JP6534564B2 - Surface protection film - Google Patents

Description

  The present invention relates to a surface protection film. The present invention also relates to an optical member and an electronic member to which such a surface protective film is attached.

  LCDs, organic ELs, touch panels using them, lens parts of cameras, optical members such as electronic devices and electronic members are generally exposed to prevent scratches on the surface during processing, assembly, inspection, transportation, etc. A surface protection film is attached to the surface side.

  Such a surface protective film usually has a base material layer and an adhesive layer, and a separator is provided to protect the surface of the adhesive layer. Such a surface protective film is attached to an adherend such as an optical member or an electronic member after peeling off the separator to expose the pressure-sensitive adhesive layer, and then, when it is not necessary to protect the surface, optical It peels from adherends, such as a member and an electronic member (for example, patent documents 1 and 2). For this reason, it is required that a trigger for peeling from the adherend can be easily obtained and that the peeling can be light.

  In the manufacturing process of an optical member or an electronic member, in order to detect a defective product, it is required to detect a flaw or foreign matter mixing on the optical member or the electronic member.

  However, since the optical member and the electronic member which stuck the conventional surface protection film have high transparency as a whole, there exists a problem that the detection rate of the flaw in a manufacturing process or foreign material mixing is low.

JP 2005-306996 A JP 2005-309071 A

  An object of the present invention is to provide a surface protection film which can easily obtain a trigger for peeling from an adherend, can be lightly peeled, and has a high detection rate of scratches and inclusion of foreign matter. Moreover, the subject of this invention is providing the optical member and electronic member by which such a surface protection film was stuck.

The surface protection film of the present invention is
It is a surface protection film having a substrate layer mainly composed of a polyester resin and an adhesive layer,
The base layer is a colored base layer containing a black pigment,
The total light transmittance of the surface protective film is 5% or less,
Triggering force at a peeling speed of 0.3 m / min and a peeling angle of 90 degrees against glass of the surface protective film is 1 N / 25 mm or less,
The peeling force at a peeling speed of 0.3 m / min and a peeling angle of 180 degrees with respect to glass of the surface protective film is 0.1 N / 25 mm or less,
The wetting rate of the surface protective film to glass is 0.05 cm ² / sec or more.

  In one embodiment, the pressure-sensitive adhesive layer contains at least one pressure-sensitive adhesive selected from a urethane-based pressure-sensitive adhesive and an acrylic pressure-sensitive adhesive.

  The optical member of the present invention is obtained by sticking the surface protection film of the present invention.

  The electronic member of the present invention is obtained by sticking the surface protection film of the present invention.

  ADVANTAGE OF THE INVENTION According to this invention, the trigger of peeling from a to-be-adhered body can be obtained easily, and it can peel lightly, and also can provide the surface protection film with a high detection rate of a flaw and foreign substance mixing. Further, according to the present invention, it is possible to provide an optical member or an electronic member to which such a surface protective film is attached.

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

«Surface protection film»
The surface protection film of the present invention has a substrate layer mainly composed of a polyester resin and an adhesive layer.

  FIG. 1 is a schematic cross-sectional view of a surface protection film according to one embodiment of the present invention. The surface protection film 10 is provided with the base material layer 1 and the adhesive layer 2 in this order. The surface protective film of the present invention may further have any appropriate other layer, as required. For example, as shown in FIG. 1, the separator 3 may be provided on the side of the pressure-sensitive adhesive layer 2 opposite to the base layer 1.

  The separator may be composed of a single layer or may be composed of a plurality of layers.

  The thickness of the separator may be set to any appropriate thickness depending on the application. From the viewpoint of sufficiently expressing the effects of the present invention, it is preferably 20 μm to 100 μm, more preferably 25 μm to 90 μm, still more preferably 30 μm to 80 μm, and particularly preferably 35 μm to 70 μm.

  Any appropriate material may be adopted as the material of the separator as long as the effects of the present invention are not impaired. Such materials include, for example, plastics, paper, metal films, non-woven fabrics and the like. Among such materials, preferably, it is plastic. The separator may be composed of one type of material or may be composed of two or more types of materials.

  For the surface of the base material layer 1 where the pressure-sensitive adhesive layer 2 is not attached, for example, fatty acid amide, polyethylene imine, long chain alkyl type to the base material layer for the purpose of forming a wound body which can be easily unwound. An additive etc. can be added and a mold release process can be performed, or the coat layer which consists of arbitrary appropriate release agents, such as a silicone type, a long chain alkyl type, and a fluorine type, can be provided.

  The thickness of the surface protective film of the present invention may be set to any appropriate thickness depending on the application. From the viewpoint of sufficiently expressing the effects of the present invention, it is preferably 25 μm to 135 μm, more preferably 30 μm to 120 μm, still more preferably 35 μm to 100 μm, and particularly preferably 35 μm to 75 μm.

  The surface protective film of the present invention has a total light transmittance of 5% or less, preferably 4.5% or less, more preferably 4% or less, and still more preferably 3.5% or less, in particular Preferably it is 3% or less. The lower limit value of the total light transmittance is preferably 0%. By adjusting the total light transmittance of the surface protection film of the present invention within the above range, it is possible to provide a surface protection film having a high detection rate of flaws and contamination. The details of the method of measuring the total light transmittance will be described later.

  The surface protective film of the present invention has a trigger peeling force of 1 N / 25 mm or less, preferably 0.8 N / 25 mm or less, at a peeling speed of 0.3 m / min and a peeling angle of 90 degrees to glass. It is 0.5 N / 25 mm or less, more preferably 0.3 N / 25 mm or less, particularly preferably 0.1 N / 25 mm or less, and most preferably 0.08 N / 25 mm or less. The lower limit value of this trigger peeling force is preferably 0.01 N / 25 mm. The surface protection film of the present invention attached to the adherend by adjusting the trigger peeling force at a peeling speed of 0.3 m / min and a peeling angle of 90 degrees to glass within the above range of the surface protective film of the present invention to glass A trigger for the peeling of the In addition, the detail of the measuring method of the said trigger peeling force is mentioned later.

  The surface protective film of the present invention has a peeling speed of 0.3 m / min and a peeling force of 0.1 N / 25 mm or less, preferably 0.08 N / 25 mm or less, at a peeling angle of 180 degrees with respect to glass, more preferably Is 0.06 N / 25 mm or less, more preferably 0.05 N / 25 mm or less, particularly preferably 0.04 N / 25 mm or less, and most preferably 0.03 N / 25 mm or less. The lower limit value of this peeling force is preferably 0.005 N / 25 mm. The surface protective film of the present invention attached to an adherend by adjusting the peeling force at a peeling speed of 0.3 m / min and a peeling angle of 180 degrees of the surface protective film of the present invention to glass within the above range It can be lightly peeled off. In addition, the detail of the measuring method of the said peeling force is mentioned later.

Wetting rate for the glass of the surface protective film of the present invention is 0.05 cm ² / sec or more, preferably 0.08 cm ² / sec or more, more preferably 0.1 cm ² / sec or more, more preferably It is 1 cm ² / sec or more, particularly preferably 5 cm ² / sec or more, and most preferably 10 cm ² / sec or more. The upper limit of the wetting rate is preferably 1000 cm ² / sec, more preferably 100 cm ² / sec, still more preferably 50 cm ² / sec, and particularly preferably 20 cm ² / sec. By adjusting the wetting speed of the surface protection film of the present invention to the glass within the above range, it is possible to suppress the inclusion of air bubbles and foreign matter, and to provide a surface protection film having a high detection rate of scratches and foreign matter contamination. In addition, the detail of the measuring method of the said wetting speed is mentioned later.

The surface protective film of the present invention is, as described above,
(A) total light transmittance is 5% or less,
(B) That the trigger peeling force at a peeling speed of 0.3 m / min and a peeling angle of 90 degrees with respect to glass is 1 N / 25 mm or less,
(C) Peeling speed of 0.3 m / min or less and peeling force at a peeling angle of 180 degrees to glass of 0.1 N / 25 mm or less,
(D) the wetting speed to glass is 0.05 cm ² / sec or more,
By satisfying all the requirements described above, a trigger for peeling from the adherend can be easily obtained, the peeling can be light, and the detection rate of scratches and foreign matter contamination can be increased.

<Base layer>
The base material layer contains polyester resin as a main component. Specifically, the content ratio of the polyester resin in the base material layer is preferably 50 wt% to 99.99 wt%, more preferably 70 wt% to 99.95 wt%, and still more preferably 90. % By weight to 99.9% by weight, particularly preferably 92% by weight to 99.7% by weight, and most preferably 95% by weight to 99.5% by weight. By adjusting the content ratio of the polyester resin in the base material layer within the above range, a trigger for peeling from the adherend can be easily obtained, and light peeling can be performed, and furthermore, the detection rate of scratches and foreign matter contamination Can provide a higher surface protection film.

  Examples of the polyester resin include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate and the like. The polyester resin in the base material layer may be only one type or two or more types.

  The base material layer may consist of a single layer, or may consist of a plurality of layers. The base material layer may be unstretched or stretched.

  The thickness of the substrate layer may be set to any appropriate thickness depending on the application. From the viewpoint of sufficiently expressing the effects of the present invention, it is preferably 20 μm to 150 μm, more preferably 25 μm to 125 μm, still more preferably 30 μm to 100 μm, and particularly preferably 35 μm to 75 μm.

  The base layer is a colored base layer containing a black pigment. By using a base material layer as a colored base material layer containing a black pigment, it is possible to provide a surface protection film having a high detection rate of flaws and contamination. Furthermore, when using a means using a black pigment as a means to make a base material layer a colored base material layer, for example, when making a base material layer a colored base material layer by a means which provides a colored layer (for example, printing layer) In comparison with the above, the problem of the reduction of the coloring effect due to the dropping of the colored layer and the problem of the contamination of the production line due to the dropping of the colored layer can be reduced. In addition, by forming the base material layer as a colored base material layer containing a black pigment, the base material layer uniformly colored by uniform dispersion of the black pigment can be obtained. Can provide a surface protection film with a high detection rate of

  As the black pigment, any suitable black pigment can be adopted as long as the effects of the present invention are not impaired. As such black pigments, for example, carbon black, titanium black, black chromium oxide, black iron oxide, carbon nanotubes, aniline black, perylene pigments, C.I. I. Solvent black 123 etc. are mentioned. The black pigment is preferably carbon black.

  The content ratio of the black pigment in the base layer is preferably 0.01% by weight to 30% by weight, more preferably 0.05% by weight to 20% by weight, and still more preferably 0.1% by weight It is 10% by weight, particularly preferably 0.3% by weight to 5% by weight, and most preferably 0.5% by weight to 1% by weight. By adjusting the content ratio of the black pigment in the base material layer within the above range, it is possible to provide a surface protection film having a higher detection rate of flaws and foreign matter contamination. In addition, by adjusting the content ratio of the black pigment in the base material layer to the above range, it is possible to obtain a uniformly colored base material layer by uniformly dispersing the black pigment. It is possible to provide a surface protection film having a higher detection rate of contamination.

  As a method of incorporating a black pigment in the base material layer, it may be added before, during or after polymerization for producing a polyester resin. As such a method, for example, there is a compounded pellet method in which a black pigment is directly melted, dispersed and added to a polyester resin in an extruder.

  The substrate layer may contain any appropriate additive, as needed. As an additive which may be contained in a base material layer, an antioxidant, an ultraviolet absorber, a light stabilizer, an antistatic agent, a filler, a pigment etc. are mentioned, for example. The type, number, and amount of additives that can be contained in the substrate layer can be appropriately set depending on the purpose.

  Any appropriate antioxidant may be employed as the antioxidant. Examples of such antioxidants include phenol-based antioxidants, phosphorus-based processing heat stabilizers, lactone-based processing heat stabilizers, sulfur-based heat stabilizers, phenol / phosphorus-based antioxidants, and the like. The content ratio of the antioxidant is preferably 1% by weight or less, more preferably 0.5% by weight or less, and further preferably 0.01% by weight to 0% with respect to the polyester resin in the base material layer. .2% by weight.

  Any appropriate ultraviolet absorber may be employed as the ultraviolet absorber. As such an ultraviolet absorber, a benzotriazole type ultraviolet absorber, a triazine type ultraviolet absorber, a benzophenone series ultraviolet absorber etc. are mentioned, for example. The content ratio of the ultraviolet light absorber is preferably 2% by weight or less, more preferably 1% by weight or less, and still more preferably 0.01% by weight to 0.5% by weight with respect to the polyester resin in the base material layer. It is weight%.

  Any appropriate light stabilizer may be employed as the light stabilizer. Examples of such light stabilizers include hindered amine light stabilizers and benzoate light stabilizers. The content ratio of the light stabilizer is preferably 2% by weight or less, more preferably 1% by weight or less, and still more preferably 0.01% by weight to 0.5% with respect to the polyester resin in the base material layer. It is weight%.

  As the filler, any suitable filler may be employed. As such a filler, inorganic fillers other than a black pigment etc. are mentioned, for example. The content ratio of the filler is preferably 20% by weight or less, more preferably 10% by weight or less, still more preferably 0.01% by weight to 10% by weight, based on the polyester resin in the base material layer. is there.

  Furthermore, as additives, for the purpose of imparting antistatic properties, surfactants, inorganic salts, polyhydric alcohols, metal compounds, inorganic antistatic agents such as carbon, low molecular weight antistatic agents, high molecular weight antistatics Agents are also mentioned.

  The base material layer can be produced by any appropriate method as long as the effects of the present invention are not impaired. For example, in a film forming apparatus having an extruder, in which a chip of a dried polyester resin, a master chip of a dried black pigment, and other additives as necessary are mixed in that the effects of the present invention are sufficiently exhibited Is fed to an extruder heated to 260 to 300 ° C., melted, introduced into a T die cap and extruded. This molten sheet is contact-cooled and solidified by static electricity on a drum cooled to a surface temperature of 10 to 60 ° C. to produce an unstretched film. The unstretched film obtained in this manner may be used as it is, or may be biaxially stretched mainly in the longitudinal direction and the transverse direction to form a sheet of the necessary optimum thickness. Stretching may be sequentially biaxial stretching, or simultaneously biaxial stretching in two directions. In addition, re-stretching may be performed in the longitudinal and / or transverse directions. In an example of sequential biaxial stretching, an unstretched film is led to a group of rolls heated to 70 to 120 ° C., stretched 2-5 times in the longitudinal direction (longitudinal direction, ie, the advancing direction of the film), and rolls of 20 to 30 ° C. Cool in groups. Subsequently, the film stretched in the longitudinal direction is guided to a tenter while being gripped with clips by a clip, and is stretched 2-5 times in a direction (lateral direction) perpendicular to the longitudinal direction in an atmosphere heated to 90 to 150 ° C. The area ratio of stretching (longitudinal stretching ratio × lateral stretching ratio) is preferably 6 to 20 times. If the area magnification is less than 6 times, the strength of the resulting film tends to be insufficient, and if it is more than 20 times, the film tends to be broken at the time of stretching. The biaxially stretched film thus obtained is uniformly annealed through a heat treatment process at 150 to 238 ° C. for 1 to 30 seconds in a tenter to complete crystal orientation and to impart planarity and dimensional stability. Thereafter, the process is cooled to room temperature to finish the winding process, and after slitting to an appropriate size, the base material layer can be obtained. In the heat treatment step, if necessary, a relaxation treatment of 3 to 12% may be performed in the lateral direction or the longitudinal direction. Moreover, also when producing the unstretched sheet close | similar to this method and simultaneously biaxially stretching, it is preferable that the area ratio of extending | stretching is 6 to 20 times. Also, after biaxial stretching, the film may be re-stretched in either or both of the longitudinal and transverse directions. In addition, it is preferable to appropriately select the stretching temperature and the magnification in accordance with the amount of the black pigment and other additives to be added to the polyester resin.

<Pressure-sensitive adhesive layer>
The pressure-sensitive adhesive layer preferably contains at least one pressure-sensitive adhesive selected from a urethane-based pressure-sensitive adhesive and an acrylic pressure-sensitive adhesive. Since the pressure-sensitive adhesive layer contains at least one kind of pressure-sensitive adhesive selected from urethane-based pressure-sensitive adhesives and acrylic pressure-sensitive adhesives, the pressure-sensitive adhesive layer has a light trigger peeling force, a light peel strength of 180 degrees and a high wetting speed. In combination with the specific base material layer adopted in the present invention, a trigger for peeling from the adherend can be easily obtained, and light peeling can be achieved. Furthermore, the detection rate of flaws and foreign matter contamination Can provide a higher surface protection film.

  The pressure-sensitive adhesive layer may be composed of a single layer or may be composed of a plurality of layers.

  The thickness of the pressure-sensitive adhesive layer may be set to any appropriate thickness depending on the application. From the viewpoint of sufficiently expressing the effects of the present invention, the thickness is preferably 5 μm to 50 μm, more preferably 6 μm to 40 μm, still more preferably 7 μm to 30 μm, and particularly preferably 8 μm to 20 μm.

  The content ratio of the pressure-sensitive adhesive in the pressure-sensitive adhesive layer is preferably 96 to 100% by weight, more preferably 97 to 100% by weight, still more preferably 98 to 100% by weight. Particularly preferably, it is 99% by weight to 100% by weight. By adjusting the content ratio of the pressure-sensitive adhesive in the pressure-sensitive adhesive layer to the above-mentioned range, the pressure-sensitive adhesive layer can be made as a pressure-sensitive peeling force is light, a 180 degree peeling force is light, and a wetting speed is fast. By combining with a specific base material layer to be adopted, a trigger for peeling from an adherend can be easily obtained, and light peeling can be provided, and further, a surface protection film having a higher detection rate of flaws and foreign matter contamination is provided. can do.

[Urethane-based adhesive]
The urethane-based pressure-sensitive adhesive contains a polyurethane-based resin.

  The lower limit of the content of the polyurethane resin in the urethane-based adhesive is preferably 40% by weight or more, more preferably 50% by weight or more, still more preferably 55% by weight or more, and further preferably 60% by weight or more, particularly preferably 65% by weight or more, most preferably 70% by weight or more, and the upper limit thereof is preferably 99.999% by weight or less, more preferably 99.99% by weight Or less, more preferably 99.9% by weight or less, still more preferably 99% by weight or less, particularly preferably 95% by weight or less, and most preferably 90% by weight or less. By adjusting the content of the polyurethane resin in the urethane adhesive within the above range, it is possible to make the pressure-sensitive adhesive layer lighter in trigger peeling force, lighter in 180 degree peel peeling force, and faster in wetting speed In combination with the specific base material layer adopted in the present invention, a trigger for peeling from the adherend is easily obtained, and light peeling is possible, and furthermore, the detection rate of scratches and foreign matter contamination is higher A surface protection film can be provided.

  The polyurethane resin may be only one kind or two or more kinds.

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

  As a polyol (A), only 1 type may be sufficient and 2 or more types may be sufficient.

  Any appropriate polyol may be adopted as the polyol (A) as long as it has two or more OH groups. As such a polyol (A), for example, a polyol (diol) having 2 OH groups, a polyol (triol) having 3 OH groups, a polyol (tetraol) having 4 OH groups, 5 OH groups The polyol (pentaol) which has individuality, the polyol (hexaol) which has six OH groups, etc. are mentioned.

  In the present invention, as the polyol (A), preferably, a polyol (triol) having 3 OH groups is adopted as an essential component. Thus, when a polyol (triol) having three OH groups is adopted as an essential component as the polyol (A), for example, the pressure-sensitive adhesive layer has a light trigger peeling force, a light 180 degree peel peeling force, and a high wetting speed. In combination with the specific base material layer adopted in the present invention, it is possible to provide a surface protection film having a higher detection rate of flaws and contamination. The content ratio of the polyol (triol) having three OH groups in the polyol (A) is preferably 50% by weight to 100% by weight, more preferably 70% by weight to 100% by weight, and still more preferably It is 80% by weight to 100% by weight, more preferably 90% by weight to 100% by weight, particularly preferably 95% by weight to 100% by weight, and most preferably substantially 100% by weight.

  The polyol (A) preferably contains a polyol having a number average molecular weight Mn of 400 to 20,000. 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% by weight to 100% by weight, more preferably 70% by weight to 100% by weight, and still more preferably It is 90 wt% to 100 wt%, particularly preferably 95 wt% to 100 wt%, and most preferably substantially 100 wt%. By adjusting the content ratio of the polyol having a number average molecular weight Mn of 400 to 20,000 in the polyol (A) within the above range, the trigger peeling power is lighter, the 180 degree peel peeling power is lighter, and the wetting speed is A faster pressure-sensitive adhesive layer can be obtained, and by combining with a specific base material layer adopted in the present invention, a trigger for peeling from an adherend can be easily obtained, and light peeling can be performed, and furthermore, a scratch It is possible to provide a surface protection film having a higher detection rate of foreign matter and contamination.

  In the present invention, when a polyol (triol) having three OH groups is adopted as an essential component as the polyol (A), preferably, a triol having a number average molecular weight Mn of 700 to 20,000 and a number average molecular weight Mn of 2,000 to More preferably, 6000 triol and triol having a number average molecular weight Mn of 400 to 1900 are used, more preferably a triol having a number average molecular weight Mn of 800 to 15000 and a triol having a number average molecular weight Mn of 2000 to 5000, More preferably, a triol having a molecular weight Mn of 500 to 1800, more 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 1,500 Use in combination with triol. When these three types of triols are used in combination, the pressure-sensitive adhesive layer can have a lighter trigger peeling force, a lighter 180 degree peel peeling force, and a faster wetting speed, and the specific substrate employed in the present invention By combining with the layer, a trigger for peeling from the adherend can be easily obtained, and it is possible to provide a surface protection film which can be lightly peeled and further has a higher detection rate of scratches and inclusion of foreign matter.

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

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

  As the polyol component, for example, ethylene glycol, diethylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2-butyl-2-ethyl-1 , 3-propanediol, 2,4-diethyl-1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 2-methyl -1,8-octanediol, 1,8-decanediol, octadecanediol, glycerin, trimethylolpropane, pentaerythritol, hexanetriol, polypropylene glycol and the like.

  Examples of the acid component include succinic acid, methyl succinic acid, adipic acid, pimelic acid, azelaic acid, sebacic acid, 1,12-dodecanedioic acid, 1,14-tetradecanedioic acid, dimer acid, 2-methyl-1, 4-cyclohexanedicarboxylic acid, 2-ethyl-1,4-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, isophthalic acid, terephthalic acid, 1,4-naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid And these acid anhydrides and the like.

  Examples of polyether polyols include water, low molecular weight polyols (such as propylene glycol, ethylene glycol, glycerin, trimethylolpropane and pentaerythritol), bisphenols (such as bisphenol A), dihydroxybenzenes (such as catechol, resorcinol and hydroquinone), etc. The polyether polyol obtained by addition-polymerizing alkylene oxides, such as ethylene oxide, a propylene oxide, a butylene oxide, as an initiator is mentioned. Specifically, for example, polyethylene glycol, polypropylene glycol, polytetramethylene glycol and the like can be mentioned.

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

  As the polycarbonate polyol, for example, a polycarbonate polyol obtained by subjecting the above-mentioned polyol component and phosgene to a polycondensation reaction; the above-mentioned polyol component and the above-mentioned polyol component, dimethyl carbonate, diethyl carbonate, diprovir carbonate, diisopropyl carbonate, dibutyl carbonate, ethyl butyl carbonate, ethylene carbonate, Polycarbonate polyols obtained by ester exchange condensation of propylene carbonate, diphenyl carbonate, diesters of carbonic acid such as dibenzyl carbonate, etc. Copolycarbonate polyols obtained by using two or more of the above-mentioned polyol components in combination; Polycarbonate polyols obtained by esterification reaction with compounds; Various polycarbonate polyols mentioned above and hydroxyl group-containing compounds Polycarbonate polyols obtained by transesterification reaction; polycarbonate polyols obtained by transesterification reaction of the above-mentioned various polycarbonate polyols and ester compounds; polycarbonate polyols obtained by transesterification reaction of the above various polycarbonate polyols and hydroxyl group-containing compounds; Examples include polyester-based polycarbonate polyols obtained by subjecting the above-described various polycarbonate polyols and dicarboxylic acid compounds to a polycondensation reaction; and copolymerized polyether-based polycarbonate polyols obtained by copolymerizing the above-mentioned various polycarbonate polyols and alkylene oxides.

  Examples of castor oil-based polyols include castor oil-based polyols obtained by reacting castor oil fatty acid with the above-mentioned polyol component. Specifically, for example, a castor oil-based polyol obtained by reacting castor oil fatty acid and polypropylene glycol can be mentioned.

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

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

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

  As a polyfunctional alicyclic isocyanate compound, for example, 1,3-cyclopentene diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, Hydrogenated tolylene diisocyanate, hydrogenated tetramethyl xylylene diisocyanate and the like can be mentioned.

  As a polyfunctional aromatic diisocyanate compound, for example, phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,2′-diphenylmethane diisocyanate, 4,4′-diphenylmethane diisocyanate, 4 4,4'-toluidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, xylylene diisocyanate and the like.

  Examples of the polyfunctional isocyanate compound (B) include trimethylolpropane adducts of various polyfunctional isocyanate compounds as described above, a biuret reacted with water, and a trimer having an isocyanurate ring. Moreover, you may use these together.

  The content of the polyfunctional isocyanate compound (B) is preferably 5% by weight to 60% by weight, and more preferably 8% by weight to 60% by weight, based on the polyol (A). %, More preferably 10% by weight to 60% by weight. By adjusting the content ratio of the polyfunctional isocyanate compound (B) within the above range, the pressure-sensitive adhesive layer can have a lighter peel force, a lighter 180 degree peel peel force, and a faster wetting speed, By combining with the specific base material layer adopted in the present invention, a trigger for peeling from the adherend can be easily obtained, and peeling can be lightly carried out, and furthermore, surface protection with a higher detection rate of scratches and foreign matter contamination A film can be provided.

  The equivalent ratio of NCO groups to OH groups in the polyol (A) and the polyfunctional isocyanate compound (B) is, as NCO group / OH group, more than 1.0 and 5.0 or less, preferably 1.1 to It is 5.0, More preferably, it is 1.2-4.0, More preferably, it is 1.5-3.5, Most preferably, it is 1.8-3.0. By adjusting the equivalent ratio of NCO group / OH group within the above range, it is possible to make the pressure-sensitive adhesive layer lighter in trigger peeling force, lighter in 180 degree peel peeling force, and faster in wetting speed. In combination with the specific base material layer adopted in the above, a trigger for peeling from the adherend can be easily obtained, and it is possible to lightly peel, and further, a surface protection film having a higher detection rate of scratches and foreign matter contamination. Can be provided.

  The polyurethane 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 other than the polyol (A) and the polyfunctional isocyanate compound (B), as long as the effects of the present invention are not impaired. As such other components, for example, catalysts, resin components other than polyurethane resins, tackifiers, inorganic fillers, organic fillers, metal powders, pigments, foils, softeners, plasticizers, Antiaging agents, conductive agents, antioxidants, ultraviolet light absorbers, light stabilizers, surface lubricants, leveling agents, corrosion inhibitors, heat resistant stabilizers, polymerization inhibitors, lubricants, solvents and the like.

  The polyurethane-based resin preferably contains an anti-deterioration agent such as an antioxidant, an ultraviolet light absorber, or a light stabilizer. Since the polyurethane resin contains the anti-deterioration agent, it is possible to be excellent in the adhesive residue prevention property, such as adhesive residue hardly occurring on the adherend even when stored in a heated state after being attached to the adherend. One type of antidegradant may be used, or two or more types may be used. An antioxidant is particularly preferably used as the antidegradant.

  The content ratio of the antidegradant is preferably 0.01% by weight to 20% by weight, more preferably 0.02% by weight to 15% by weight, more preferably 0. 1% by weight, relative to the polyol (A). It is 03 wt% to 10 wt%, more preferably 0.05 wt% to 7 wt%, still more preferably 0.1 wt% to 5 wt%, particularly preferably 0.1 wt% to 3 % By weight, most preferably 0.1% by weight to 1% by weight. By adjusting the content ratio of the deterioration preventing agent within the above range, the adhesive residue prevention property is further enhanced such that the adhesive residue is less likely to occur on the adherend even when stored in a heated state after being attached to the adherend It can become superior. When the content ratio of the deterioration inhibitor is too small, there is a possibility that the adhesive residue preventing property can not be sufficiently expressed. When the content ratio of the deterioration inhibitor is too large, there is a possibility that the problem of being disadvantageous in cost occurs, the problem that the adhesive property can not be maintained, or the problem of the contamination of the adherend may occur. .

  Examples of the antioxidant include radical chain inhibitors, peroxide decomposers and the like.

  As a radical chain inhibiting agent, a phenolic antioxidant, an amine antioxidant, etc. are mentioned, for example.

  As a peroxide decomposition agent, sulfur system antioxidant, phosphorus system antioxidant, etc. are mentioned, for example.

  As a phenolic antioxidant, a monophenol type antioxidant, a bisphenol type | system | group antioxidant, polymeric high molecular type phenol type antioxidant etc. are mentioned, for example.

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

  Examples of bisphenol-based antioxidants include 2,2′-methylenebis (4-methyl-6-t-butylphenol), 2,2′-methylenebis (4-ethyl-6-t-butylphenol), and 4,4 ′. -Thiobis (3-methyl-6-t-butylphenol), 4,4'-butylidenebis (3-methyl-6-t-butylphenol), 3,9-bis [1,1-dimethyl-2- [β- ( 3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl] 2,4,8,10-tetraoxaspiro [5,5] undecane and the like.

  Examples of high molecular weight phenolic antioxidants include 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl-2,4, 6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tetrakis- [methylene-3- (3 ′, 5′-di-tert-butyl-4′-hydroxyphenyl) propionate] methane Bis [3,3′-bis- (4′-hydroxy-3′-t-butylphenyl) butyric acid] glycol ester, 1,3,5-tris (3 ′, 5′-di-t-butyl 4'-hydroxybenzyl) -S-triazine-2,4,6- (1H, 3H, 5H) trione, tocophenol and the like.

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

  Examples of phosphorus antioxidants include triphenyl phosphite, diphenyl isodecyl phosphite, phenyl diisodecyl phosphite and the like.

  Examples of the UV absorber include benzophenone UV absorber, benzotriazole UV absorber, salicylic acid UV absorber, oxalic acid anilide UV absorber, cyanoacrylate UV absorber, triazine UV absorber and the like. Be

  As a benzophenone series ultraviolet absorber, for example, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2,2 ' -Dihydroxy-4-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone, bis (2-methoxy-4-hydroxy-5-benzoylphenyl) And methane).

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

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

  As a cyanoacrylate type ultraviolet absorber, 2-ethylhexyl 2-cyano-3,3'-diphenyl acrylate, ethyl 2-cyano-3,3'-diphenyl acrylate etc. are mentioned, for example.

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

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

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

  The antidegradant is preferably an antidegradant having a hindered phenol structure. When the deterioration inhibitor having a hindered phenol structure is included as the deterioration inhibitor, the content ratio thereof is preferably 0.01% by weight to 10% by weight, more preferably 0.05% by weight with respect to the polyol (A). % By weight to 10% by weight, more preferably 0.1% by weight to 10% by weight. By adjusting the content ratio of the antidegradant having a hindered phenol structure within the above range, adhesive residue is less likely to occur on the adherend even when stored in a heated state after being attached to the adherend And may be further improved by the adhesive residue prevention property. When the content ratio of the antidegradant having a hindered phenol structure is too small, there is a possibility that the adhesive residue preventing property can not be sufficiently expressed. If the content ratio of the antidegradant having a hindered phenol structure is too large, problems such as cost disadvantage may occur, adhesion characteristics may not be maintained, or the adherend may be contaminated. It may occur.

  As a deterioration inhibitor having a hindered phenol structure, for example, a group having a large steric hindrance such as a tertiary butyl group is bonded to at least one of adjacent carbon atoms of an aromatic ring carbon atom to which an OH group of phenol is bonded Any antidegradant may be employed as long as it is an antidegradant having a hindered phenol structure. By using a specific anti-deterioration agent such as an anti-deterioration agent having such a hindered phenol structure, it is considered that the effect of suppressing the molecular weight reduction of the polyol becomes very large compared to the prior art, and hence the adhesive residue The effect that the prevention property is remarkably excellent compared with the past can be expressed.

  Specific examples of the antidegradants having such a hindered phenol structure include, for example, dibutyl hydroxytoluene (BHT); trade name “IRGANOX 1010” (manufactured by BASF), trade name “IRGANOX 1010 FF” (manufactured by BASF), products Name "IRGANOX1035" (BASF), trade name "IRGANOX1035FF" (BASF), trade name "IRGANOX1076" (BASF), trade name "IRGANOX1076FD" (BASF), trade name "IRGANOX1076DWJ" (BASF), product name Name "IRGANOX 1098" (BASF), trade name "IRGANOX 1135" (BASF), trade name "IRGANOX 1330" (BASF), trade name "IRGANOX 1726" (BASF), Product name "IRGANOX 1425WL" (manufactured by BASF), trade name "IRGANOX 1520L" (manufactured by BASF), trade name "IRGANOX 245" (manufactured by BASF), trade name "IRGANOX245FF" (manufactured by BASF), trade name "IRGANOX 259" (manufactured by BASF), trade name Hindered phenolic antioxidants such as name “IRGANOX 3114” (manufactured by BASF), trade name “IRGANOX 565” (manufactured by BASF), trade name “IRGANOX 295” (manufactured by BASF); trade name “TINUVIN P” (manufactured by BASF), trade name Name "TINUVIN P FL" (manufactured by BASF), trade name "TINUVIN 234" (manufactured by BASF), trade name "TINUVIN 326" (manufactured by BASF), trade name "TINUVIN 326 FL" (manufactured by BASF), trade name "T Benzotriazole-based ultraviolet absorbers such as NUVIN 328 "(manufactured by BASF), trade name" TINUVIN 329 "(manufactured by BASF), trade name" TINUVIN 329 FL "(manufactured by BASF); trade name" TINUVIN 213 "(manufactured by BASF), trade name" TINUVIN 571 " Liquid ultraviolet absorbers such as BASF (trade name); triazine ultraviolet absorbers such as "TINUVIN 1577ED" (manufactured by BASF); Benzoate ultraviolet absorbers such as "TINUVIN 120" (manufactured by BASF); trade name "TINUVIN 144" Hindered amine light stabilizers such as BASF (manufactured by BASF); and the like.

  The polyurethane-based resin preferably contains a fatty acid ester. When the polyurethane resin contains a fatty acid ester, the wetting speed can be improved. The fatty acid ester may be only one kind or two or more kinds.

  The content ratio of the fatty acid ester is preferably 5% by weight to 50% by weight, more preferably 7% by weight to 40% by weight, and still more preferably 8% by weight to 35% by weight with respect to the polyol (A). Particularly preferably 9 wt% to 30 wt%, and most preferably 10 wt% to 20 wt%. By adjusting the content rate of the fatty acid ester within the above range, the wetting speed can be further improved. If the content ratio of the fatty acid ester is too small, the wetting speed may not be sufficiently improved. When the content ratio of fatty acid ester is too large, there is a possibility that a problem that is disadvantageous in cost occurs, a problem that the adhesive property can not 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 It is. By adjusting the number average molecular weight Mn of the fatty acid ester within the above range, the wetting speed can be further improved. If the number average molecular weight Mn of the fatty acid ester is too small, the wetting speed may not be improved even if the number of addition parts is large. If the number average molecular weight Mn of the fatty acid ester is too large, the curing property of the pressure-sensitive adhesive at the time of drying may be deteriorated, and there is a possibility that the adhesion property is not retained and the other adhesion properties are adversely affected.

  As a fatty acid ester, any suitable fatty acid ester can be adopted as long as the effects of the present invention are not impaired. As such fatty acid ester, for example, polyoxyethylene bisphenol A laurate, butyl stearate, 2-ethylhexyl palmitate, 2-ethylhexyl stearate, monoglyceride benylate, cetyl 2-ethylhexanoate, myristic acid Isopropyl, isopropyl palmitate, cholesteryl isostearate, lauryl methacrylate, coconut fatty acid methyl, lauryl laurate, methyl oleate, methyl stearate, myristyl myristate, octyldodecyl myristate, pentaerythritol monooleate, pentaerythritol monostearate , Pentaerythritol tetrapalmitate, stearyl stearate, isotridecyl stearate, triglycerides of 2-ethylhexanoate , Butyl laurate, and the like octyl oleate.

  The polyurethane resin preferably contains a leveling agent. By including the leveling agent in the polyurethane resin, it is possible to prevent the appearance unevenness due to the skin. The leveling agent may be only one type, or two or more types.

  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 with respect to the polyol (A). .003% by weight to 0.1% by weight, particularly preferably 0.004% by weight to 0.05% by weight, and most preferably 0.005% by weight 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 due to the skin of the eye. If the content ratio of the leveling agent is too small, it may be impossible to prevent the appearance unevenness due to the skin. When the content ratio of the leveling agent is too large, there may be a problem of being disadvantageous in cost, a problem that the adhesive property can not be maintained, or a problem that the adherend is contaminated.

  Any appropriate leveling agent may be employed as the leveling agent as long as the effects of the present invention are not impaired. As such a leveling agent, an acrylic type leveling agent, a fluorine type leveling agent, a silicon type leveling agent etc. are mentioned, for example. As the acrylic leveling agent, Polyflow No. 1 36, polyflow no. 56, Polyflow No. 85HF, polyflow no. Examples include 99C (made by Kyoeisha Chemical Co., Ltd.). As a fluorine-type leveling agent, Megafac F470N, Megafac F556 (all are products made by DIC), etc. are mentioned. As a silicon type leveling agent, Grandic PC4100 (made by DIC Corporation) etc. are mentioned.

  As a method of curing a composition containing a polyol (A) and a polyfunctional isocyanate compound (B) to obtain a polyurethane resin, the effects of the present invention, such as a urethanization reaction method using bulk polymerization or solution polymerization, etc. Any appropriate method may be adopted without loss. However, in the case of a conventional polyurethane-based resin obtained through so-called urethane prepolymer, there is a possibility that the effects of the present invention can not be exhibited, so a composition containing a polyol (A) and a polyfunctional isocyanate compound (B) The method for curing the product to obtain the polyurethane resin is preferably a method other than the method for obtaining the polyurethane resin via the urethane prepolymer.

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

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

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

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

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

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

  Examples of lead-based compounds include lead oleate, lead 2-ethylhexanoate, lead benzoate and lead naphthenate.

  Examples of cobalt-based compounds include cobalt 2-ethylhexanoate and cobalt benzoate.

  Examples of zinc-based compounds include zinc naphthenate and zinc 2-ethylhexanoate.

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

  The catalyst may be used alone or in combination of two or more. In addition, a catalyst and a crosslinking retarder may be used in combination. The amount of the catalyst is preferably 0.02 wt% to 0.10 wt%, more preferably 0.02 wt% to 0.08 wt%, further preferably 0 with respect to the polyol (A). It is from 0.22% by weight to 0.06% by weight, particularly preferably from 0.02% by weight to 0.05% by weight. By adjusting the amount of the catalyst within the above range, the pressure-sensitive adhesive layer having a light trigger peeling force, a light 180 degree peel peeling force, and a high wetting speed can be obtained, and the specific substrate layer employed in the present invention In combination with the above, it is possible to easily obtain a trigger for peeling from the adherend, to lightly peel, and to provide a surface protection film having a higher detection rate of scratches and inclusions of foreign matter.

  The urethane-based pressure-sensitive adhesive may contain an ionic liquid containing a fluoroorganic anion. When the urethane-based pressure-sensitive adhesive contains an ionic liquid containing a fluoroorganic anion, it is possible to provide a urethane-based pressure-sensitive adhesive which is very excellent in antistatic property. The ionic liquid that may be contained in the urethane-based pressure-sensitive adhesive may be only one type, or two or more types.

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

  The ionic liquid may be any suitable ionic liquid as long as it does not impair the effects of the present invention, as long as it is an ionic liquid containing a fluoroorganic anion. Such an ionic liquid is preferably an ionic liquid composed of a fluoroorganic anion and an onium cation. By employing an ionic liquid composed of a fluoroorganic anion and an onium cation as the ionic liquid, it is possible to provide a urethane-based pressure-sensitive adhesive which is extremely excellent in antistatic property.

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

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

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

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

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

  In the general formula (4), Z represents a nitrogen atom, a sulfur atom or a phosphorus atom, and R1, Rm, Rn and Ro are the same or different and each represent a hydrocarbon group having 1 to 20 carbon atoms, It may contain atoms. However, when Z is a sulfur atom, there is no Ro.

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

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

  Specific examples of the cation represented by the general formula (1) include, for example, 1-ethyl pyridinium cation, 1-butyl pyridinium cation, 1-hexyl pyridinium cation, 1-ethyl-3-methyl pyridinium cation, 1-butyl -3-methylpyridinium cation, 1-hexyl-3-methylpyridinium cation, 1-butyl-4-methylpyridinium cation, 1-octyl-4-methylpyridinium cation, 1-butyl-3,4-dimethylpyridinium cation, Pyridinium cations such as 1,1-dimethylpyrrolidinium cation; 1-ethyl-1-methylpyrrolidinium cation, 1-methyl-1-propylpyrrolidinium cation, 1-methyl-1-butylpyrrolidinium cation, 1-Methyl-1-pentyl pyrrolidini Mu-cation, 1-methyl-1-hexylpyrrolidinium cation, 1-methyl-1-heptylpyrrolidinium cation, 1-ethyl-1-propylpyrrolidinium cation, 1-ethyl-1-butylpyrrolidinium cation 1-ethyl-1-pentyl pyrrolidinium cation, 1-ethyl-1-hexyl pyrrolidinium cation, 1-ethyl-1-heptyl pyrrolidinium cation, 1,1-dipropyl pyrrolidinium cation Pyrrolidinium cations such as 1-propyl-1-butylpyrrolidinium cation, 1,1-dibutylpyrrolidinium cation; 1-propylpiperidinium cation, 1-pentylpiperidinium cation, 1-methyl-1-one Ethyl piperidinium cation, 1-methyl-1-propyl piperidinium cation 1-methyl-1-butylpiperidinium cation, 1-methyl-1-pentylpiperidinium cation, 1-methyl-1-hexyl piperidinium cation, 1-methyl-1-heptylpiperidinium cation, 1-ethyl-1-propylpiperidinium cation, 1-ethyl-1-butylpiperidinium cation, 1-ethyl-1-pentylpiperidinium cation, 1-ethyl-1-hexyl piperidinium cation, 1-ethyl-1-propylpiperidinium cation Ethyl-1-heptylpiperidinium cation, 1-propyl-1-butylpiperidinium cation, 1,1-dimethylpiperidinium cation, 1,1-dipropylpiperidinium cation, 1,1-dibutylpinium Piperidinium cations such as peridinium cation; 2-methyl-1-pyrroline cation; 1-d And the like. Ethyl 2-phenylindole cation; 1,2-dimethylindole cation; 1-ethylcarbazole cation; and the like.

  Among these, from the viewpoint that the effects of the present invention can be further developed, 1-ethylpyridinium cation, 1-butylpyridinium cation, 1-hexylpyridinium cation, 1-ethyl-3-methylpyridinium cation, 1 Pyridinium cations such as -butyl-3-methylpyridinium cation, 1-hexyl-3-methylpyridinium cation, 1-butyl-4-methylpyridinium cation, 1-octyl-4-methylpyridinium cation, etc .; Methyl pyrrolidinium cation, 1-methyl-1-propyl pyrrolidinium cation, 1-methyl-1-butyl pyrrolidinium cation, 1-methyl-1-pentyl pyrrolidinium cation, 1-methyl-1-hexyl Pyrrolidinium cation, 1-methyl-1-he Tyl pyrrolidinium cation, 1-ethyl-1-propyl pyrrolidinium cation, 1-ethyl-1-butyl pyrrolidinium cation, 1-ethyl-1-pentyl pyrrolidinium cation, 1-ethyl-1-hexyl Pyrrolidinium cation, pyrrolidinium cation such as 1-ethyl-1-heptylpyrrolidinium cation; 1-methyl-1-ethylpiperidinium cation, 1-methyl-1-propylpiperidinium cation, 1- Methyl-1-butylpiperidinium cation, 1-methyl-1-pentylpiperidinium cation, 1-methyl-1-hexyl piperidinium cation, 1-methyl-1-heptylpiperidinium cation, 1-ethyl 1-propyl piperidinium cation, 1-ethyl 1-butyl piperidinium cut 1-ethyl-1-pentylpiperidinium cation 1-ethyl-1-hexyl piperidinium cation 1-ethyl-1-heptylpiperidinium cation 1-propyl-1-butyl piperidinium cation And the like, and more preferably 1-hexylpyridinium cation, 1-ethyl-3-methylpyridinium cation, 1-butyl-3-methylpyridinium cation, 1-octyl-4-methyl Pyridinium cation, 1-methyl-1-propylpyrrolidinium cation, 1-methyl-1-propylpiperidinium cation.

  As a cation represented by General formula (2), an imidazolium cation, a tetrahydro pyrimidinium cation, a dihydro pyrimidinium cation etc. are mentioned, for example.

  Specific examples of the cation represented by the general formula (2) include, for example, 1,3-dimethylimidazolium cation, 1,3-diethylimidazolium cation, 1-ethyl-3-methylimidazolium cation, 1-butyl -3-Methylimidazolium cation, 1-hexyl-3-methylimidazolium cation, 1-octyl-3-methylimidazolium cation, 1-decyl-3-methylimidazolium cation, 1-dodecyl-3-methylimidazo Lithium cation, 1-tetradecyl-3-methylimidazolium cation, 1,2-dimethyl-3-propylimidazolium cation, 1-ethyl-2,3-dimethylimidazolium cation, 1-butyl-2,3-dimethylimidazo Lithium cation, 1-hexyl-2,3-dimethylimidazo Imidazolium cations such as lithium cations; 1,3-dimethyl-1,4,5,6-tetrahydropyrimidinium cation, 1,2,3-trimethyl-1,4,5,6-tetrahydropyrimidinium cation, 1 2,2,3,4-Tetramethyl-1,4,5,6-tetrahydropyrimidinium cation, 1,2,3,5-Tetramethyl-1,4,5,6-tetrahydropyrimidinium cation, etc. Tetrahydropyrimidinium cation; 1,3-dimethyl-1,4-dihydropyrimidinium cation, 1,3-dimethyl-1,6-dihydropyrimidinium cation, 1,2,3-trimethyl-1,4- Dihydropyrimidinium cation, 1,2,3-trimethyl-1,6-dihydropyrimidinium cation, 1,2,3,4-tetramethyl-1 4-dihydropyrimidinium cation, 1,2,3,4-tetramethyl-1,6-dihydropyrimidinium dihydropyrimidinium cation, such as cations; and the like.

  Among these, 1,3-dimethylimidazolium cation, 1,3-diethylimidazolium cation, 1-ethyl-3-methylimidazolium cation, 1 -Butyl-3-methylimidazolium cation, 1-hexyl-3-methylimidazolium cation, 1-octyl-3-methylimidazolium cation, 1-decyl-3-methylimidazolium cation, 1-dodecyl-3- And imidazolium cations such as methylimidazolium cation and 1-tetradecyl-3-methylimidazolium cation, more preferably 1-ethyl-3-methylimidazolium cation and 1-hexyl-3-methylimidazolium cation is there.

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

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

  As a cation represented by General formula (4), a tetraalkyl ammonium cation, a trialkyl sulfonium cation, a tetraalkyl phosphonium cation, a part of said alkyl group is substituted by an alkenyl group, an alkoxyl group, and also an epoxy group, for example And the like.

  Specific examples of the cation represented by the general formula (4) include, for example, tetramethyl ammonium cation, tetraethyl ammonium cation, tetrabutyl ammonium cation, tetrapentyl ammonium cation, tetrahexyl ammonium cation, tetraheptyl ammonium cation, triethyl methyl ammonium Cation, tributylethyl ammonium cation, trimethylpropyl ammonium cation, trimethyldecyl ammonium cation, N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium cation, glycidyl trimethyl ammonium cation, trimethyl sulfonium cation, triethyl sulfonium cation , Tributylsulfonium cation, trihexylsulfonium cation , Diethyl methyl sulfonium cation, dibutyl ethyl sulfonium cation, dimethyl decyl sulfonium cation, tetramethyl phosphonium cation, tetraethyl phosphonium cation, tetrabutyl phosphonium cation, tetrahexyl phosphonium cation, tetraoctyl phosphonium cation, triethyl methyl phosphonium cation, tributyl ethyl phosphonium cation, A trimethyl decyl phosphonium cation, a diallyl dimethyl ammonium cation, etc. are mentioned.

  Among these, preferred are triethyl methyl ammonium cation, tributyl ethyl ammonium cation, trimethyl decyl ammonium cation, diethyl methyl sulfonium cation, dibutyl ethyl sulfonium cation, dimethyl decyl sulfonium cation, from the viewpoint that the effects of the present invention can be further developed. Asymmetric tetraalkylammonium cations such as triethylmethylphosphonium cation, tributylethylphosphonium cation, trimethyldecylphosphonium cation, trialkylsulfonium cation, tetraalkylphosphonium cation, N, N-diethyl-N-methyl-N- (2-methoxy Ethyl) ammonium cation, glycidyl trimethyl ammonium cation, diallyl dimethyl ammonium And 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-dimethylammonium cation -N-propyl-N-hexylammonium cation, N, N-dimethyl- -Propyl-N-heptylammonium cation, N, N-dimethyl-N-butyl-N-hexylammonium cation, N, N-diethyl-N-butyl-N-heptylammonium cation, N, N-dimethyl-N-pentyl -N-hexylammonium cation, N, N-dimethyl-N, N-dihexylammonium cation, trimethylheptylammonium cation, N, N-diethyl-N-methyl-N-propylammonium cation, N, N-diethyl-N- Methyl-N-pentylammonium cation, N, N-diethyl-N-methyl-N-heptylammonium cation, N, N-diethyl-N-propyl-N-pentylammonium cation, triethylpropylammonium cation, triethylpentylammonium Cation, triethylheptyl ammonium cation, N, N-dipropyl-N-methyl-N-ethyl ammonium cation, N, N-dipropyl-N-methyl-N-pentyl ammonium cation, N, N-dipropyl-N-butyl-N -Hexyl ammonium cation, N, N-dipropyl-N, N-dihexyl ammonium cation, N, N-dibutyl-N-methyl-N-pentyl ammonium cation, N, N-dibutyl-N-methyl-N-hexyl ammonium cation And trioctylmethyl ammonium cation, N-methyl-N-ethyl-N-propyl-N-pentyl ammonium cation and the like, and more preferably trimethylpropyl ammonium cation.

  Any appropriate fluoroorganic anion may be employed as the fluoroorganic anion that can constitute the ionic liquid, as long as the effects of the present invention are not impaired. Such fluoro organic anions may be completely fluorinated (perfluorinated) or partially fluorinated.

  As such a fluoro organic anion, for example, fluorinated aryl sulfonate, perfluoro alkane sulfonate, bis (fluoro sulfonyl) imide, bis (perfluoro alkane sulfonyl) imide, cyano perfluoro alkane sulfonyl amide, bis (cyano) Perfluoroalkanesulfonyl methide, cyano-bis- (perfluoroalkanesulfonyl) methide, tris (perfluoroalkanesulfonyl) methide, trifluoroacetate, perfluoroalkylate, tris (perfluoroalkanesulfonyl) methide, (perfluoroalkane And sulfonyl) trifluoroacetamide and the like.

  Among these fluoro organic anions, more preferably perfluoro alkyl sulfonate, bis (fluoro sulfonyl) imide, bis (perfluoro alkane sulfonyl) imide, more specifically, for example, trifluoromethane sulfonate, pentafluoro ethane Sulfonate, heptafluoropropanesulfonate, nonafluorobutanesulfonate, bis (fluorosulfonyl) imide, bis (trifluoromethanesulfonyl) imide.

As a specific example of the ionic liquid which may be contained in a urethane type pressure sensitive adhesive, it may be used suitably chosen from the combination of the above-mentioned cation ingredient and the above-mentioned anion ingredient. Specific examples of such an ionic liquid include, for example, 1-hexylpyridinium bis (fluorosulfonyl) imide, 1-ethyl-3-methylpyridinium trifluoromethanesulfonate, 1-ethyl-3-methylpyridinium pentafluoroethanesulfonate, 1-ethyl-3-methylpyridinium heptafluoropropanesulfonate, 1-ethyl-3-methylpyridinium nonafluorobutanesulfonate, 1-butyl-3-methylpyridinium trifluoromethanesulfonate, 1-butyl-3-methylpyridinium bis (trifluoromethane) Sulfonyl) imide, 1-butyl-3-methylpyridinium bis (pentafluoroethanesulfonyl) imide, 1-octyl-4-methylpyridinium bis (fluorosulfonyl) imime 1,1-dimethylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-ethylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-propylpyrrolidinium bis (trifluoromethanesulfonyl) ) Imide, 1-methyl-1-propylpyrrolidinium bis (fluorosulfonyl) imide, 1-methyl-1-butylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-pentylpyrrolidinium bis ( Trifluoromethanesulfonyl) imide, 1-Methyl-1-hexylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-heptylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-ethyl-1-one Propyl piro Dinium bis (trifluoromethanesulfonyl) imide, 1-ethyl-1-butylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-ethyl-1-pentylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-ethyl-1-one Hexyl pyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-ethyl-1-heptyl pyrrolidinium bis (trifluoromethane sulfonyl) imide, 1, 1-dipropyl pyrrolidinium bis (trifluoromethane sulfonyl) imide, 1 -Propyl-1-butylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1,1-dibutylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-propylpiperidinium bis (trifluoromethanesulfonyl) Nil) imide, 1-pentylpiperidinium bis (trifluoromethanesulfonyl) imide, 1,1-dimethylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-ethylpiperidinium bis (trifluoromethanesulfonyl) Imide, 1-methyl-1-propylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-propylpiperidinium bis (fluorosulfonyl) imide, 1-methyl-1-butylpiperidinium bis (trifluoro) (Lomethanesulfonyl) imide, 1-methyl-1-pentylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-hexylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-heptylpiperi Dinium bis (trifluoromethanesulfonyl) imide, 1-ethyl-1-propylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-ethyl-1-butyl piperidinium bis (trifluoromethanesulfonyl) imide, 1-ethyl-1-one Pentylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-ethyl-1-hexylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-ethyl-1-heptylpiperidinium bis (trifluoromethanesulfonyl) imide, 1,1-dipropylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-propyl-1-butylpiperidinium bis (trifluoromethanesulfonyl) imide, 1,1-dibutylpiperidinium bis (trifluoro) Tan sulfonyl) imide, 1, 1-dimethyl pyrrolidinium bis (pentafluoro ethane sulfonyl) imide, 1-methyl 1-ethyl pyrrolidinium bis (penta fluoro ethane sulfonyl) imide, 1-methyl 1- propyl pyrrolidine Nium bis (pentafluoroethane sulfonyl) imide, 1-methyl-1-butyl pyrrolidinium bis (pentafluoro ethane sulfonyl) imide, 1-methyl-1-pentyl pyrrolidinium bis (pentafluoroethane sulfonyl) imide, 1- Methyl-1-hexylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-heptylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-propylpyrrolidinium bis ( Pentafluoroethane Lufnyl) imide, 1-ethyl-1-butylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-pentylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-hexyl Pyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-heptylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1,1-dipropylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-propyl-1-butylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1,1-dibutylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-propylpiperidinium bis (pentafluoroethanesulfonyl) imide , 1- Pentylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1,1-dimethylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-ethylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1 -Methyl-1-propylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-butylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-pentylpiperidinium bis (pentamer) Fluoroethanesulfonyl) imide, 1-methyl-1-hexylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-heptylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl- 1- Propi Piperidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-butyl piperidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-pentyl piperidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-hexylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-heptylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1,1-dipropylpiperidinium bis (Pentafluoroethanesulfonyl) imide, 1-propyl-1-butylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1,1-dibutylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-3- Methyl imidazol Mutrifluoroacetate, 1-ethyl-3-methylimidazolium heptafluorobutyrate, 1-ethyl-3-methylimidazolium trifluoromethanesulfonate, 1-ethyl-3-methylimidazolium heptafluoropropanesulfonate, 1-ethyl-3 -Methylimidazolium nonafluorobutanesulfonate, 1-ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide, 1-ethyl-3-methylimidazolium bis (fluorosulfonyl) imide, 1-ethyl-3-methylimidazo Lithium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-3-methylimidazolium tris (trifluoromethanesulfonyl) methide, 1-butyl-3-methylimidazolium trifluoroacetate 1-Butyl-3-methylimidazolium heptafluorobutyrate, 1-butyl-3-methylimidazolium trifluoromethanesulfonate, 1-butyl-3-methylimidazolium perfluorobutanesulfonate, 1-butyl-3-methyl Imidazolium bis (trifluoromethanesulfonyl) imide, 1-hexyl-3-methylimidazolium trifluoromethanesulfonate, 1-hexyl-3-methylimidazolium bis (fluorosulfonyl) imide, 1,2-dimethyl-3-propylimidazo Lithium bis (trifluoromethanesulfonyl) imide, 1-ethyl-2,3,5-trimethylpyrazolium bis (trifluoromethanesulfonyl) imide, 1-propyl-2,3,5-trimethylpyrazolium bis (trifluoro) Methanesulfonyl) imide, 1-butyl-2,3,5-trimethylpyrazolium bis (trifluoromethanesulfonyl) imide, 1-ethyl-2,3,5-trimethylpyrazolium bis (pentafluoroethanesulfonyl) imide, 1-propyl-2,3,5-trimethylpyrazolium bis (pentafluoroethanesulfonyl) imide, 1-butyl-2,3,5-trimethylpyrazolium bis (pentafluoroethanesulfonyl) imide, 1-ethyl- 2,3,5-Trimethylpyrazolium (trifluoromethanesulfonyl) trifluoroacetamide, 1-propyl-2,3,5-trimethylpyrazolium (trifluoromethanesulfonyl) trifluoroacetamide, 1-butyl-2,3, 5-trimethyl pyrazolium (trifluoro Tansulfonylyl) trifluoroacetamide, trimethylpropylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-ethyl-N-propylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-ethyl- N-Butylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-ethyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-ethyl-N-hexylammonium bis ( Trifluoromethanesulfonyl) imide, N, N-Dimethyl-N-ethyl-N-heptylammonium bis (trifluoromethanesulfonyl) imide, N, N-Dimethyl-N-ethyl-N-nonylammonium bis (Tri Fluoromethanesulfonyl) imide, N, N-dimethyl-N, N-dipropylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-propyl-N-butylammonium bis (trifluoromethanesulfonyl) imide, N N, N-Dimethyl-N-propyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-propyl-N-hexylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N -Propyl-N-heptylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-butyl-N-hexylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-butyl-N-heptylaryl Monium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N-pentyl-N-hexylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl-N, N-dihexylammonium bis (trifluoromethanesulfonyl) imide, Trimethylheptylammonium bis (trifluoromethanesulfonyl) imide, N, N-diethyl-N-methyl-N-propylammonium bis (trifluoromethanesulfonyl) imide, N, N-diethyl-N-methyl-N-pentylammonium bis (trifluoro) Lomethanesulfonyl) imide, N, N-diethyl-N-methyl-N, N-heptylammonium bis (trifluoromethanesulfonyl) imide, N, N-diethyl-N-propyl-N-pentylamine Aluminum bis (trifluoromethanesulfonyl) imide, triethylpropylammonium bis (trifluoromethanesulfonyl) imide, triethylpentylammonium bis (trifluoromethanesulfonyl) imide, triethylheptylammonium bis (trifluoromethanesulfonyl) imide, N, N-dipropyl-N-methyl -N-ethylammonium bis (trifluoromethanesulfonyl) imide, N, N-dipropyl-N-methyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, N, N-dipropyl-N-butyl-N-hexylammonium bis (Trifluoromethanesulfonyl) imide, N, N-dipropyl-N, N-dihexylammonium bis (trifluoromethanesulfonyl) imide, N , N-dibutyl-N-methyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, N, N-dibutyl-N-methyl-N-hexylammonium bis (trifluoromethanesulfonyl) imide, trioctylmethylammonium bis ( Trifluoromethanesulfonyl) imide, N-methyl-N-ethyl-N-propyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, 1-butylpyridinium (trifluoromethanesulfonyl) trifluoroacetamide, 1-butyl-3-methyl Pyridinium (trifluoromethanesulfonyl) trifluoroacetamide, 1-ethyl-3-methylimidazolium (trifluoromethanesulfonyl) trifluoroacetamide, tetrahexyl ammonium Di (trifluoromethanesulfonyl) imide, diallyldimethylammonium trifluoromethanesulfonate, diallyldimethylammonium bis (trifluoromethanesulfonyl) imide, diallyldimethylammonium bis (pentafluoroethanesulfonyl) imide, N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium trifluoromethanesulfonate, N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium bis (trifluoromethanesulfonyl) imide, N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium bis (pentafluoroethane sulfonyl) imide, glycidyl trimethyl ammonium trifluoromethane sulfonate, glycidyl trimethyl ammonium Aluminum bis (trifluoromethane sulfonyl) imide, glycidyl trimethyl ammonium bis (pentafluoro ethane sulfonyl) imide, diallyl dimethyl ammonium bis (trifluoro methane sulfonyl) imide, diallyl dimethyl bis (penta fluoro ethane sulfonyl) imide, lithium bis (trifluoro methane sulfonyl) Imide, lithium bis (fluorosulfonyl) imide and the like can be mentioned.

  Among these ionic liquids, more preferably 1-hexyl pyridinium bis (fluorosulfonyl) imide, 1-ethyl-3-methyl pyridinium trifluoromethane sulfonate, 1-ethyl 3-methyl pyridinium pentafluoroethane sulfonate, 1- Ethyl-3-methylpyridinium heptafluoropropanesulfonate, 1-ethyl-3-methylpyridinium nonafluorobutanesulfonate, 1-butyl-3-methylpyridinium trifluoromethanesulfonate, 1-butyl-3-methylpyridinium bis (trifluoromethanesulfonyl) Imide, 1-octyl-4-methylpyridinium bis (fluorosulfonyl) imide, 1-methyl-1-propylpyrrolidinium bis (trifluoromethanesulfonyl) imime 1-methyl-1-propylpyrrolidinium bis (fluorosulfonyl) imide, 1-methyl-1-propylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-propylpiperidinium bis (fluorosulfonyl) ) Imide, 1-ethyl-3-methylimidazolium trifluoromethanesulfonate, 1-ethyl-3-methylimidazolium heptafluoropropanesulfonate, 1-ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide, 1-ethyl -3-Methylimidazolium bis (fluorosulfonyl) imide, 1-hexyl-3-methylimidazolium bis (fluorosulfonyl) imide, trimethylpropylammonium bis (trifluoromethanesulfonyl) imide, Chiumubisu (trifluoromethanesulfonyl) imide, lithium bis (fluorosulfonyl) imide.

  Although an ionic liquid may use a commercially available thing, it is also possible to synthesize | combine as follows. The method of synthesizing the ionic liquid is not particularly limited as long as the target ionic liquid can be obtained, but generally, the document "ionic liquid-forefront of development and future-" (CMC Publishing Co., Ltd. The halide method, the hydroxide method, the acid ester method, the complex formation method, the neutralization method and the like as described in the publication) are used.

  In the following, regarding the halide method, the hydroxide method, the acid ester method, the complex formation method, and the neutralization method, the synthesis method is described using a nitrogen-containing onium salt as an example, but other sulfur-containing onium salts, phosphorus-containing onium salts And other ionic liquids can be obtained by the same method.

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

Resulting anion structure of an objective ionic liquid halide (A ^-) acid (HA) or a salt with (MA, M is a cation which forms ammonium, lithium, sodium, a salt with an objective anion such as potassium ) To obtain the target ionic liquid (R ₄ NA).

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

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

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

The target ionic liquid (R ₄ NA) can be obtained by using the reactions of reaction formulas (10) to (11) in the same manner as the above-mentioned halogenation method for the obtained acid ester. In addition, it is also possible to obtain an ionic liquid directly by using methyl trifluoromethanesulfonate, methyl trifluoroacetate or the like as an acid ester.

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

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

  The compounding amount of the ionic liquid can not be uniquely defined because it changes depending on the compatibility of the polymer to be used and the ionic liquid, but generally it is preferably 0. 0 to 100 parts by weight of the polyurethane resin. It is 001 parts by weight to 50 parts by weight, more preferably 0.01 parts by weight to 40 parts by weight, still more preferably 0.01 parts by weight to 30 parts by weight, particularly preferably 0.01 parts by weight to 20 parts by weight Parts by weight, most preferably 0.01 parts by weight to 10 parts by weight. By adjusting the compounding amount of the ionic liquid within the above range, it is possible to provide a urethane-based pressure-sensitive adhesive which is very excellent in antistatic property. If the amount of the ionic liquid is less than 0.01 parts by weight, sufficient antistatic properties may not be obtained. When the amount of the ionic liquid exceeds 50 parts by weight, the contamination of the adherend tends to increase.

  The urethane-based pressure-sensitive adhesive may contain, in addition to the polyurethane-based resin and the ionic liquid as described above, any other appropriate components as long as the effects of the present invention are not impaired. As such other components, for example, resin components other than polyurethane resins, tackifiers, inorganic fillers, organic fillers, metal powders, pigments, foils, softeners, plasticizers, antiaging Agents, conductive agents, ultraviolet light absorbers, antioxidants, light stabilizers, surface lubricants, leveling agents, corrosion inhibitors, heat resistant stabilizers, polymerization inhibitors, lubricants, solvents and the like.

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

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

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

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

  The polyether-modified silicone oil may, for example, be a side-chain polyether-modified silicone oil or a both-end-type polyether-modified silicone oil. Among these, a polyether modified silicone oil of both ends is preferred in that the effects of the present invention can be sufficiently sufficiently exhibited.

[Acrylic adhesive]
An acrylic adhesive contains an acrylic polymer.

  The lower limit of the content of the acrylic polymer in the acrylic pressure-sensitive adhesive is preferably 40% by weight or more, more preferably 50% by weight or more, still more preferably 55% by weight or more, and further preferably It is 60% by weight, particularly preferably 65% by weight, most preferably 70% by weight, and the upper limit thereof is preferably 99.999% by weight or less, more preferably 99.99% by weight or less It is more preferably 99.9% by weight or less, still more preferably 99% by weight or less, particularly preferably 95% by weight or less, and most preferably 90% by weight or less. By adjusting the content ratio of the acrylic polymer in the acrylic pressure-sensitive adhesive within the above range, the pressure-sensitive adhesive layer may have a lighter trigger peeling force, a lighter 180 degree peel peeling force, and a faster wetting speed. In combination with the specific base material layer adopted in the present invention, a trigger for peeling from the adherend is easily obtained, and light peeling is possible, and furthermore, the detection rate of scratches and foreign matter contamination is higher A surface protection film can be provided.

  The acrylic polymer is a polymer containing an acrylic monomer (a monomer having a (meth) acryloyl group in the molecule) as a constituent monomer component.

  The acrylic polymer may be only one type or two or more types. The acrylic monomer may be only one kind or two or more kinds.

  The acrylic polymer preferably contains (meth) acrylic acid alkyl ester as a monomer component constituting the polymer. Examples of (meth) acrylic acid alkyl esters include hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, n-nonyl (meth) acrylate and isononyl (Meth) acrylate, n-decyl (meth) acrylate, isodecyl (meth) acrylate, n-dodecyl (meth) acrylate, n-tridecyl (meth) acrylate, n-tetradecyl (meth) acrylate, etc. having 6 to 14 carbon atoms The (meth) acrylic acid alkyl ester which has an alkyl group is mentioned. Among these, (meth) acrylic acid alkyl ester having an alkyl group having 7 to 13 carbon atoms is preferable, more preferably 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, n-decyl (meth) acrylate, isodecyl (meth) acrylate, n-dodecyl (meth) acrylate, n-tridecyl (meth) acrylate. The (meth) acrylic acid alkyl ester may be used alone or in combination of two or more.

  The content ratio of the (meth) acrylic acid alkyl ester to the total monomer components (100% by weight) constituting the acrylic polymer is preferably 70% by weight to 98% by weight, more preferably 80% by weight to 98% by weight More preferably, it is 85 wt% to 98 wt%, and particularly preferably 90 wt% to 98 wt%. By adjusting the content ratio of (meth) acrylic acid alkyl ester to the total monomer component (100% by weight) constituting the acrylic polymer within the above range, the trigger peeling force is lighter and the 180 degree peel peeling force is more The pressure-sensitive adhesive layer can be light and has a faster wetting speed, and when it is combined with the specific base material layer adopted in the present invention, a trigger for peeling from an adherend can be easily obtained, and light peeling can be obtained. Further, it is possible to provide a surface protection film having a higher detection rate of scratches and foreign matter contamination.

  The monomer component constituting the acrylic polymer preferably further contains a hydroxyl group-containing monomer. Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl ( Meta) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxy lauryl (meth) acrylate, (4-hydroxymethylcyclohexyl) methyl acrylate, N-methylol (meth) acrylamide, vinyl alcohol, allyl alcohol, 2- Hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol monovinyl ether and the like can be mentioned. The hydroxyl group-containing monomer may be only one type or two or more types.

  The content ratio of the hydroxyl group-containing monomer to the total monomer components (100% by weight) constituting the acrylic polymer is preferably 0.1% by weight to 15% by weight, more preferably 0.5% by weight to 13% by weight More preferably, it is 2 wt% to 10 wt%, and particularly preferably 3 wt% to 8 wt%. By adjusting the content ratio of the hydroxyl group-containing monomer to the total monomer component (100% by weight) constituting the acrylic polymer within the above range, the crosslinking point is formed and the cohesive force is obtained, so that the trigger peeling force is more A pressure-sensitive adhesive layer that is lighter, has a lighter 180 degree peel force, and has a faster wetting speed, and when combined with the specific base material layer adopted in the present invention, facilitates the trigger for peeling from the adherend Thus, it is possible to provide a surface protection film which can be lightly peeled, can be lightly peeled, and can have a higher detection rate of flaws and contamination.

  The monomer component constituting the acrylic polymer may contain, for example, a polyfunctional monomer from the viewpoint of being able to introduce a crosslinked structure into the acrylic polymer and obtaining an appropriate cohesive force.

  As polyfunctional monomers, for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6 hexanediol di (meth) acrylate 2.) Acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, divinylbenzene, N, N'-methylenebisacrylamide and the like. The polyfunctional monomer may be only one kind or two or more kinds.

  The content ratio of the polyfunctional monomer to the total monomer component (100% by weight) constituting the acrylic polymer is preferably 0.1% by weight to 30% by weight, more preferably 0.1% by weight to 10% by weight is there. By adjusting the content ratio of the polyfunctional monomer to the total monomer component (100% by weight) constituting the acrylic polymer within the above range, the crosslinking point is formed and the cohesive force is obtained, so the trigger peeling force is lighter. The pressure-sensitive adhesive layer can have a lighter peel strength of 180 degrees and a faster wetting speed, and when combined with the specific base material layer adopted in the present invention, the trigger for peeling from the adherend can be easily made. It is possible to provide a surface protection film which is obtained, which can be lightly peeled, and which further has a higher detection rate of scratches and contamination.

  The monomer component constituting the acrylic polymer may contain an alkylene oxide group-containing reactive monomer. The alkylene oxide group-containing reactive monomer may be only one type or two or more types.

  The average addition mole number of the oxyalkylene unit of the alkylene oxide group-containing reactive monomer is preferably 3 to 40, more preferably 4 from the viewpoint of compatibility with the surfactant when the surfactant is used. It is -35, More preferably, it is 5-30. The contamination reduction effect of the to-be-protected body by surfactant use may be efficiently obtained by adjusting the average added mole number of the oxyalkylene unit of an alkylene oxide group containing reactive monomer in the said range. The end of the oxyalkylene chain may be a hydroxyl group or may be substituted by another functional group or the like.

  The content ratio of the alkylene oxide group-containing reactive monomer to the total monomer component (100% by weight) constituting the acrylic polymer is preferably 10% by weight or less, more preferably 7% by weight or less, and further preferably 5 It is at most weight%, particularly preferably at most 3 weight%, most preferably at most 1 weight%. By adjusting the content ratio of the alkylene oxide group-containing reactive monomer to the total monomer component (100% by weight) constituting the acrylic polymer within the above range, the contamination reduction effect of the substance to be protected by the use of the surfactant is efficiently performed. It can be obtained.

  Preferred examples of the oxyalkylene unit of the alkylene oxide group-containing reactive monomer include those having an alkylene group having 1 to 6 carbon atoms, and examples thereof include an oxymethylene group, an oxyethylene group, an oxypropylene group, an oxybutylene group and the like. Can be mentioned. The hydrocarbon group of the oxyalkylene chain may be linear or branched.

  The alkylene oxide group-containing reactive monomer is preferably, for example, a reactive monomer having an ethylene oxide group. By using an acrylic polymer having a reactive monomer having an ethylene oxide group as a component, the compatibility between the acrylic polymer and the surfactant is improved, bleeding to an adherend is suitably suppressed, and contamination resistance is low. Acrylic pressure-sensitive adhesives can be obtained.

  Examples of the alkylene oxide group-containing reactive monomer include (meth) acrylic acid alkylene oxide adducts; reactive surfactants having reactive substituents such as acryloyl group, methacryloyl group and allyl group in the molecule; Be

  Examples of (meth) acrylic acid alkylene oxide adducts include polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, polyethylene glycol-polypropylene glycol (meth) acrylate, polyethylene glycol-polybutylene glycol (meth) acrylate, and polypropylene Glycol-polybutylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, ethoxy polyethylene glycol (meth) acrylate, butoxy polyethylene glycol (meth) acrylate, octoxy polyethylene glycol (meth) acrylate, lauroxy polyethylene glycol (meth) Acrylate, stearoxy polyethylene glycol (meth) acid Relate, phenoxy polyethylene glycol (meth) acrylate, methoxy polypropylene glycol (meth) acrylate, octoxypolyethylene glycol - polypropylene glycol (meth) acrylate.

  As a reactive surfactant as the alkylene oxide group-containing reactive monomer, for example, an anionic reactive surfactant having a (meth) acryloyl group or an allyl group, a nonionic reactive surfactant, a cationic reactive surfactant An activator etc. are mentioned.

  Examples of the anionic reactive surfactant include those represented by Formula (A1) to Formula (A10).

R ¹ in the formula (A1) represents hydrogen or a methyl group, R ² represents a hydrocarbon group having 1 to 30 carbon atoms or an acyl group, X represents an anionic hydrophilic group, and R ³ and R ⁴ are the same. Alternatively, it represents an alkylene group having 1 to 6 carbon atoms, and the average addition mole number m and n is 0 to 40, provided that (m + n) is a number of 3 to 40.

R ¹ in formula (A2) represents hydrogen or a methyl group, R ² and R ⁷ are the same or different, each represent an alkylene group having 1 to 6 carbon atoms, and R ³ and R ⁵ are the same or different, hydrogen Or an alkyl group, R ⁴ and R ⁶ are the same or different and each represents hydrogen, an alkyl group, a benzyl group or a styrene group, X represents an anionic hydrophilic group, and the average addition mole number m and n is 0 to 40 However, (m + n) represents the number of 3-40.

R ¹ in the formula (A3) represents hydrogen or a methyl group, R ² represents an alkylene group having 1 to 6 carbon atoms, X represents an anionic hydrophilic group, and the average addition mole number n is a number of 3 to 40 Represents

R ¹ in the formula (A4) represents hydrogen or a methyl group, R ² represents a hydrocarbon group having 1 to 30 carbon atoms or an acyl group, R ³ and R ⁴ are the same or different, and have 1 to 6 carbon atoms And X represents an anionic hydrophilic group, and the average addition mole number m and n are 0 to 40, provided that (m + n) is a number of 3 to 40.

R ¹ in the formula (A5) represents a hydrocarbon group, an amino group or a carboxylic acid residue, R ² represents an alkylene group having 1 to 6 carbon atoms, and X represents an anionic hydrophilic group, and the average addition mole number n represents a number of 3 to 40.

R ¹ in the formula (A6) represents a hydrocarbon group having 1 to 30 carbon atoms, R ² represents hydrogen or a hydrocarbon group having 1 to 30 carbon atoms, R ³ represents hydrogen or a propenyl group, and R ⁴ represents carbon Represents an alkylene group of the number 1 to 6, X represents an anionic hydrophilic group, and the average addition mole number n represents a number of 3 to 40.

R ¹ in the formula (A7) represents hydrogen or a methyl group, R ² and R ⁴ are the same or different, each represent an alkylene group having 1 to 6 carbon atoms, and R ³ represents a hydrocarbon group having 1 to 30 carbon atoms M represents hydrogen, an alkali metal, an ammonium group, or an alkanol ammonium group, and the average addition mole number m and n represent 0 to 40, provided that (m + n) represents a number of 3 to 40.

R ¹ and R ⁵ in the formula (A8) are the same or different and each represents a hydrogen or methyl group, R ² and R ⁴ are the same or different, each represents an alkylene group having 1 to 6 carbon atoms, and R ³ is a carbon M represents a hydrogen, an alkali metal, an ammonium group, or an alkanol ammonium group, and the average addition mole number m and n is 0 to 40, provided that (m + n) is a number of 3 to 40. Represents

R ¹ in the formula (A9) represents an alkylene group having 1 to 6 carbon atoms, R ² represents a hydrocarbon group having 1 to 30 carbon atoms, and M represents hydrogen, an alkali metal, an ammonium group or an alkanol ammonium group And the average added mole number n represents a number of 3 to 40.

R ¹ , R ² and R ³ in the formula (A10) are the same or different and each represents hydrogen or a methyl group, R ⁴ is a hydrocarbon group having 0 to 30 carbon atoms (in the case of 0 carbon atoms, R ⁴ is R ⁵ and R ⁶ are the same or different and each represents an alkylene group having 1 to 6 carbon atoms, X represents an anionic hydrophilic group, and the average addition mole number m and n is 0 to 40. However, (m + n) represents the number of 3-40.

  X in Formula (A1)-Formula (A6) and Formula (A10)-Formula (A10) represents an anionic hydrophilic group. As an anionic hydrophilic group, what is represented by Formula (a1)-Formula (a2) is mentioned.

M ¹ in the formula (a1) represents hydrogen, an alkali metal, an ammonium group or an alkanolammonium group.

M ² and M ³ in the formula (a2) are the same or different and each represents hydrogen, an alkali metal, an ammonium group or an alkanolammonium group.

  Examples of nonionic reactive surfactants include those represented by formulas (N1) to (N6).

R ¹ in formula (N1) represents hydrogen or a methyl group, R ² represents a hydrocarbon group having 1 to 30 carbon atoms or an acyl group, R ³ and R ⁴ are the same or different, and have 1 to 6 carbon atoms And the average addition mole number m and n is 0 to 40, provided that (m + n) is a number of 3 to 40.

R ¹ in the formula (N2) represents hydrogen or a methyl group, R ² , R ³ and R ⁴ are the same or different and each represents an alkylene group having 1 to 6 carbon atoms, and the average addition mole number n, m, and l is 0-40, and represents the number used as (n + m + 1) becoming 3-40.

R ¹ in the formula (N3) represents hydrogen or a methyl group, R ² and R ³ are the same or different, each represent an alkylene group having 1 to 6 carbon atoms, and R ⁴ represents a hydrocarbon group having 1 to 30 carbon atoms Or an acyl group, and the average added number of moles m and n is 0 to 40, provided that (m + n) is a number of 3 to 40.

R ¹ and R ² in the formula (N4) are the same or different and each represent a hydrocarbon group having 1 to 30 carbon atoms, R ³ represents hydrogen or a propenyl group, and R ⁴ is an alkylene group having 1 to 6 carbon atoms And the average added mole number n represents a number of 3 to 40.

R ¹ and R ³ in the formula (N5) are the same or different and each represent an alkylene group having 1 to 6 carbon atoms, and R ² and R ⁴ are the same or different and each is a hydrogen or hydrocarbon group having 1 to 30 carbon atoms Or an acyl group, and the average added number of moles m and n is 0 to 40, provided that (m + n) is a number of 3 to 40.

R ¹ , R ² and R ³ in the formula (N6) are the same or different and each represents a hydrogen or methyl group, R ⁴ is a hydrocarbon group having 0 to 30 carbon atoms (in the case of 0 carbon atoms, R ⁴ is absent) And R ⁵ and R ⁶ are the same or different and each represents an alkylene group having 1 to 6 carbon atoms, and the average addition mole number m and n is 0 to 40, provided that (m + n) is 3 to 40. Represents a number.

  As the alkylene oxide group-containing reactive monomer, for example, Blenmer PME-400, Blenmer PME-1000, Blenmer 50 POEP-800B (all of which are manufactured by NOF Corporation), Latemle PD-420, Latemle PD-430 (all of which are described above) You may use commercial products, such as Kao Corporation make, Adekaria soap ER-10, Adekaria soap NE-10 (all, all are Asahi Denka Kogyo Co., Ltd. make).

  The monomer component constituting the acrylic polymer may contain monomers (other monomers) other than (meth) acrylic acid alkyl ester, hydroxyl group-containing monomer, polyfunctional monomer, and alkylene oxide group-containing reactive monomer . As other monomers, for example, cyano group-containing monomer, vinyl ester monomer, aromatic vinyl monomer, amide group-containing monomer, imide group-containing monomer, amino group-containing monomer, epoxy group-containing monomer, vinyl ether monomer, N-acryloyl morpholine, etc. Can be mentioned. Among these, cyano group-containing monomers, vinyl ester monomers, and aromatic vinyl monomers are preferable from the viewpoint of improving cohesive strength and heat resistance. From the viewpoint of improving adhesion and having a functional group acting as a crosslinking point, amide group-containing monomers, imide group-containing monomers, amino group-containing monomers, epoxy group-containing monomers, vinyl ether monomers, and N-acryloyl morpholine are preferable. The other monomers may be only one type or two or more types.

  Examples of cyano group-containing monomers include acrylonitrile and methacrylonitrile.

  Examples of vinyl ester monomers include vinyl esters such as vinyl acetate, vinyl propionate and vinyl laurate.

  Examples of the aromatic vinyl monomer include styrene, chlorostyrene, chloromethylstyrene, α-methylstyrene, and other substituted styrenes.

  Examples of the amide group-containing monomer include acrylamide, methacrylamide, diethyl acrylamide, N-vinyl pyrrolidone, N, N-dimethyl acrylamide, N, N-dimethyl methacrylamide, N, N-diethyl acrylamide, N, N-diethyl methacryl Amide, N, N'-methylenebisacrylamide, N, N-dimethylaminopropyl acrylamide, N, N-dimethylaminopropyl methacrylamide, diacetone acrylamide and the like can be mentioned.

  Examples of the imide group-containing monomer include cyclohexyl maleimide, isopropyl maleimide, N-cyclohexyl maleimide, itaconimide and the like.

  Examples of the amino group-containing monomer include aminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, and N, N-dimethylaminopropyl (meth) acrylate.

  Examples of the epoxy group-containing monomer include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, allyl glycidyl ether and the like.

  Examples of vinyl ether monomers include methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether and the like.

  The content ratio of the other monomer to the total monomer component (100% by weight) constituting the acrylic polymer is preferably 0 to 40% by weight, more preferably more than 0% by weight and 40% by weight or less. Is more than 0% by weight and not more than 35% by weight, particularly preferably more than 0% by weight and not more than 30% by weight.

  The monomer component constituting the acrylic polymer includes a carboxyl group-containing monomer, a sulfo group-containing monomer, a phosphoric acid group-containing monomer, and an acid anhydride group-containing monomer from the viewpoint of suppressing the increase in adhesion to the adherend. Preferably not. That is, it is preferable that the other monomers do not include a carboxyl group-containing monomer, a sulfo group-containing monomer, a phosphoric acid group-containing monomer, and an acid anhydride group-containing monomer.

  An acrylic polymer can be obtained by polymerizing the monomer component which comprises this acrylic polymer. Examples of the polymerization method include solution polymerization, emulsion polymerization, bulk polymerization, suspension polymerization, photopolymerization (active energy ray polymerization) and the like. Among these, solution polymerization is preferable from the viewpoint of cost and productivity. The resulting acrylic polymer may be any of random copolymer, block copolymer, alternating copolymer, graft copolymer and the like.

  Examples of the method of solution polymerization include a method of dissolving a monomer component, a polymerization initiator and the like in a solvent and heating to polymerize to obtain an acrylic polymer solution containing an acrylic polymer.

  Various common solvents can be used as a solvent used for solution polymerization. Such solvents include, for example, aromatic hydrocarbons such as toluene, benzene and xylene; esters such as ethyl acetate and n-butyl acetate; aliphatic hydrocarbons such as n-hexane and n-heptane; cyclohexane And organic solvents such as alicyclic hydrocarbons such as methylcyclohexane; ketones such as methyl ethyl ketone and methyl isobutyl ketone; and the like. The solvent may be only one type, or two or more types.

  The compounding ratio of the solvent is, for example, preferably 10 parts by weight to 1000 parts by weight, more preferably 50 parts by weight to 500 parts by weight with respect to the total amount (100 parts by weight) of monomer components constituting the acrylic polymer. .

  As a polymerization initiator used for solution polymerization, a peroxide type polymerization initiator, an azo type polymerization initiator etc. are mentioned, for example. Examples of peroxide type polymerization initiators include peroxy carbonate, ketone peroxide, peroxy ketal, hydroperoxide, dialkyl peroxide, diacyl peroxide, peroxy ester and the like, and more specifically, Benzoyl peroxide, t-butyl hydroperoxide, di-t-butyl peroxide, t-butyl peroxybenzoate, dicumyl peroxide, 1,1-bis (t-butyl peroxy) -3,3,5- Trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclododecane and the like can be mentioned. As the azo polymerization initiator, for example, 2,2'-azobisisobutyronitrile, 2,2'-azobis-2-methylbutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile) ), 2,2′-azobis (2-methylpropionic acid) dimethyl, 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 1,1′-azobis (cyclohexane-1-carbonitrile) ), 2,2′-azobis (2,4,4-trimethylpentane), 4,4′-azobis-4-cyanovaleric acid, 2,2′-azobis (2-amidinopropane) dihydrochloride, 2,2 '-Azobis [2- (5-methyl-2-imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobis (2-methylpropionamidine) disulfate 2,2'-azobis (N, N'-dimethylene isobutyl amidine) hydrochloride, 2,2'-azobis etc. [N-(2-carboxyethyl) -2-methylpropionamidine] hydrate and the like. The polymerization initiator may be only one type, or two or more types.

  The blending ratio of the polymerization initiator is, for example, preferably 0.01 parts by weight to 5 parts by weight, more preferably 0.05 parts by weight, with respect to the total amount (100 parts by weight) of the monomer components constituting the acrylic polymer. ~ 3 parts by weight.

  In solution polymerization, as heating temperature at the time of heating and polymerizing, 50 degreeC-80 degreeC is mentioned, for example. As heating time, 1 hour-24 hours are mentioned, for example.

  The weight average molecular weight of the acrylic polymer is preferably 100,000 to 5,000,000, more preferably 200,000 to 4,000,000, and still more preferably 300,000 to 3,000,000. By adjusting the weight-average molecular weight of the acrylic polymer within the above range, the pressure-sensitive adhesive layer can be made to have a lighter trigger peeling force, a lighter 180 degree peel peeling force, and a faster wetting speed. In combination with the specific base material layer adopted in the above, a trigger for peeling from the adherend can be easily obtained, and it is possible to lightly peel, and further, a surface protection film having a higher detection rate of scratches and foreign matter contamination. Can be provided. If the weight average molecular weight is less than 100,000, the cohesion may be small, and adhesive residue is generated on the adherend surface after peeling off the surface protective film of the present invention, and the adherend surface after peeling off There is a possibility that the effect of uniform wettability and adhesiveness can not be obtained. When the weight average molecular weight exceeds 5,000,000, the wettability of the surface of the adherend after peeling off the surface protective film of the present invention may be insufficient.

  The glass transition temperature (Tg) of the acrylic polymer is preferably 0 ° C. or less, more preferably −10 ° C. or less. By adjusting the glass transition temperature of the acrylic polymer within the above range, it is possible to make the pressure-sensitive adhesive layer lighter in trigger peeling force, lighter in 180 degree peel peeling force, and faster in wetting speed. In combination with the specific base material layer adopted in the above, a trigger for peeling from the adherend can be easily obtained, and it is possible to lightly peel, and further, a surface protection film having a higher detection rate of scratches and foreign matter contamination. Can be provided. When the glass transition temperature is higher than 0 ° C., the wettability of the surface of the adherend after peeling the surface protective film of the present invention may be insufficient. The glass transition temperature of the acrylic polymer can be adjusted by changing the composition ratio of the monomer components constituting the acrylic polymer.

  The glass transition temperature (Tg) can be determined by the following equation, where Tgn (° C.) is the glass transition temperature of the homopolymer obtained from each monomer.

  1 / (Tg + 273) =. SIGMA. [Wn / (Tgn + 273)]

  In the formula, Tg (° C) is the glass transition temperature of the copolymer, Wn (-) is the weight fraction of each monomer, Tgn (° C) is the glass transition temperature of the homopolymer obtained from each monomer, and n is each Represents the type.

The acid value of the acrylic polymer is preferably 15 or less. The acid value is measured using an automatic titrator (manufactured by Hiranuma Sangyo Co., Ltd., COM-550), and can be calculated by the following equation.
A = {(Y−X) × f × 5.611} / M
A: Acid value Y: Titration of sample solution (ml)
X: Titrate (ml) of a solution of only 50 g of mixed solvent
f: Factor M of titration solution: Weight of polymer sample (g)
The measurement conditions are as follows.
Sample solution: About 0.5 g of a polymer sample was dissolved in 50 g of a mixed solvent (toluene / 2-propanol / distilled water = 50 / 49.5 / 0.5, weight ratio) to prepare a sample solution.
Titration solution: 0.1 N, 2-propanol potassium hydroxide solution (manufactured by Wako Pure Chemical Industries, for petroleum product neutralization value test)
Electrode: Glass electrode; GE-101, comparative electrode; RE-201
Measurement mode: Petroleum product neutralization number test 1

  The acrylic pressure-sensitive adhesive may contain a surfactant from the viewpoint of further improving the wettability of the surface protection film of the present invention.

  As a surfactant, for example, polyoxyalkylene fatty acid esters, polyoxyalkylene sorbitan fatty acid esters, polyoxyalkylene sorbitol fatty acid esters, polyoxyalkylene alkyl ethers, polyoxyalkylene alkyl allyl ethers, polyoxyalkylene alkyl Nonionic surfactants such as phenyl ethers, polyoxyalkylene derivatives, polyoxyalkylene alkylamines, polyoxyalkylene alkylamine fatty acid esters, sulfonates such as sodium alkylbenzene sulfonate, alkyl sulfates such as sodium lauryl sulfate Salts, dialkylaryl sulfonates, sulfosuccinates such as dialkylsulfosuccinic acid alkali metal salts, higher fatty acid alkali metal salts, poly Anionic surfactants such as xyalkylene alkyl ether sulfuric acid ester salts, polyoxyalkylene alkyl ether phosphoric acid ester salts, polyoxyalkylene alkyl phenyl ether sulfuric acid ester salts, polyoxyalkylene alkyl phenyl ether phosphoric acid ester salts, alkylene oxide groups And cationic surfactants and amphoteric surfactants. The molecule may have a reactive substituent such as (meth) acryloyl group or allyl group. The surfactant may be used alone or in combination of two or more.

  As the surfactant, anionic surfactants are preferable in that they can sufficiently exhibit the effects of the present invention. As an anionic surfactant capable of obtaining particularly excellent effects, polyoxyalkylene alkyl phenyl ether sulfate salts (in particular, polyoxyethylene nonyl propenyl phenyl ether sulfate ammonium), dialkyl sulfosuccinic acid alkali metal salts (especially sodium dioctyl sulfosuccinate) Can be mentioned. Moreover, the compound mentioned by Formula (1) and Formula (2) is also mentioned as surfactant from which the outstanding effect is acquired.

  R in the formula (1) represents a hydrocarbon group having 1 to 12 carbon atoms (in particular, a hydrocarbon group having 10 carbon atoms or a hydrocarbon group having 12 carbon atoms), X represents an anionic hydrophilic group, and an average addition mole The number n represents a number of 3 to 40.

式（２）中のＸはアニオン性親水基を表す。

X in Formula (2) represents an anionic hydrophilic group.

  As an anionic hydrophilic group in the compound mentioned by the compound mentioned by Formula (1), and a formula (2), what is represented by Formula (a1)-(a2) is mentioned.

  As a compound mentioned by a formula (1), polyoxyethylene 1- (allyloxy methyl) alkyl ether ammonium sulfate etc. are mentioned, for example. As a compound mentioned by a formula (2), polyoxyethylene styrenated phenyl ether ammonium sulfate etc. are mentioned, for example.

  As the anionic surfactant, a general commercially available product can be used. For example, trade name "Aqualon HS-10" (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), trade name "Neocor P" (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) And trade name "Hightenol N-08" (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.). In addition, trade name "High tenor NF-13" (made by Dai-ichi Kogyo Seiyaku Co., Ltd.), trade name "High tenor NF-17" (made by Dai-ichi Kogyo Seiyaku Co., Ltd.), trade name "Aqualon KH-10" (No. And the like.

  The blending amount of the surfactant is preferably 0.1% by weight to 4% by weight, more preferably 0.15% by weight to 3% by weight, based on the total weight (100% by weight) of the pressure-sensitive adhesive layer. is there.

  The compounding amount of the surfactant is preferably 0.2 parts by weight to 4 parts by weight, more preferably 0.2 parts by weight to 3 parts by weight, and more preferably 100 parts by weight of the acrylic polymer. 0.3 to 3 parts by weight. By adjusting the compounding amount of the surfactant to 100 parts by weight of the acrylic polymer within the above range, the pressure-sensitive adhesive layer has a lighter trigger peeling force, a lighter 180 degree peel peeling force, and a faster wetting speed. In combination with the specific base material layer adopted in the present invention, a trigger for peeling from the adherend can be easily obtained, and light peeling can be achieved, and furthermore, the detection rate of flaws and foreign matter contamination is Higher surface protection films can be provided.

  The acrylic pressure-sensitive adhesive may contain a crosslinking agent from the viewpoint of obtaining a suitable cohesion. As a crosslinking agent, an isocyanate type crosslinking agent, an epoxy type crosslinking agent, a melamine type crosslinking agent, an aziridine type crosslinking agent, a metal chelate type crosslinking agent etc. are mentioned, for example. Among these, isocyanate crosslinking agents and epoxy crosslinking agents are preferable in that the effects of the present invention can be sufficiently exhibited. The crosslinking agent may be only one type, or two or more types.

  As an isocyanate type crosslinking agent, for example, lower aliphatic polyisocyanates such as butylene diisocyanate and hexamethylene diisocyanate, cycloaliphatic diisocyanates such as cyclopentylene diisocyanate, cyclohexylene diisocyanate and isophorone diisocyanate, 2,4-tolylene diisocyanate Isocyanate, aromatic isocyanates such as 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, trimethylolpropane / tolylene diisocyanate trimer adduct (trade name "Corronate L" manufactured by Nippon Polyurethane Industry Co., Ltd.), trimethylolpropane / Hexamethylene diisocyanate trimer adduct (trade name "Corronate HL" manufactured by Nippon Polyurethane Industry Co., Ltd.), isocyanine of hexamethylene diisocyanate Over door body (trade name "Coronate HX" manufactured by Nippon Polyurethane Industry Co., Ltd.), and the like isocyanate adducts such as.

  Examples of epoxy crosslinking agents include bisphenol A, epoxy resins of epichlorohydrin type, ethylene glycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, 1,6-hexanediol glycidyl ether, trimethylol Propane triglycidyl ether, diglycidyl aniline, diamine glycidyl amine, N, N, N ', N'-tetraglycidyl-m-xylene diamine (trade name "TETRAD-X" manufactured by Mitsubishi Gas Chemical Co., Ltd.), 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane (trade name "TETRAD-C" manufactured by Mitsubishi Gas Chemical Co., Ltd.) and the like.

  The compounding amount of the crosslinking agent is preferably 0.01% by weight to 15% by weight, more preferably 0.5% by weight to 10% by weight based on the total weight (100% by weight) of the pressure-sensitive adhesive layer. .

  The compounding amount of the crosslinking agent is preferably 0.01 parts by weight to 15 parts by weight, more preferably 0.5 parts by weight to 10 parts by weight, and still more preferably 2 parts by weight with respect to 100 parts by weight of the acrylic polymer. It is from 9 to 10 parts by weight, particularly preferably from 6 to 8 parts by weight. By adjusting the compounding amount of the crosslinking agent to 100 parts by weight of the acrylic polymer within the above range, the pressure-sensitive adhesive layer has a lighter trigger peeling force, a lighter 180 degree peel peeling force, and a faster wetting speed. In combination with the specific base material layer adopted in the present invention, a trigger for peeling from the adherend can be easily obtained, and light peeling is possible, and furthermore, the detection rate of flaws and foreign matter contamination is higher It is possible to provide a high surface protection film.

  The acrylic pressure-sensitive adhesive may contain a crosslinking catalyst. Examples of the crosslinking catalyst include metal-based crosslinking catalysts (in particular, tin-based crosslinking catalysts) such as tetra-n-butyltitanate, tetraisopropyltitanate, ferric nasem, butyltin oxide, and dioctyltin dilaurate. The crosslinking catalyst may be only one type or two or more types.

  The compounding amount of the crosslinking catalyst is preferably 0.004% by weight to 0.05% by weight, more preferably 0.004% by weight to 0.03% by weight based on the total weight (100% by weight) of the pressure-sensitive adhesive layer. It is weight%.

  The blending amount of the crosslinking catalyst is preferably 0.001 to 0.05 parts by weight, and more preferably 0.003 to 0.04 parts by weight with respect to 100 parts by weight of the acrylic polymer. More preferably, it is 0.005 parts by weight to 0.03 parts by weight. By adjusting the blending amount of the crosslinking catalyst with respect to 100 parts by weight of the acrylic polymer within the above range, the pressure-sensitive adhesive layer having a lighter trigger peeling force, a lighter 180 degree peel peeling force, and a faster wetting speed In combination with the specific base material layer adopted in the present invention, a trigger for peeling from the adherend can be easily obtained, and light peeling is possible, and furthermore, the detection rate of flaws and foreign matter contamination is higher It is possible to provide a high surface protection film. In addition, by adjusting the blending amount of the crosslinking catalyst with respect to 100 parts by weight of the acrylic polymer within the above range, the crosslinking rapidly proceeds, and therefore, the productivity can be improved.

  The acrylic pressure-sensitive adhesive may contain a crosslinking retarder. As the crosslinking retarder, for example, β-keto esters such as methyl acetoacetate, ethyl acetoacetate, octyl acetoacetate, oleyl acetoacetate, lauryl acetoacetate, stearyl acetoacetate, acetylacetone, 2,4-hexanedione, benzoylacetone and the like And β-diketones of Among these, acetylacetone is preferable in that the effects of the present invention can be sufficiently expressed. The crosslinking retarder may be only one kind or two or more kinds.

  The compounding amount of the crosslinking retarder is preferably 0.1% by weight to 10% by weight, more preferably 0.1% by weight to 3% by weight, based on the total weight (100% by weight) of the pressure-sensitive adhesive layer. is there.

  The compounding amount of the crosslinking retarder is preferably 0.1 parts by weight to 10 parts by weight, more preferably 0.1 parts by weight to 5 parts by weight, more preferably 0.1 parts by weight to 100 parts by weight of the acrylic polymer. 0.1 parts by weight to 3 parts by weight. By adjusting the compounding amount of the crosslinking retarder with respect to 100 parts by weight of the acrylic polymer within the above range, the pressure-sensitive adhesive layer is lighter in trigger peeling force, lighter in 180 degree peel peeling force, and faster in wetting speed In combination with the specific base material layer adopted in the present invention, a trigger for peeling from the adherend can be easily obtained, and light peeling can be achieved, and furthermore, the detection rate of flaws and foreign matter contamination is Higher surface protection films can be provided. Moreover, the usable life time of an acrylic adhesive can be extended by adjusting the compounding quantity of the crosslinking retarder with respect to 100 weight part of acrylic polymers in the said range.

  The acrylic pressure-sensitive adhesive may contain a solvent. As a solvent, the solvent used for the above-mentioned solution polymerization method is mentioned, for example.

  The acrylic pressure-sensitive adhesive may contain additives such as a plasticizer, an anti-aging agent, a coloring agent (such as a pigment and a dye), an antistatic agent, and a tackifying resin as long as the effects of the present invention are not impaired.

  The acrylic pressure-sensitive adhesive can be prepared, for example, by mixing an acrylic polymer, a crosslinking agent, a crosslinking catalyst, a crosslinking retarder, other additives, and the like.

«Method of manufacturing surface protection film»
The surface protection film of the present invention can be produced by any appropriate method.

  The surface protection film of the present invention can be preferably obtained by producing a laminate of a base material layer and an adhesive layer.

The laminate of the base material layer and the pressure-sensitive adhesive layer is, for example,
(1) A method of applying a solution of a forming material of a pressure-sensitive adhesive layer or a hot melt on a substrate layer,
(2) A method of transferring the pressure-sensitive adhesive layer formed on the separator according to (1) onto the base layer,
(3) A method of extruding and forming a pressure-sensitive adhesive layer forming material on a substrate layer,
(4) A method of extruding the base material layer and the pressure-sensitive adhesive layer in two or more layers,
(5) A method of single-layer laminating a pressure-sensitive adhesive layer on a substrate layer or a method of laminating a pressure-sensitive adhesive layer in combination with a laminate layer,
(6) A method of laminating two or more layers of a pressure-sensitive adhesive layer and a base layer-forming material such as a film or a laminate layer,
Etc. can be prepared by any suitable method.

«Applications»
The surface protective film of the present invention can easily obtain a trigger for peeling from an adherend, can be lightly peeled, and has a high detection ratio of scratches and foreign matter contamination, so the surface protection of optical members and electronic members Can be suitably used. That is, the optical member of the present invention is one to which the surface protection film of the present invention is adhered. The electronic member of the present invention is obtained by sticking the surface protection film of the present invention.

  EXAMPLES Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to these examples. In addition, the test and evaluation method in an Example etc. are as follows. The term "parts" means "parts by weight" unless otherwise specified, and the term "%" means "% by weight" unless otherwise specified.

<Weight average molecular weight>
A weight average molecular weight says what was obtained by measuring by gel permeation chromatography (GPC) method. More specifically, for example, using a trade name "HLC-8220GPC" (manufactured by Tosoh Corp.) as a GPC measurement apparatus, measurement can be performed under the following conditions, and calculated using a standard polystyrene conversion value.
(Molecular weight measurement conditions)
Sample concentration: 0.2% by weight (tetrahydrofuran solution)
Sample injection volume: 10 μL
Sample column: TSKguard column Super HZ-H (one) + TSK gel Super HZ M-H (two)
・ Reference column; TSKgel SuperH-RC (one)
Eluent: tetrahydrofuran (THF)
・ Flow rate: 0.6 mL / min
・ Detector: Differential refractometer (RI)
・ Column temperature (measurement temperature): 40 ° C

<Total ray transmittance>
The total light transmittance was measured using a haze meter (Model HM-150, manufactured by Murakami Color Research Laboratory) according to the method prescribed in JIS K7361 "Test method of total light transmittance of plastic-transparent material".

<Cause Peeling Force at a Peeling Speed of 0.3 m / min and Peeling Angle of 90 ° to Glass>
After pasting the adhesive layer side of the surface protection film cut to 25 mm width and peeling the separator on the surface of a glass plate (Matsunami Glass Industry Co., Ltd., trade name: micro slide glass S) using a 2 kg roller , Leave for 20 minutes at 23 ° C, 50% RH, peel at 90 ° peel angle, 0.3 m / min peel speed, read the maximum force at the point when the surface protective film starts to peel, trigger peel force And

<Peeling force at a peeling speed of 0.3 m / min and peeling angle of 180 ° to glass>
After pasting the adhesive layer side of the surface protection film cut to 25 mm width and peeling the separator on the surface of a glass plate (Matsunami Glass Industry Co., Ltd., trade name: micro slide glass S) using a 2 kg roller It was left to stand for 20 minutes under conditions of 23 ° C. and 50% RH, and was peeled off under conditions of a peeling angle of 180 degrees and a peeling speed of 0.3 m / min, and the peeling force of the surface protective film was measured.

<Wet speed on glass>
(1) A part of the adhesive layer surface of the test piece (the surface protective film cut into 2.5 cm × 15.0 cm) is an adherend (glass plate (manufactured by Matsunami Glass Industry Co., Ltd., trade name: micro slide glass) While in contact with S), the angle was held by hand so as to be 20 degrees to 30 degrees.
(2) Next, the test piece was released from the hand, and the adhesive layer surface of the test piece was in contact with the glass plate, and was recorded by a video camera as wetting and spreading from the contact portion in one direction. In the case of (1) above, when the part of the adhesive layer surface of the test piece was wet and spread from the part other than the part which was in contact with the glass plate of the adherend, the measurement and recording were not performed.
(3) The time until all the test pieces are wet and spread is recorded, and the wetting speed (cm ² / sec) = measurement area (25 cm ² ) / the number of seconds recorded (sec) is calculated, and the wetting speed (cm ² / sec) ).
(4) In addition, measurement was performed independently 3 times and the average value was adopted. Moreover, the measurement was performed in the environment of a clean room of class 10000 (temperature 23 ° C., humidity 50% RH).

<Easy inspection>
A glass plate (made by Matsunami Glass Industry Co., Ltd., trade name: micro slide glass S) is scratched with a length of about 2 mm with a glass cut, and a surface protection film is attached to the surface opposite to the scratched surface. ○, if the flaw could be easily confirmed visually, × if the confirmation was difficult.

Dropout of colored layer
The surface of the surface protective film opposite to the pressure-sensitive adhesive layer was rubbed three times with waste impregnated with ethyl acetate, and when no color transfer was confirmed on the waste, it was evaluated as ○, and when it was confirmed, it was evaluated as x.

Production Example 1 Production of Colored Substrate (A) A colored substrate (A) was a polyethylene terephthalate film (Toray Industries, Lumirror X30, thickness = 50 μm) into which carbon black was kneaded in an amount of less than 1%. ).

Production Example 2 Production of Transparent Base Material (B) A transparent polyethylene terephthalate film (Toray Industries, Inc., Lumirror S10, thickness = 38 μm) was used as a transparent base material (B).

Production Example 3 Production of Colored Substrate (C) On one surface of a transparent polyethylene terephthalate film (Toray Industries, Inc., Lumirror S10, thickness = 38 μm), a black ink is applied five or more times by gravure printing. The treated one was used as a colored substrate (C).

Example 1
As a polyol, 85 parts by weight of Preminor S3011 (manufactured by Asahi Glass Co., Ltd., Mn = 10000), 13 parts by weight of Sannix GP3000 (manufactured by Sanyo Chemical Industries, Ltd., Mn = 3000), Sannics GP1000 (manufactured by Sanyo Chemical Industries, Mn = 1000) 2.) 2 parts by weight and, as a polyfunctional isocyanate compound, Coronate HX (Nippon Polyurethane Industry Co., Ltd.): 18 parts by weight as a polyfunctional isocyanate compound, catalyst (manufactured by Nippon Kagaku Sangyo Co., Ltd., trade name: Nasem No. 2 Iron): 0.08 parts by weight, Irganox 1010 (manufactured by BASF): 0.5 parts by weight as an antidegradant, Isopropyl myristate (trade name: Exepearl IPM): 30 parts by weight as a wetting additive, diluted Add 210 parts by weight of ethyl acetate as a solvent and stir with a disper To obtain a urethane-based pressure-sensitive adhesive composition.
The resulting urethane-based pressure-sensitive adhesive composition is applied to the colored base material (A) obtained in Production Example 1 with an applicator so that the thickness after drying is 10 μm, and the drying temperature is 130 ° C., and the drying time is 2 minutes It was cured and dried under the conditions. Thus, a pressure-sensitive adhesive layer composed of a urethane-based pressure-sensitive adhesive (A) was produced on the colored base material (A). Next, the surface of the pressure-sensitive adhesive layer was bonded to a silicone-treated surface of a 25-μm-thick polyester resin whose one surface was subjected to silicone treatment, to obtain a surface protective film (1).
The results are shown in Table 1.

Example 2
As a polyol, 85 parts by weight of Preminor S3011 (manufactured by Asahi Glass Co., Ltd., Mn = 10000), 13 parts by weight of Sannix GP3000 (manufactured by Sanyo Chemical Industries, Ltd., Mn = 3000), Sannics GP1000 (manufactured by Sanyo Chemical Industries, Mn = 1000) 2.) 2 parts by weight and, as a polyfunctional isocyanate compound, Coronate HX (Nippon Polyurethane Industry Co., Ltd.): 18 parts by weight as a polyfunctional isocyanate compound, catalyst (manufactured by Nippon Kagaku Sangyo Co., Ltd., trade name: Nasem No. 2 Iron): 0.08 parts by weight, Irganox 1010 (manufactured by BASF): 0.5 parts by weight as an antidegradant, Isopropyl myristate (trade name: Exepearl IPM): 30 parts by weight as a wettability additive, charged 1-ethyl-3-methylimidazolium bis (full) as an inhibitor Rosulfonyl) imide (Daiichi Pharmaceutical Co., Ltd., trade name: Eleccel AS110): 1.25 parts by weight, modified silicone (Shin-Etsu Chemical make, trade name: KF-6004): 0.01 parts by weight, acetic acid as a dilution solvent Ethyl: 210 parts by weight was blended and stirred by a disper to obtain a urethane-based pressure-sensitive adhesive composition.
The resulting urethane-based pressure-sensitive adhesive composition is applied to the colored base material (A) obtained in Production Example 1 with an applicator so that the thickness after drying is 10 μm, and the drying temperature is 130 ° C., and the drying time is 2 minutes It was cured and dried under the conditions. Thus, a pressure-sensitive adhesive layer composed of a urethane-based pressure-sensitive adhesive (B) was produced on the colored substrate (A). Next, the surface of the pressure-sensitive adhesive layer was bonded with a silicone-treated surface of a 25-μm-thick polyester resin whose one surface was subjected to silicone treatment, to obtain a surface protective film (2).
The results are shown in Table 1.

[Example 3]
200 parts by weight of 2-ethylhexyl acrylate, 8 parts by weight of 2-hydroxyethyl acrylate, 2,2'-azobis as a polymerization initiator, in a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen gas inlet tube, and a cooler 0.4 parts by weight of isobutyro nitrile and 312 parts by weight of ethyl acetate as a solvent are charged, nitrogen gas is introduced while gently stirring, and the liquid temperature in the flask is kept at around 65 ° C. to carry out a polymerization reaction for 6 hours, An acrylic polymer solution (40% by weight) was prepared. The weight average molecular weight of the acrylic polymer was 540,000, the glass transition temperature (Tg) was -68 ° C, and the acid value was 0.0.
The above acrylic polymer solution (40% by weight) is diluted to 20% by weight with ethyl acetate, and 100 parts by weight of the solid content in this solution is an isocyanurate of hexamethylene diisocyanate as a crosslinking agent (manufactured by Nippon Polyurethane Industry Co., Ltd.) , Trade name: Coronate HX): 4 parts by weight, Dibutyltin dilaurate as a crosslinking catalyst (manufactured by Tokyo Fine Chemical Co., Ltd., trade name: Envirizer OL-1, 0.5 wt% ethyl acetate solution): 0.015 parts by weight, crosslinked As a retarder, 3 parts by weight of acetylacetone was added to the total amount of the solvent, and the mixture was mixed and stirred to obtain an acrylic pressure-sensitive adhesive composition.
The resulting acrylic pressure-sensitive adhesive composition is applied to the colored substrate (A) obtained in Production Example 1 with an applicator so that the thickness after drying is 10 μm, and the drying temperature is 130 ° C., and the drying time is 2 minutes. It was cured and dried under the conditions. Thus, a pressure-sensitive adhesive layer comprising an acrylic pressure-sensitive adhesive (A) was produced on the colored base material (A). Next, the surface of the pressure-sensitive adhesive layer was bonded to a silicone-treated surface of a 25-μm-thick polyester resin whose one surface was subjected to silicone treatment, to obtain a surface protective film (3).
The results are shown in Table 1.

Example 4
200 parts by weight of 2-ethylhexyl acrylate, 8 parts by weight of 2-hydroxyethyl acrylate, 2,2'-azobis as a polymerization initiator, in a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen gas inlet tube, and a cooler 0.4 parts by weight of isobutyro nitrile and 312 parts by weight of ethyl acetate as a solvent are charged, nitrogen gas is introduced while gently stirring, and the liquid temperature in the flask is kept at around 65 ° C. to carry out a polymerization reaction for 6 hours, An acrylic polymer solution (40% by weight) was prepared. The weight average molecular weight of the acrylic polymer was 540,000, the glass transition temperature (Tg) was -68 ° C, and the acid value was 0.0.
The above acrylic polymer solution (40% by weight) is diluted to 20% by weight with ethyl acetate, and 100 parts by weight of the solid content in this solution is an isocyanurate of hexamethylene diisocyanate as a crosslinking agent (manufactured by Nippon Polyurethane Industry Co., Ltd.) Trade name: Coronate HX): 5 parts by weight, anionic surfactant surfactant polyoxyethylene nonylpropenyl phenyl ether ammonium sulfate (Daiichi Kogyo Seiyaku Co., Ltd., trade name: Aqualon HS-10): 0.3 parts by weight 0.015 parts by weight of dibutyltin dilaurate as a crosslinking catalyst (trade name: Envirizer OL-1, 0.5 wt% ethyl acetate solution, manufactured by Tokyo Fine Chemical Co., Ltd.), and acetylacetone as a crosslinking retarder with respect to the total solvent amount of 3 A weight part was added and mixed and stirred to obtain an acrylic pressure-sensitive adhesive composition.
The resulting acrylic pressure-sensitive adhesive composition is applied to the colored substrate (A) obtained in Production Example 1 with an applicator so that the thickness after drying is 10 μm, and the drying temperature is 130 ° C., and the drying time is 2 minutes. It was cured and dried under the conditions. Thus, a pressure-sensitive adhesive layer comprising an acrylic pressure-sensitive adhesive (B) was produced on the colored base material (A). Next, the surface of the pressure-sensitive adhesive layer was bonded with a silicone-treated surface of a 25-μm-thick polyester resin whose one surface was subjected to silicone treatment, to obtain a surface protective film (4).
The results are shown in Table 1.

Comparative Example 1
As a polyol, 85 parts by weight of Preminor S3011 (manufactured by Asahi Glass Co., Ltd., Mn = 10000), 13 parts by weight of Sannix GP3000 (manufactured by Sanyo Chemical Industries, Ltd., Mn = 3000), Sannics GP1000 (manufactured by Sanyo Chemical Industries, Mn = 1000) 2.) 2 parts by weight and, as a polyfunctional isocyanate compound, Coronate HX (Nippon Polyurethane Industry Co., Ltd.): 18 parts by weight as a polyfunctional isocyanate compound, catalyst (manufactured by Nippon Kagaku Sangyo Co., Ltd., trade name: Nasem No. 2 Iron): 0.08 parts by weight, Irganox 1010 (manufactured by BASF): 0.5 parts by weight as an antidegradant, Isopropyl myristate (trade name: Exepearl IPM): 30 parts by weight as a wetting additive, diluted Add 210 parts by weight of ethyl acetate as a solvent and stir with a disper To obtain a urethane-based pressure-sensitive adhesive composition.
The resulting urethane-based pressure-sensitive adhesive composition is applied to the transparent substrate (B) obtained in Production Example 2 with an applicator so that the thickness after drying is 10 μm, and the drying temperature is 130 ° C., and the drying time is 2 minutes It was cured and dried under the conditions. Thus, a pressure-sensitive adhesive layer composed of a urethane-based pressure-sensitive adhesive (A) was produced on the transparent substrate (B). Next, the surface of the pressure-sensitive adhesive layer was bonded with a silicone-treated surface of a 25-μm-thick polyester resin whose one surface was treated with silicone to obtain a surface protective film (C1).
The results are shown in Table 1.

Comparative Example 2
In a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen gas inlet tube, and a cooler, 190 parts by weight of butyl acrylate, 5 parts by weight of acrylic acid, 2,2'-azobisisobutyro nitrile as a polymerization initiator Charge 4 parts by weight of ethyl acetate as a solvent and 312 parts by weight of ethyl acetate as a solvent, introduce nitrogen gas with gentle stirring, keep the liquid temperature in the flask at around 65 ° C, carry out polymerization reaction for 6 hours, 40% by weight) was prepared. The weight average molecular weight of the acrylic polymer was 540,000, the glass transition temperature (Tg) was -68 ° C, and the acid value was 0.0.
The above acrylic polymer solution (40% by weight) is diluted to 20% by weight with ethyl acetate, and 1,3-bis (N, N-glycidylaminomethyl) as a crosslinking agent with respect to 100 parts by weight of the solid content in this solution 6.) Cyclohexane (Mitsubishi Gas Chemical Co., Ltd., trade name: TETRAD-C): 6 parts by weight was added and mixed and stirred to obtain an acrylic pressure-sensitive adhesive composition.
The resulting acrylic pressure-sensitive adhesive composition is applied to the colored substrate (A) obtained in Production Example 1 with an applicator so that the thickness after drying is 10 μm, and the drying temperature is 130 ° C., and the drying time is 2 minutes. It was cured and dried under the conditions. Thus, a pressure-sensitive adhesive layer comprising an acrylic pressure-sensitive adhesive (C) was produced on the colored base material (A). Next, the surface of the pressure-sensitive adhesive layer was bonded to a silicone-treated surface of a 25-μm-thick polyester resin whose one surface was treated with silicone to obtain a surface protective film (C2).
The results are shown in Table 1.

Comparative Example 3
As a polyol, 85 parts by weight of Preminor S3011 (manufactured by Asahi Glass Co., Ltd., Mn = 10000), 13 parts by weight of Sannix GP3000 (manufactured by Sanyo Chemical Industries, Ltd., Mn = 3000); 2.) 2 parts by weight and, as a polyfunctional isocyanate compound, Coronate HX (Nippon Polyurethane Industry Co., Ltd.): 18 parts by weight as a polyfunctional isocyanate compound, catalyst (manufactured by Nippon Kagaku Sangyo Co., Ltd., trade name: Nasem No. 2 Iron): 0.08 parts by weight, Irganox 1010 (manufactured by BASF): 0.5 parts by weight as an antidegradant, Isopropyl myristate (trade name: Exepearl IPM): 30 parts by weight as a wetting additive, diluted Add 210 parts by weight of ethyl acetate as a solvent and stir with a disper To obtain a urethane-based pressure-sensitive adhesive composition.
The resulting urethane-based pressure-sensitive adhesive composition is applied to the colored base material (C) obtained in Production Example 3 with an applicator so that the thickness after drying is 10 μm, and the drying temperature is 130 ° C., and the drying time is 2 minutes It was cured and dried under the conditions. Thus, a pressure-sensitive adhesive layer composed of a urethane-based pressure-sensitive adhesive (A) was produced on the colored substrate (C). Next, the surface of the pressure-sensitive adhesive layer was bonded with a silicone-treated surface of a 25-μm-thick polyester resin whose one surface was treated with silicone to obtain a surface protective film (C3).
The results are shown in Table 1.

[Example 5]
The separator of the surface protection film (1) obtained in Example 1 is peeled off, and the adhesive layer side is adhered to a polarizing plate (trade name "TEG1465DUHC" manufactured by Nitto Denko Corporation) as an optical member to protect the surface An optical member having a film attached was obtained.

[Example 6]
The separator of the surface protective film (2) obtained in Example 2 is peeled off, and the adhesive layer side is adhered to a polarizing plate (trade name "TEG1465DUHC" manufactured by Nitto Denko Corporation), which is an optical member, and the surface The optical member to which the protective film was stuck was obtained.

[Example 7]
The separator of the surface protective film (3) obtained in Example 3 is peeled off, and the adhesive layer side is adhered to a polarizing plate (trade name "TEG1465DUHC" manufactured by Nitto Denko Corporation), which is an optical member, and the surface The optical member to which the protective film was stuck was obtained.

Example 8
The separator of the surface protective film (4) obtained in Example 4 is peeled off, and the adhesive layer side is adhered to a polarizing plate (trade name "TEG1465DUHC" manufactured by Nitto Denko Corporation), which is an optical member, and the surface The optical member to which the protective film was stuck was obtained.

[Example 9]
The separator of the surface protective film (1) obtained in Example 1 is peeled off, and the adhesive layer side is attached to a conductive film (trade name "ELECRISTA V270L-TFMP" manufactured by Nitto Denko Corporation) which is an electronic member. It attached, and obtained the electronic member by which the surface protection film was stuck.

[Example 10]
The separator of the surface protective film (2) obtained in Example 2 is peeled off, and the adhesive layer side is attached to the conductive film (trade name "ELECRISTA V270L-TFMP" manufactured by Nitto Denko Corporation) which is an electronic member. It attached, and obtained the electronic member by which the surface protection film was stuck.

[Example 11]
The separator of the surface protective film (3) obtained in Example 3 is peeled off, and the adhesive layer side is adhered to a conductive film (trade name "ELECRISTA V270L-TFMP" manufactured by Nitto Denko Corporation) which is an electronic member. It attached, and obtained the electronic member by which the surface protection film was stuck.

[Example 12]
The separator of the surface protective film (4) obtained in Example 4 is peeled off, and the adhesive layer side is adhered to a conductive film (trade name "ELECRISTA V270L-TFMP" manufactured by Nitto Denko Corporation) which is an electronic member. It attached, and obtained the electronic member by which the surface protection film was stuck.

  The surface protection film of the present invention can be suitably used for surface protection of optical members and electronic members.

1 substrate layer 2 pressure sensitive adhesive layer 3 separator 10 surface protection film

Claims (4)

A surface protective film having an adhesive layer and the colored base layer as a main component a polyester resin containing a black pigment,
The polyester resin is at least one selected from the group consisting of polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate.
The total light transmittance of the surface protective film is 5% or less,
Triggering force at a peeling speed of 0.3 m / min and a peeling angle of 90 degrees against glass of the surface protective film is 1 N / 25 mm or less,
The peeling force at a peeling speed of 0.3 m / min and a peeling angle of 180 degrees with respect to glass of the surface protective film is 0.1 N / 25 mm or less,
The wetting speed of the surface protective film to glass is 0.05 cm ² / sec or more.
Surface protection film.   The surface protection film according to claim 1, wherein the pressure-sensitive adhesive layer contains at least one pressure-sensitive adhesive selected from a urethane-based pressure-sensitive adhesive and an acrylic pressure-sensitive adhesive.   The optical member by which the surface protection film of Claim 1 or 2 was stuck. The electronic member by which the surface protection film of Claim 1 or 2 was stuck.

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