Table 13.

[Example 101]

Except for adding 1 part by weight of a side chain type polyether-modified silicone oil (KF-353, manufactured by Shin-Etsu Chemical Co., Ltd.) as a formulation when manufacturing a urethane-based adhesive composition, In the same manner as in Example 5, an adhesive layer containing a urethane-based adhesive (101) on a substrate was prepared.

Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one surface was bonded to the surface of the adhesive layer to obtain a surface protection film (101).

The evaluation results are shown in Table 13.

[Example 102]

Except for adding 1 part by weight of a side chain type polyether-modified silicone oil (KF-353, manufactured by Shin-Etsu Chemical Co., Ltd.) as a formulation when manufacturing a urethane-based adhesive composition, In the same manner as in Example 6, an adhesive layer containing a urethane-based adhesive (102) on a substrate was prepared.

Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one surface is adhered to the surface of the adhesive layer to obtain a surface protection film (102).

The evaluation results are shown in Table 13.

[Example 103]

Except for adding 1 part by weight of a side chain type polyether-modified silicone oil (KF-353, manufactured by Shin-Etsu Chemical Co., Ltd.) as a formulation when manufacturing a urethane-based adhesive composition, In the same manner as in Example 7, an adhesive layer containing a urethane-based adhesive (103) on a substrate was prepared.

Then, a silicone-treated surface of a substrate containing a polyester resin with a thickness of 25 μm, which is silicone-treated on one side, is adhered to the surface of the adhesive layer to obtain a surface protection film (103).

The evaluation results are shown in Table 13.

[Example 104]

Except for adding 1 part by weight of a side chain type polyether-modified silicone oil (KF-353, manufactured by Shin-Etsu Chemical Co., Ltd.) as a formulation when manufacturing a urethane-based adhesive composition, In the same manner as in Example 8, an adhesive layer containing a urethane-based adhesive (104) on a substrate was prepared.

Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one surface was bonded to the surface of the adhesive layer to obtain a surface protection film (104).

The evaluation results are shown in Table 13.

[Comparative Example 1]

Except that fatty acid ester and 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) fluorenimide were not used, the same method as in Example 1 was used to prepare a base material containing carbamic acid. Adhesive layer of ethyl-based adhesive (C1).

Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one surface was bonded to the surface of the adhesive layer to obtain a surface protection film (C1).

The evaluation results are shown in Table 14.

[Comparative Example 2]

Except that 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) fluorenimine was not used, a urethane-based adhesive was produced on the substrate in the same manner as in Example 1 Adhesive layer of the agent (C2).

Then, a silicone-treated surface of a substrate containing a polyester resin with a thickness of 25 μm, which is silicone-treated on one side, is adhered to the surface of the adhesive layer to obtain a surface protective film (C2).

The evaluation results are shown in Table 14.

[Comparative Example 3]

In addition to not using fatty acid esters and 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) fluorenimide; 0.08 parts by weight of EMBILIZER OL-1 (manufactured by Tokyo Fine Chemicals Co., Ltd.) ) In the same manner as in Example 1 except that 0.04 parts by weight of Nacem Ferric Iron was used as a catalyst, an adhesive layer containing a urethane-based adhesive (C3) on a substrate was prepared.

Then, a silicone-treated surface of a substrate containing a polyester resin having a thickness of 25 μm and subjected to a silicone treatment on one side was bonded to the surface of the adhesive layer to obtain a surface protective film (C3).

The evaluation results are shown in Table 14.

[Comparative Example 4]

Except that 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) fluorenimine is not used; furthermore, 0.08 parts by weight of EMBILIZER OL-1 (manufactured by Tokyo Fine Chemicals Co., Ltd.) is used instead of 0.04 weight An adhesive layer containing a urethane-based adhesive (C4) on a substrate was prepared in the same manner as in Example 1 except that Nacem Ferric Iron was used as a catalyst.

Next, a 25 μm-thick polyester resin containing polysiloxane will be treated on one side. The silicone-treated surface of the base material was bonded to the surface of the adhesive layer to obtain a surface protection film (C4).

The evaluation results are shown in Table 14.

[Example 105]

The surface protective film (4) obtained in Example 4 was attached to a polarizing plate (manufactured by Nitto Denko Corporation, trade name "TEG1465DUHC") as an optical member to obtain an optical member with a surface protective film attached thereto.

[Example 106]

The surface protective film (8) obtained in Example 8 was attached to a polarizing plate as an optical member (Manufactured by Nitto Denko Corporation, trade name "TEG1465DUHC"), an optical member with a surface protective film attached was obtained.

[Example 107]

The surface protective film (12) obtained in Example 12 was attached to a polarizing plate (manufactured by Nitto Denko Corporation, trade name "TEG1465DUHC") as an optical member, and an optical member to which a surface protective film was attached was obtained.

[Example 108]

The surface protective film (16) obtained in Example 16 was attached to a polarizing plate (manufactured by Nitto Denko Corporation, trade name "TEG1465DUHC") as an optical member, and an optical member to which a surface protective film was attached was obtained.

[Example 109]

The surface protective film (20) obtained in Example 20 was attached to a polarizing plate (manufactured by Nitto Denko Corporation, trade name "TEG1465DUHC") as an optical member to obtain an optical member with a surface protective film attached thereto.

[Example 110]

The surface protective film (24) obtained in Example 24 was attached to a polarizing plate (manufactured by Nitto Denko Corporation, trade name "TEG1465DUHC") as an optical member, and an optical member with a surface protective film attached was obtained.

[Example 111]

The surface protective film (28) obtained in Example 28 was attached to a polarizing plate (manufactured by Nitto Denko Corporation, trade name "TEG1465DUHC") as an optical member, to obtain an optical member with a surface protective film attached thereto.

[Example 112]

The surface protective film (32) obtained in Example 32 was attached to a polarizing plate (manufactured by Nitto Denko Corporation, trade name "TEG1465DUHC") as an optical member, and an optical member with a surface protective film attached was obtained.

[Example 113]

The surface protective film (36) obtained in Example 36 was attached to a polarizing plate (manufactured by Nitto Denko Corporation, trade name "TEG1465DUHC") as an optical member to obtain an optical member with a surface protective film attached thereto.

[Example 114]

The surface protective film (40) obtained in Example 40 was attached to a polarizing plate (manufactured by Nitto Denko Corporation, trade name "TEG1465DUHC") as an optical member to obtain an optical member with a surface protective film attached thereto.

[Example 115]

The surface protective film (44) obtained in Example 44 was attached to a polarizing plate (manufactured by Nitto Denko Corporation, trade name "TEG1465DUHC") as an optical member, and an optical member with a surface protective film attached was obtained.

[Example 116]

The surface protective film (48) obtained in Example 48 was attached to a polarizing plate (manufactured by Nitto Denko Corporation, trade name "TEG1465DUHC") as an optical member, and an optical member to which a surface protective film was attached was obtained.

[Example 117]

The surface protective film (52) obtained in Example 52 was attached to a polarizing plate (manufactured by Nitto Denko Corporation, trade name "TEG1465DUHC") as an optical member, and an optical member to which a surface protective film was attached was obtained.

[Example 118]

The surface protective film (56) obtained in Example 56 was attached to a polarizing plate (manufactured by Nitto Denko Corporation, trade name "TEG1465DUHC") as an optical member to obtain an optical member with a surface protective film attached thereto.

[Example 119]

The surface protective film (60) obtained in Example 60 was attached to polarized light as an optical member Plate (manufactured by Nitto Denko Corporation, trade name "TEG1465DUHC") to obtain an optical member with a surface protective film attached thereto.

[Example 120]

The surface protective film (60) obtained in Example 60 was attached to a polarizing plate (manufactured by Nitto Denko Corporation, trade name "TEG1465DUHC") as an optical member, and an optical member with a surface protective film attached was obtained.

[Embodiment 121]

The surface protective film (64) obtained in Example 64 was attached to a polarizing plate (manufactured by Nitto Denko Corporation, trade name "TEG1465DUHC") as an optical member, and an optical member to which a surface protective film was attached was obtained.

[Example 122]

The surface protective film (68) obtained in Example 68 was attached to a polarizing plate (manufactured by Nitto Denko Corporation, trade name "TEG1465DUHC") as an optical member to obtain an optical member to which a surface protective film was attached.

[Example 123]

The surface protective film (72) obtained in Example 72 was attached to a polarizing plate (manufactured by Nitto Denko Corporation, trade name "TEG1465DUHC") as an optical member, and an optical member to which a surface protective film was attached was obtained.

[Example 124]

The surface protective film (76) obtained in Example 76 was attached to a polarizing plate (manufactured by Nitto Denko Corporation, trade name "TEG1465DUHC") as an optical member to obtain an optical member with a surface protective film attached thereto.

[Example 125]

The surface protective film (80) obtained in Example 80 was attached to a polarizing plate (manufactured by Nitto Denko Corporation, trade name "TEG1465DUHC") as an optical member to obtain an optical member with a surface protective film attached thereto.

[Example 126]

The surface protective film (84) obtained in Example 84 was attached to a polarizing plate (manufactured by Nitto Denko Corporation, trade name "TEG1465DUHC") as an optical member, and an optical member to which a surface protective film was attached was obtained.

[Example 127]

The surface protective film (88) obtained in Example 88 was attached to a polarizing plate (manufactured by Nitto Denko Corporation, trade name "TEG1465DUHC") as an optical member to obtain an optical member with a surface protective film attached thereto.

[Example 128]

The surface protective film (92) obtained in Example 92 was attached to a polarizing plate (manufactured by Nitto Denko Corporation, trade name "TEG1465DUHC") as an optical member to obtain an optical member with a surface protective film attached thereto.

[Example 129]

The surface protective film (96) obtained in Example 96 was attached to a polarizing plate (manufactured by Nitto Denko Corporation, trade name "TEG1465DUHC") as an optical member to obtain an optical member with a surface protective film attached thereto.

[Example 130]

The surface protective film (100) obtained in Example 100 was attached to a polarizing plate (manufactured by Nitto Denko Corporation, trade name "TEG1465DUHC") as an optical member, and an optical member to which a surface protective film was attached was obtained.

[Example 131]

The surface protective film (104) obtained in Example 104 was attached to a polarizing plate (manufactured by Nitto Denko Corporation, trade name "TEG1465DUHC") as an optical member, and an optical member with a surface protective film attached was obtained.

[Example 132]

The surface protection film (4) obtained in Example 4 was attached to the electrical conductivity as an electronic component Film (manufactured by Nitto Denko Corporation, trade name "ELECRYSTA V270L-TFMP"), and an electronic component with a surface protective film attached.

[Example 133]

The surface protection film (8) obtained in Example 8 was attached to a conductive film as an electronic component (manufactured by Nitto Denko Corporation, trade name "ELECRYSTA V270L-TFMP") to obtain an electron with a surface protection film attached thereto. member.

[Example 134]

The surface protection film (12) obtained in Example 12 was attached to a conductive film (manufactured by Nitto Denko Corporation, trade name "ELECRYSTA V270L-TFMP") as an electronic component, and an electron with a surface protection film attached was obtained. member.

[Example 135]

The surface protection film (16) obtained in Example 16 was attached to a conductive film (manufactured by Nitto Denko Corporation, trade name "ELECRYSTA V270L-TFMP") as an electronic component, and an electron with a surface protection film attached was obtained. member.

[Example 136]

The surface protection film (20) obtained in Example 20 was attached to a conductive film (manufactured by Nitto Denko Corporation, trade name "ELECRYSTA V270L-TFMP") as an electronic component, and an electron with a surface protection film attached was obtained member.

[Example 137]

The surface protection film (24) obtained in Example 24 was attached to a conductive film (manufactured by Nitto Denko Corporation, trade name "ELECRYSTA V270L-TFMP") as an electronic component, and an electron with the surface protection film attached was obtained. member.

[Example 138]

The surface protection film (28) obtained in Example 28 was attached to a conductive film (manufactured by Nitto Denko Corporation, trade name "ELECRYSTA V270L-TFMP") as an electronic component, and an electron with the surface protection film attached was obtained member.

[Example 139]

The surface protection film (32) obtained in Example 32 was attached to a conductive film (manufactured by Nitto Denko Corporation, trade name "ELECRYSTA V270L-TFMP") as an electronic component, and an electron with a surface protection film attached was obtained. member.

[Example 140]

The surface protection film (36) obtained in Example 36 was attached to a conductive film as an electronic component (manufactured by Nitto Denko Corporation, trade name "ELECRYSTA V270L-TFMP") to obtain an electron with a surface protection film attached thereto. member.

[Example 141]

The surface protective film (40) obtained in Example 40 was attached to a conductive film (manufactured by Nitto Denko Corporation, trade name "ELECRYSTA V270L-TFMP") as an electronic component, and an electron with the surface protective film attached was obtained. member.

[Example 142]

The surface protection film (44) obtained in Example 44 was attached to a conductive film as an electronic component (manufactured by Nitto Denko Corporation, trade name "ELECRYSTA V270L-TFMP") to obtain an electron with a surface protection film attached thereto. member.

[Example 143]

The surface protection film (48) obtained in Example 48 was attached to a conductive film (manufactured by Nitto Denko Corporation, trade name "ELECRYSTA V270L-TFMP") as an electronic component, and an electron with the surface protection film attached was obtained. member.

[Example 144]

The surface protective film (52) obtained in Example 52 was attached to a conductive film as an electronic component (manufactured by Nitto Denko Corporation, trade name "ELECRYSTA V270L-TFMP") to obtain an electron with the surface protective film attached thereto. member.

[Example 145]

The surface protection film (56) obtained in Example 56 was attached to a conductive material as an electronic component A protective film (manufactured by Nitto Denko Corporation, trade name "ELECRYSTA V270L-TFMP") was obtained as an electronic component with a surface protective film attached.

[Example 146]

The surface protection film (56) obtained in Example 56 was attached to a conductive film (manufactured by Nitto Denko Corporation, trade name "ELECRYSTA V270L-TFMP") as an electronic component, and an electron with a surface protection film attached was obtained. member.

[Example 147]

The surface protection film (60) obtained in Example 60 was attached to a conductive film as an electronic component (manufactured by Nitto Denko Corporation, trade name "ELECRYSTA V270L-TFMP") to obtain an electron with a surface protection film attached thereto. member.

[Example 148]

The surface protection film (64) obtained in Example 64 was attached to a conductive film (manufactured by Nitto Denko Corporation, trade name "ELECRYSTA V270L-TFMP") as an electronic component, and an electron with the surface protection film attached was obtained member.

[Example 149]

The surface protection film (68) obtained in Example 68 was attached to a conductive film (manufactured by Nitto Denko Corporation, trade name "ELECRYSTA V270L-TFMP") as an electronic component, and an electron with a surface protection film attached was obtained member.

[Example 150]

The surface protection film (72) obtained in Example 72 was attached to a conductive film (manufactured by Nitto Denko Corporation, trade name "ELECRYSTA V270L-TFMP") as an electronic component, and an electron with the surface protection film attached was obtained. member.

[Embodiment 151]

The surface protection film (76) obtained in Example 76 was attached to a conductive film (manufactured by Nitto Denko Corporation, trade name "ELECRYSTA V270L-TFMP") as an electronic component, and an electron with a surface protection film attached was obtained. member.

[Example 152]

The surface protective film (80) obtained in Example 80 was attached to a conductive film (manufactured by Nitto Denko Corporation, trade name "ELECRYSTA V270L-TFMP") as an electronic component, and an electron with the surface protective film attached was obtained. member.

[Embodiment 153]

The surface protection film (84) obtained in Example 84 was attached to a conductive film (manufactured by Nitto Denko Corporation, trade name "ELECRYSTA V270L-TFMP") as an electronic component, and an electron with the surface protection film attached was obtained. member.

[Example 154]

The surface protection film (88) obtained in Example 88 was attached to a conductive film (manufactured by Nitto Denko Corporation, trade name "ELECRYSTA V270L-TFMP") as an electronic component, and an electron with the surface protection film attached was obtained member.

[Example 155]

The surface protection film (92) obtained in Example 92 was attached to a conductive film (manufactured by Nitto Denko Corporation, trade name "ELECRYSTA V270L-TFMP") as an electronic component, and an electron with a surface protection film attached was obtained. member.

[Example 156]

The surface protection film (96) obtained in Example 96 was attached to a conductive film (manufactured by Nitto Denko Corporation, trade name "ELECRYSTA V270L-TFMP") as an electronic component, and an electron with a surface protection film attached was obtained. member.

[Example 157]

The surface protection film (100) obtained in Example 100 was attached to a conductive film (manufactured by Nitto Denko Corporation, trade name "ELECRYSTA V270L-TFMP") as an electronic component, and an electron with a surface protection film attached was obtained. member.

[Example 158]

The surface protective film (104) obtained in Example 104 was attached as a guide for electronic components. Electrical film (manufactured by Nitto Denko Corporation, trade name "ELECRYSTA V270L-TFMP"), an electronic component with a surface protective film attached.

[Industrial availability]

The urethane-based adhesive of the present invention can be used for any appropriate application. The urethane-based adhesive of the present invention is preferably excellent in antistatic properties and excellent in paste residue resistance or reworkability. Therefore, the surface protective film is used as an adhesive layer for a surface protective film. It can be preferably used for surface protection of optical components or electronic components.

Claims (7)

A urethane-based adhesive comprising a urethane-based resin, and the urethane-based resin is obtained by hardening a composition containing a polyol (A) and a polyfunctional isocyanate compound (B) Urethane-based resin; the polyol (A) contains a polyol having a number average molecular weight Mn of 400 to 20,000; the equivalents of the NCO group and the OH group in the polyol (A) and the polyfunctional isocyanate compound (B) The ratio is more than 1.0 and 5.0 or less in terms of NCO group / OH group; the urethane-based adhesive contains an ionic liquid containing a fluorine organic anion. The urethane-based adhesive according to claim 1, wherein the ionic liquid is composed of the fluorine organic anion and the onium cation. The urethane-based adhesive according to claim 2, wherein the onium cation is at least one selected from the group consisting of a nitrogen-containing cation, a sulfur-containing cation, and a phosphorus-containing cation. The urethane-based adhesive according to any one of claims 1 to 3, wherein the content ratio of the polyfunctional isocyanate compound (B) to the polyol (A) is 5 to 60% by weight. A surface protection film comprising: a base material layer; and an adhesive layer, the adhesive layer including the urethane-based adhesive according to any one of claims 1 to 4. An optical member to which a surface protective film as claimed in claim 5 is attached. An electronic component having a surface protective film as claimed in claim 5.