JP2017008173A - Surface protective film - Google Patents

Abstract

Provided is a surface protective film that can be easily peeled off from an adherend, can be peeled lightly, and has a high detection rate of scratches and foreign matter. Moreover, provision of the optical member and electronic member which such a surface protection film was stuck. A surface protective film 10 having a base material layer 1 mainly composed of a polyester resin and an adhesive layer 2, wherein the base material layer 1 is a colored base material layer having a colored layer 11, and the surface protection. The total light transmittance of the film 10 is 5% or less, and the surface peelability of the surface protective film 10 with respect to the glass is 0.3 m / min and the peel strength at a peel angle of 90 degrees is 1 N / 25 mm or less. 10 for a glass having a peel rate of 0.3 m / min, a peel force of 180 N at a peel angle of 0.1 N / 25 mm or less, and a wetting rate of the surface protective film 10 on the glass of 0.05 cm 2 / sec or more. Protective film 10. [Selection] Figure 1

Description

  The present invention relates to a surface protective 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 EL, touch panels using these, lens parts of cameras, optical members and electronic members such as electronic devices are generally exposed to prevent scratches on the surface during processing, assembly, inspection, transportation, etc. A surface protective 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 applied to an adherend such as an optical member or an electronic member after peeling the separator and exposing the pressure-sensitive adhesive layer. It peels from adherends, such as a member and an electronic member (for example, patent documents 1, 2). For this reason, it is required that a trigger for peeling from the adherend can be easily obtained and that light peeling can be performed.

  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 a foreign matter contamination on the optical member or the electronic member.

  However, since the optical member and the electronic member to which the conventional surface protective film is attached have high transparency as a whole, there is a problem that the detection rate of scratches and foreign matters in the manufacturing process is low.

JP-A-2005-306996 JP 2005-309071 A

  An object of the present invention is to provide a surface protective film that can be easily peeled off from an adherend, can be easily peeled off, and has a high detection rate of scratches and 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 protective film of the present invention is
A surface protective film having a base material layer mainly composed of a polyester resin and an adhesive layer,
The substrate layer is a colored substrate layer having a colored layer;
The total light transmittance of the surface protective film is 5% or less,
With respect to the glass of the surface protective film, the peeling speed is 0.3 m / min, the trigger peeling force at a peeling angle of 90 degrees is 1 N / 25 mm or less,
With respect to the glass of the surface protective film, the peeling force at a peeling speed of 0.3 m / min and a peeling angle of 180 degrees is 0.1 N / 25 mm or less,
The wetting speed of the surface protective film to glass is 0.05 cm ² / second or more.

  As 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.

  In one embodiment, the colored layer is a printed layer.

  The optical member of the present invention has the surface protective film of the present invention attached thereto.

  The electronic member of the present invention is obtained by attaching the surface protective film of the present invention.

  According to the present invention, it is possible to provide a surface protective film that can be easily peeled off from an adherend, can be easily peeled off, and has a high detection rate of scratches and foreign matter. Moreover, according to this invention, the optical member and electronic member to which such a surface protection film was stuck can be provided.

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

≪Surface protection film≫
The surface protective film of this invention has a base material layer which has a polyester resin as a main component, and an adhesive layer.

  FIG. 1 is a schematic cross-sectional view of a surface protective film according to one embodiment of the present invention. The surface protective film 10 includes a base material layer 1 and an 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, you may have the separator 3 in the surface on the opposite side to the base material layer 1 of the adhesive layer 2. As shown in FIG.

  As shown in FIG. 1, the base material layer 1 has a colored layer 11. As for the colored layer 11, Preferably, as shown in FIG. 1, the base material layer 1 has the colored layer 11 in the outermost part on the opposite side to the adhesive layer 2 of this base material layer 1. As shown in FIG.

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

  The thickness of the separator can be set to any appropriate thickness depending on the application. From the viewpoint of sufficiently expressing the effects of the present invention, the thickness is preferably 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 can be adopted as a material for the separator as long as the effects of the present invention are not impaired. Examples of such a material include plastic, paper, metal film, and non-woven fabric. Among such materials, plastic is preferable. The separator may be composed of one kind of material or may be composed of two or more kinds of materials.

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

  The thickness of the surface protective film of the present invention can be set to any appropriate thickness depending on the application. From the viewpoint of fully expressing the effects of the present invention, the thickness is preferably 35 μm to 145 μm, more preferably 40 μm to 130 μm, still more preferably 45 μm to 110 μm, and particularly preferably 45 μm to 85 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, still more preferably 3.5% or less, particularly Preferably it is 3% or less. The lower limit of the total light transmittance is preferably 0%. By adjusting the total light transmittance of the surface protective film of the present invention within the above range, it is possible to provide a surface protective film having a high detection rate of scratches and foreign matters. In addition, the detail of the measuring method of the said total light transmittance is mentioned later.

  The surface protective film of the present invention has a peeling strength of 0.3 N / min and a peeling angle of 90 ° with respect to glass of 1 N / 25 mm or less, preferably 0.8 N / 25 mm or less, more preferably 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 of the trigger peeling force is preferably 0.01 N / 25 mm. The surface protective film of the present invention affixed to an adherend by adjusting the trigger peel force at a peel rate of 0.3 m / min and a peel angle of 90 degrees with respect to the glass within the above range. The trigger for peeling is easily obtained. The details of the method for measuring the trigger peel force will be described later.

  The surface protective film of the present invention has a peel rate of 0.3 m / min and a peel angle of 180 degrees with respect to glass of 0.1 N / 25 mm or less, preferably 0.08 N / 25 mm or less, 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 the peeling force is preferably 0.005 N / 25 mm. The surface protective film of the present invention affixed to the adherend is adjusted by adjusting the peeling force at a peeling speed of 0.3 m / min and a peeling angle of 180 degrees to the glass of the surface protective film of the present invention. Can be peeled lightly. 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 1 cm ² / second or more, particularly preferably 5 cm ² / second or more, and most preferably 10 cm ² / second 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 protective film of the present invention to the glass within the above range, it is possible to provide a surface protective film that suppresses entrainment of bubbles and foreign matters and has a high detection rate of scratches and foreign matters. Details of the method for measuring the wetting rate will be described later.

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

<Base material layer>
A base material layer has a polyester resin as a main component. Specifically, the content ratio of the polyester resin other than the colored layer portion in the base material layer is preferably 50% by weight to 100% by weight, more preferably 70% by weight to 100% by weight, Preferably they are 90 weight%-100 weight%, Especially preferably, they are 92 weight%-100 weight%, Most preferably, they are 95 weight%-100 weight%. By adjusting the content ratio of the polyester resin other than the colored layer portion 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 easily performed. It is possible to provide a surface protective film having a higher detection rate of scratches and foreign matter contamination.

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

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

  The thickness of the base material layer can be set to any appropriate thickness depending on the application. From the viewpoint of fully expressing the effects of the present invention, the thickness 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 material layer is a colored base material layer having a colored layer. The base material layer preferably has a colored layer on the outermost part of the base material layer opposite to the pressure-sensitive adhesive layer. The colored layer may be a single layer or two or more layers.

  The colored layer is preferably a black layer from the viewpoint that the effects of the present invention are sufficiently exhibited.

  The colored layer can be formed by any appropriate method as long as the effects of the present invention are not impaired. Examples of such a method include a method of forming a colored layer by a printing method such as a gravure printing method, a flexographic printing method, an offset printing method, a relief printing method, and a screen printing method. For example, when a black layer is formed, a gravure printing method, a screen printing method, or the like is performed.

  The thickness of the colored layer is preferably 0.5 μm to 20 μm, more preferably 1 μm to 15 μm, still more preferably 3 μm to 15 μm, and particularly preferably 5 μm, from the viewpoint of sufficiently expressing the effects of the present invention. 10 μm.

  The base material layer may contain any appropriate additive as required. Examples of the additive that can be contained in the base material layer include an antioxidant, an ultraviolet absorber, a light stabilizer, an antistatic agent, a filler, and a pigment. The kind, number, and amount of additives that can be contained in the base material layer can be appropriately set according to the purpose.

  Any appropriate antioxidant can be adopted as the antioxidant. Examples of such antioxidants include phenol-based antioxidants, phosphorus-based processing heat stabilizers, lactone-based processing heat stabilizers, sulfur-based heat-resistant stabilizers, phenol-phosphorus-based antioxidants, and the like. The content of the antioxidant is preferably 1% by weight or less, 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.

  Arbitrary appropriate ultraviolet absorbers can be employ | adopted as a ultraviolet absorber. Examples of such UV absorbers include benzotriazole UV absorbers, triazine UV absorbers, and benzophenone UV absorbers. The content ratio of the ultraviolet absorber is preferably 2% by weight or less, more preferably 1% by weight or less, further preferably 0.01% by weight to 0.5% with respect to the polyester resin in the base material layer. % By weight.

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

  Any appropriate filler can be adopted as the filler. Examples of such fillers include inorganic fillers other than black pigments. The content 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 with respect to 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, and high molecular weight antistatic agents. Agents are also included.

  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 dry polyester resin chip, a dry black pigment master chip, and other additives are mixed as necessary, in order to sufficiently exhibit the effects of the present invention Is supplied to an extruder heated to 260 to 300 ° C., melted, introduced into a T die die, and extruded. This molten sheet is closely 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 thus obtained may be used as it is, or may be formed into a sheet having a necessary and optimum thickness by biaxially stretching mainly in the longitudinal direction and the transverse direction. Stretching may be sequential biaxial stretching or simultaneous biaxial stretching in two directions at the same time. Further, re-stretching may be performed in the longitudinal and / or transverse direction. In an example of sequential biaxial stretching, an unstretched film is led to a roll group heated to 70 to 120 ° C., and stretched 2 to 5 times in the longitudinal direction (longitudinal direction, that is, the traveling direction of the film) to roll at 20 to 30 ° C. Cool in groups. Subsequently, both ends of the film stretched in the longitudinal direction are guided to a tenter while being gripped by clips, and stretched 2 to 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. When the area magnification is less than 6 times, the strength of the obtained film tends to be insufficient, and when it exceeds 20 times, tearing tends to occur during stretching. The biaxially stretched film thus obtained is gradually and slowly cooled through a heat treatment step at 150 to 238 ° C. for 1 to 30 seconds in the tenter to complete the crystal orientation and impart flatness and dimensional stability. Then, after cooling to room temperature and winding up, the substrate layer can be obtained after slitting to an appropriate size. During the heat treatment step, a relaxation treatment of 3 to 12% may be performed in the horizontal direction or the vertical direction as necessary. Moreover, also when producing an unstretched sheet close | similar to this method and carrying out simultaneous biaxial stretching, it is preferable that the area ratio of extending | stretching is 6-20 times. In addition, after biaxial stretching, the film may be re-stretched in either the vertical or horizontal direction or in both directions. In addition, the stretching temperature and the magnification are preferably selected as appropriate in accordance with the amount of black pigment or other additive added to the polyester resin.

<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. When the pressure-sensitive adhesive layer contains at least one pressure-sensitive adhesive selected from urethane-based pressure-sensitive adhesives and acrylic pressure-sensitive adhesives, the pressure-sensitive peeling force is light, the 180-degree peel strength is light, and the wetting speed is high. In combination with the specific base material layer employed in the present invention, it is possible to easily obtain a trigger for peeling from the adherend, and it is possible to lightly peel off. 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 can be set to any appropriate thickness depending on the application. From the viewpoint of sufficiently expressing the effects of the present invention, the thickness is preferably 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, Especially preferably, it is 99 weight%-100 weight%. By adjusting the content ratio of the pressure-sensitive adhesive in the pressure-sensitive adhesive layer within the above range, it is possible to obtain a pressure-sensitive adhesive layer having a light trigger release force, a light 180 degree peel strength, and a fast wetting speed. By combining with a specific base material layer to be adopted, it is possible to easily obtain a trigger for peeling from the adherend, and it can be peeled lightly, and also provides a surface protection film with a higher detection rate of scratches and foreign matters can do.

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

  The content ratio of the polyurethane-based resin in the urethane-based 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 as a lower limit. 60% by weight or more, particularly preferably 65% by weight or more, most preferably 70% by weight or more, and the upper limit is preferably 99.999% by weight or less, more preferably 99.99% by weight. Or less, more preferably 99.9% by weight or less, further 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 polyurethane-based resin in the urethane-based pressure-sensitive adhesive within the above range, it is possible to obtain a pressure-sensitive adhesive layer with a lighter trigger peel force, a lighter 180 degree peel strength, and a faster wetting rate. In combination with the specific base material layer employed in the present invention, the trigger for peeling from the adherend can be easily obtained, and light peeling can be easily achieved, and the detection rate of scratches and foreign matter is higher. A surface protective film can be provided.

  One type of polyurethane resin may be used, or two or more types may be used.

  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.

  As the polyol (A), any appropriate polyol can be adopted as long as it is a polyol having two or more OH groups. Examples of such a polyol (A) include a polyol having 2 OH groups (diol), a polyol having 3 OH groups (triol), a polyol having 4 OH groups (tetraol), and 5 OH groups. Examples thereof include a polyol having a single number (pentaol) and a polyol having six OH groups (hexaol).

  In the present invention, a polyol (triol) having three OH groups is preferably employed as the essential component as the polyol (A). Thus, when a polyol (triol) having three OH groups as the polyol (A) is adopted as an essential component, for example, a pressure-sensitive adhesive layer with a light trigger peel force, a light 180 ° peel strength, and a fast wetting rate is obtained. In combination with the specific base material layer employed in the present invention, it is possible to provide a surface protective film having a higher detection rate of flaws and foreign matters. 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. 80 to 100% by weight, more preferably 90 to 100% by weight, particularly preferably 95 to 100% by weight, and most preferably substantially 100% by weight.

  The polyol (A) preferably includes a polyol having a number average molecular weight Mn of 400 to 20000. The content ratio of the polyol having a number average molecular weight Mn of 400 to 20000 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% by weight to 100% by weight, particularly preferably 95% by weight to 100% by weight, and most preferably substantially 100% by weight. By adjusting the content ratio of the polyol having a number average molecular weight Mn of 400-20000 in the polyol (A) within the above range, the trigger peel force is lighter, the 180 degree peel force is lighter, and the wetting speed is It can be a faster pressure-sensitive adhesive layer, and when combined with the specific base material layer employed in the present invention, the trigger for peeling from the adherend can be easily obtained, and light peeling can be easily achieved. And a surface protection film having a higher detection rate of contamination.

  In the present invention, when a polyol (triol) having three OH groups is employed as an essential component as the polyol (A), preferably a triol having a number average molecular weight Mn of 7000 to 20000 and a number average molecular weight Mn of 2000 to 2000 6000 triol and a triol having a number average molecular weight Mn of 400 to 1900, more preferably a triol having a number average molecular weight Mn of 8000 to 15000, a triol having a number average molecular weight Mn of 2000 to 5000, and a number average A triol having a molecular weight Mn of 500 to 1800 is used in combination, 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 1500. Use with triol. When these three types of triols are used in combination, the pressure-sensitive adhesive layer is lighter, the 180-degree peel strength is lighter, and the wetting speed is faster. By combining with a layer, a trigger for peeling from the adherend can be easily obtained, light peeling can be easily performed, and a surface protection film having a higher detection rate of scratches and foreign matters can be provided.

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

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

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

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

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

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

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

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

  One type of polyfunctional isocyanate compound (B) may be sufficient, and 2 or more types may be sufficient as it.

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

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

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

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

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

  The content ratio 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 of the polyfunctional isocyanate compound (B) with respect to the polyol (A). %, More preferably 10% to 60% by weight. By adjusting the content ratio of the polyfunctional isocyanate compound (B) within the above range, it is possible to obtain a pressure-sensitive adhesive layer having a lighter trigger peel force, a lighter 180 degree peel force, and a faster wetting rate. By combining with a specific base material layer adopted in the present invention, the trigger for peeling from the adherend can be easily obtained, and the surface can be peeled lightly. A film can be provided.

  In the polyol (A) and the polyfunctional isocyanate compound (B), the equivalent ratio of the NCO group to the OH group is more than 1.0 and not more than 5.0 as the NCO group / OH group, 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 obtain a pressure-sensitive adhesive layer having lighter trigger peel force, lighter 180 degree peel force, and faster wetting rate. In combination with a specific base material layer adopted in the above, a surface protective film that can be easily peeled off from the adherend, can be peeled lightly, and has a higher detection rate of scratches and foreign matter. Can be provided.

  The polyurethane-based resin is obtained by curing a composition containing the polyol (A) and the polyfunctional isocyanate compound (B). Such a composition may contain any appropriate other component other than the polyol (A) and the polyfunctional isocyanate compound (B) as long as the effects of the present invention are not impaired. Examples of such other components include catalysts, other resin components other than polyurethane resins, tackifiers, inorganic fillers, organic fillers, metal powders, pigments, foils, softeners, plasticizers, Examples thereof include an antioxidant, a conductive agent, an antioxidant, an ultraviolet absorber, a light stabilizer, a surface lubricant, a leveling agent, a corrosion inhibitor, a heat stabilizer, a polymerization inhibitor, a lubricant, and a solvent.

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

  The content ratio of the deterioration preventing agent is preferably 0.01% by weight to 20% by weight, more preferably 0.02% by weight to 15% by weight, and still more preferably 0.8% with respect to the polyol (A). 03 wt% to 10 wt%, more preferably 0.05 wt% to 7 wt%, further preferably 0.1 wt% to 5 wt%, particularly preferably 0.1 wt% to 3 wt%. % By weight, most preferably from 0.1% to 1% by weight. By adjusting the content ratio of the deterioration preventive agent within the above range, adhesive residue is less likely to remain on the adherend even if it is stored in a heated state after being attached to the adherend. Can become better. If the content ratio of the deterioration inhibitor is too small, there is a possibility that the adhesive residue preventing property cannot be sufficiently exhibited. If the content of the deterioration inhibitor is too large, there may be a problem that the cost is disadvantageous, a problem that the adhesive property cannot be maintained, or a problem that the adherend is contaminated may occur. .

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

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

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

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

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

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

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

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

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

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

  Examples of the benzophenone ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2,2 ′. -Dihydroxy-4-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone, bis (2-methoxy-4-hydroxy-5-benzoylphenyl) ) Methane.

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

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

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

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

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

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

  The deterioration inhibitor is preferably a deterioration inhibitor having a hindered phenol structure. When the deterioration inhibitor having a hindered phenol structure is included as the deterioration inhibitor, the content thereof is preferably 0.01% by weight to 10% by weight, more preferably 0.05%, based on 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 deterioration preventing agent having a hindered phenol structure within the above range, it is more difficult to produce adhesive residue on the adherend even if it is stored in a heated state after being attached to the adherend. , It can become more excellent in preventing adhesive residue. If the content ratio of the deterioration inhibitor having a hindered phenol structure is too small, there is a possibility that the adhesive residue preventing property cannot be sufficiently exhibited. If the content of the anti-degradation agent having a hindered phenol structure is too large, there may be a problem that the cost is disadvantageous, the problem that the adhesive properties cannot be maintained, or the adherend is contaminated. May occur.

  Examples of the degradation inhibitor having a hindered phenol structure include a group having a large steric hindrance such as a tertiary butyl group bonded to at least one of the adjacent carbon atoms on the aromatic ring to which the OH group of phenol is bonded. Any appropriate deterioration preventing agent can be adopted as long as it is a deterioration preventing agent having a hindered phenol structure. By using a specific degradation inhibitor called a degradation inhibitor having such a hindered phenol structure, it is considered that the effect of suppressing a decrease in the molecular weight of the polyol is greatly increased compared to the conventional one. An effect that the preventive property is remarkably superior to the conventional one can be exhibited.

  Specific examples of the degradation inhibitor having such a hindered phenol structure include, for example, dibutylhydroxytoluene (BHT); trade name “IRGANOX1010” (manufactured by BASF), trade name “IRGANOX1010FF” (manufactured by BASF), and merchandise. Name “IRGANOX1035” (BASF), product name “IRGANOX1035FF” (BASF), product name “IRGANOX1076” (BASF), product name “IRGANOX1076FD” (BASF), product name “IRGANOX1076DWJ” (BASF), product Name “IRGANOX1098” (manufactured by BASF), product name “IRGANOX1135” (manufactured by BASF), product name “IRGANOX1330” (manufactured by BASF), product name “IRGANOX1726” (manufactured by BASF), Product name “IRGANOX1425WL” (manufactured by BASF), product name “IRGANOX1520L” (manufactured by BASF), product name “IRGANOX245” (manufactured by BASF), product name “IRGANOX245FF” (manufactured by BASF), product name “IRGANOX259” (manufactured by BASF), product Hindered phenolic antioxidants such as “IRGANOX 3114” (BASF), trade name “IRGANOX565” (BASF), trade name “IRGANOX295” (BASF); trade name “TINUVIN P” (BASF), product Name “TINUVIN P FL” (BASF), product name “TINUVIN234” (BASF), product name “TINUVIN326” (BASF), product name “TINUVIN326FL” (BASF), product name “T” Benzotriazole ultraviolet absorbers such as NUVIN 328 (manufactured by BASF), trade name “TINUVIN 329” (manufactured by BASF), trade name “TINUVIN 329FL” (manufactured by BASF); trade name “TINUVIN 213” (manufactured by BASF), trade name “TINUVIN 571” Liquid UV absorbers such as (manufactured by BASF); Triazine UV absorbers such as trade name “TINUVIN1577ED” (manufactured by BASF); Benzoate UV absorbers such as trade name “TINUVIN120” (manufactured by BASF); Trade name “TINUVIN144” Hindered amine light stabilizers such as (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. 1 type of fatty acid ester may be sufficient and 2 or more types may be sufficient as it.

  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 further preferably 8% by weight to 35% by weight with respect to the polyol (A). It is particularly preferably 9 to 30% by weight, most preferably 10 to 20% by weight. By adjusting the content ratio of the fatty acid ester within the above range, the wetting rate can be further improved. If the content of the fatty acid ester is too small, the wetting rate may not be sufficiently improved. When the content ratio of the fatty acid ester is too large, there may be a problem that the cost becomes disadvantageous, a problem that the adhesive property cannot be maintained, or a problem that the adherend is contaminated.

  The number average molecular weight Mn of the fatty acid ester is preferably 200 to 400, more preferably 210 to 395, still more preferably 230 to 380, particularly preferably 240 to 360, and most preferably 270 to 340. It is. By adjusting the number average molecular weight Mn of the fatty acid ester within the above range, the wetting rate can be further improved. If the number average molecular weight Mn of the fatty acid ester is too small, the wetting rate may not be improved even if the number of added parts is large. If the number average molecular weight Mn of the fatty acid ester is too large, the curability of the pressure-sensitive adhesive at the time of drying deteriorates, and there is a possibility that it may not only affect the wettability but also adversely affect other adhesive properties.

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

  The polyurethane-based resin preferably contains a leveling agent. By including a leveling agent in the polyurethane resin, it is possible to prevent uneven appearance due to the skin. Only one type of leveling agent may be used, or two or more types may be used.

  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 still more preferably 0% with respect to the polyol (A). 0.003 wt% to 0.1 wt%, particularly preferably 0.004 wt% to 0.05 wt%, and most preferably 0.005 wt% to 0.01 wt%. By adjusting the content ratio of the leveling agent within the above range, it is possible to further prevent appearance unevenness due to the yuzu skin. If the content of the leveling agent is too small, it may not be possible to prevent uneven appearance due to yuzu skin. If the content of the leveling agent is too large, there may be a problem that the cost becomes disadvantageous, a problem that the adhesive property cannot be maintained, or a problem that the adherend is contaminated.

  Any appropriate leveling agent can be adopted as the leveling agent as long as the effects of the present invention are not impaired. Examples of such a leveling agent include an acrylic leveling agent, a fluorine leveling agent, and a silicon leveling agent. As an acrylic leveling agent, polyflow no. 36, Polyflow No. 56, Polyflow No. 85HF, Polyflow No. 99C (Isure is also Kyoeisha Chemical Co., Ltd.). Examples of the fluorine leveling agent include Megafac F470N and Megafac F556 (both manufactured by DIC). Examples of the silicon leveling agent include Grandic PC4100 (manufactured by DIC).

  As a method for obtaining a polyurethane resin by curing a composition containing a polyol (A) and a polyfunctional isocyanate compound (B), the effects of the present invention, such as a urethanization reaction method using bulk polymerization or solution polymerization, are used. Any appropriate method can be adopted as long as it is not impaired. However, since the conventional polyurethane-based resin obtained via a so-called urethane prepolymer may not exhibit the effects of the present invention, it contains a polyol (A) and a polyfunctional isocyanate compound (B). The method for obtaining the polyurethane resin by curing the product 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. Examples of such a catalyst include organometallic compounds and tertiary amine compounds.

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

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

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

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

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

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

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

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

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

  Only one type of catalyst may be used, or two or more types of catalysts may be used. A catalyst and a crosslinking retarder may be used in combination. The amount of the catalyst is preferably 0.02% by weight to 0.10% by weight, more preferably 0.02% by weight to 0.08% by weight, and still more preferably 0% with respect to the polyol (A). 0.02 wt% to 0.06 wt%, particularly preferably 0.02 wt% to 0.05 wt%. By adjusting the amount of the catalyst within the above range, it is possible to obtain a pressure-sensitive adhesive layer having a light trigger peel force, a light 180 degree peel strength, and a fast wetting rate, and is used in the present invention. In combination, the surface protective film can be easily obtained as a trigger for peeling from the adherend, can be peeled lightly, and has a higher detection rate of scratches and foreign matter.

  The urethane-based pressure-sensitive adhesive may contain an ionic liquid containing a fluoro organic anion. When the urethane-based pressure-sensitive adhesive contains an ionic liquid containing a fluoro organic anion, a urethane-based pressure-sensitive adhesive having excellent antistatic properties can be provided. The ionic liquid that can 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) that is liquid at 25 ° C.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

  Among these, the triethylmethyl ammonium cation, tributyl ethyl ammonium cation, trimethyl decyl ammonium cation, diethyl methyl sulfonium cation, dibutyl ethyl sulfonium cation, dimethyl decyl sulfonium cation, Asymmetric tetraalkylammonium cations such as triethylmethylphosphonium cation, tributylethylphosphonium cation, trimethyldecylphosphonium cation, trialkylsulfonium cation, tetraalkylphosphonium cation, N, N-diethyl-N-methyl-N- (2-methoxy) Ethyl) ammonium cation, glycidyltrimethylammonium cation, diallyldimethylammoni Cation, N, N-dimethyl-N-ethyl-N-propylammonium cation, N, N-dimethyl-N-ethyl-N-butylammonium cation, N, N-dimethyl-N-ethyl-N-pentylammonium cation, N, N-dimethyl-N-ethyl-N-hexylammonium cation, N, N-dimethyl-N-ethyl-N-heptylammonium cation, N, N-dimethyl-N-ethyl-N-nonylammonium cation, N, N-dimethyl-N, N-dipropylammonium cation, N, N-diethyl-N-propyl-N-butylammonium cation, N, N-dimethyl-N-propyl-N-pentylammonium cation, N, N-dimethyl -N-propyl-N-hexylammonium cation, N, N-dimethyl- -Propyl-N-heptylammonium cation, N, N-dimethyl-N-butyl-N-hexylammonium cation, N, N-diethyl-N-butyl-N-heptylammonium cation, N, N-dimethyl-N-pentyl -N-hexylammonium cation, N, N-dimethyl-N, N-dihexylammonium cation, trimethylheptylammonium cation, N, N-diethyl-N-methyl-N-propylammonium cation, N, N-diethyl-N- Methyl-N-pentylammonium cation, N, N-diethyl-N-methyl-N-heptylammonium cation, N, N-diethyl-N-propyl-N-pentylammonium cation, triethylpropylammonium cation, triethylpentylammonium Cation, triethylheptylammonium cation, N, N-dipropyl-N-methyl-N-ethylammonium cation, N, N-dipropyl-N-methyl-N-pentylammonium cation, N, N-dipropyl-N-butyl-N -Hexylammonium cation, N, N-dipropyl-N, N-dihexylammonium cation, N, N-dibutyl-N-methyl-N-pentylammonium cation, N, N-dibutyl-N-methyl-N-hexylammonium cation , Trioctylmethylammonium cation, N-methyl-N-ethyl-N-propyl-N-pentylammonium cation, and the like, more preferably trimethylpropylammonium cation.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

  The urethane-based pressure-sensitive adhesive may contain any appropriate other component within the range not impairing the effects of the present invention, in addition to the polyurethane-based resin and the ionic liquid as described above. Examples of such other components include other resin components other than polyurethane resins, tackifiers, inorganic fillers, organic fillers, metal powders, pigments, foils, softeners, plasticizers, and anti-aging agents. Agents, conductive agents, ultraviolet absorbers, antioxidants, light stabilizers, surface lubricants, leveling agents, corrosion inhibitors, heat stabilizers, polymerization inhibitors, lubricants, solvents and the like.

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

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

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

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

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

[Acrylic adhesive]
The acrylic pressure-sensitive adhesive contains an acrylic polymer.

  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, further preferably 55% by weight or more, and more preferably as a lower limit. 60% by weight, particularly preferably 65% by weight, most preferably 70% by weight, and the upper limit is preferably 99.999% by weight or less, more preferably 99.99% by weight or less. More preferably, it is 99.9% by weight or less, 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 acrylic polymer in the acrylic pressure-sensitive adhesive within the above range, it is possible to obtain a pressure-sensitive adhesive layer with lighter trigger peel force, lighter 180 degree peel strength, and faster wetting rate. In combination with the specific base material layer employed in the present invention, the trigger for peeling from the adherend can be easily obtained, and light peeling can be easily achieved, and the detection rate of scratches and foreign matter is higher. A surface protective 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.

  Only one type of acrylic polymer may be used, or two or more types may be used. Only one type of acrylic monomer may be used, or two or more types may be used.

  The acrylic polymer preferably contains a (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. 6 to 14 carbon atoms such as (meth) acrylate, n-decyl (meth) acrylate, isodecyl (meth) acrylate, n-dodecyl (meth) acrylate, n-tridecyl (meth) acrylate, n-tetradecyl (meth) acrylate and the like. Examples thereof include (meth) acrylic acid alkyl esters having an alkyl group. 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, and n-tridecyl (meth) acrylate. Only one (meth) acrylic acid alkyl ester may be used, or two or more may be used.

  The content ratio of the (meth) acrylic acid alkyl ester to the total monomer component (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 85% to 98% by weight, particularly preferably 90% to 98% by weight. By adjusting the content ratio of the (meth) acrylic acid alkyl ester to the total monomer component (100% by weight) constituting the acrylic polymer within the above range, the trigger peel force is lighter and the 180 degree peel peel force is more The pressure-sensitive adhesive layer can be made lighter and has a faster wetting rate. By combining with the specific base material layer employed in the present invention, the trigger for peeling from the adherend can be easily obtained, and light peeling can be easily achieved. In addition, it is possible to provide a surface protective 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 ( (Meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, (4-hydroxymethylcyclohexyl) methyl acrylate, N-methylol (meth) acrylamide, vinyl alcohol, allyl alcohol, 2- Examples thereof include hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol monovinyl ether and the like. Only one kind of hydroxyl group-containing monomer may be used, or two or more kinds thereof may be used.

  The content ratio of the hydroxyl group-containing monomer to the total monomer component (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 to 10% by weight, and particularly preferably 3 to 8% by weight. 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, a crosslinking point is formed and a cohesive force is obtained. Light, 180 degree peel strength is lighter, and the wetting speed can be made faster, and by combining with the specific base material layer adopted in the present invention, it is easy to trigger peeling from the adherend. In addition, it is possible to provide a surface protective film that can be easily peeled off and has a higher detection rate of scratches and foreign matters.

  The monomer component constituting the acrylic polymer may contain, for example, a polyfunctional monomer from the viewpoint that a crosslinked structure can be introduced into the acrylic polymer and appropriate cohesive force can be obtained.

  Examples of the polyfunctional monomer include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and 1,6 hexanediol di (meta). ) Acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, divinylbenzene, N, N′-methylenebisacrylamide and the like. Only one type of polyfunctional monomer may be used, or two or more types may be used.

  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, a crosslinking point is formed and a cohesive force can be obtained. , 180 degree peel strength is lighter and the wetting rate can be made faster, and it can be easily triggered for peeling from the adherend by combining with the specific base material layer adopted in the present invention. It is possible to provide a surface protective film that can be obtained and can be peeled lightly and has a higher detection rate of scratches and foreign matters.

  The monomer component constituting the acrylic polymer may include 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 a surfactant is used. It is -35, More preferably, it is 5-30. By adjusting the average added mole number of the oxyalkylene unit of the alkylene oxide group-containing reactive monomer within the above range, the effect of reducing the contamination of the protected substance by using the surfactant can be obtained efficiently. The terminal of the oxyalkylene chain may be a hydroxyl group or may be substituted with another functional group.

  The content ratio of the alkylene oxide group-containing reactive monomer to the total monomer components (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%. % By weight or less, particularly preferably 3% by weight or less, and most preferably 1% by weight or less. 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 effect of reducing the contamination of the protected object due to the use of the surfactant is efficiently achieved. Can be obtained.

  The oxyalkylene unit of the alkylene oxide group-containing reactive monomer preferably includes those having an alkylene group having 1 to 6 carbon atoms, such as an oxymethylene group, an oxyethylene group, an oxypropylene group, and an oxybutylene group. Is 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 constituent component, the compatibility between the acrylic polymer and the surfactant is improved, bleeding to the adherend is suitably suppressed, and low contamination An acrylic pressure-sensitive adhesive 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; It is done.

  Examples of the (meth) acrylic acid alkylene oxide adduct 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, methoxypolyethylene glycol (meth) acrylate, ethoxypolyethyleneglycol (meth) acrylate, butoxypolyethyleneglycol (meth) acrylate, octoxypolyethyleneglycol (meth) acrylate, lauroxypolyethyleneglycol (meth) Acrylate, stearoxy polyethylene glycol (meth) a Relate, phenoxy polyethylene glycol (meth) acrylate, methoxy polypropylene glycol (meth) acrylate, octoxypolyethylene glycol - polypropylene glycol (meth) acrylate.

  Examples of the reactive surfactant as an alkylene oxide group-containing reactive monomer include an anionic reactive surfactant having a (meth) acryloyl group or an allyl group, a nonionic reactive surfactant, and a cationic reactive interface. An active agent 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 Or, differently, it represents an alkylene group having 1 to 6 carbon atoms, and the average number of added moles m and n is 0 to 40, where (m + n) represents 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 and each represents an alkylene group having 1 to 6 carbon atoms, and R ³ and R ⁵ are the same or different and represent 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 number of added moles 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 added mole number n is a number of 3 to 40. Represents.

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

R ¹ in 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, X represents an anionic hydrophilic group, and the average number of moles added. n represents the number of 3-40.

In the formula (A6), R ¹ 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. X represents an anionic hydrophilic group, and the average addition mole number n represents a number of 3 to 40.

R ¹ in Formula (A7) represents hydrogen or a methyl group, R ² and R ⁴ are the same or different and each represents an alkylene group having 1 to 6 carbon atoms, and R ³ is 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 added mole number m and n are 0 to 40, where (m + n) represents a number of 3 to 40.

R ¹ and R ^{5 in} formula (A8) are the same or different and each represents hydrogen or a methyl group; R ² and R ⁴ are the same or different and each represents an alkylene group having 1 to 6 carbon atoms; R ³ is carbon A hydrocarbon group having a number of 1 to 30 is represented, M represents hydrogen, an alkali metal, an ammonium group, or an alkanol ammonium group, and the average number of added moles m and n is 0 to 40, where (m + n) is a number of 3 to 40. Represents.

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

^R 1, ^{R 2} in the formula (A10), and ^{R 3} are the same or different and each represents hydrogen or methyl, if ^{R 4} is a hydrocarbon group (0 carbon atoms containing from 0 to 30 carbon atoms ^{R 4} 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 number of added moles m and n is 0 to 40 However, (m + n) represents the number of 3-40.

  X in Formula (A1) to Formula (A6) and Formula (A10) to Formula (A10) represents an anionic hydrophilic group. Examples of the anionic hydrophilic group include those represented by formula (a1) to formula (a2).

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

  Examples of the nonionic reactive surfactant include those represented by formula (N1) to formula (N6).

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

R ¹ in 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 number of added moles n, m, and l is 0 to 40, and (n + m + 1) represents a number from 3 to 40.

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

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

R ¹ and R ^{3 in} formula (N5) are the same or different and each represents an alkylene group having 1 to 6 carbon atoms; R ² and R ⁴ are the same or different and are each a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms Or an average added mole number m and n are 0 to 40, provided that (m + n) represents a number of 3 to 40.

R ¹ , R ² , and R ^{3 in} formula (N6) are the same or different and represent hydrogen or a methyl group, and R ⁴ is a hydrocarbon group having 0 to 30 carbon atoms (in the case of 0 carbon atoms, there is no R4) R ⁵ and R ⁶ are the same or different and each represents an alkylene group having 1 to 6 carbon atoms, the average number of added moles m and n is 0 to 40, provided that (m + n) is 3 to 40 Represents a number.

  Examples of the alkylene oxide group-containing reactive monomer include Blemmer PME-400, Blemmer PME-1000, Blemmer 50POEP-800B (all of which are manufactured by NOF Corporation), Latem PD-420, Latem PD-430 (and all of which are both above) Commercial products such as Kao Corporation, Adeka Soap ER-10, and Adeka Soap NE-10 (all of which are manufactured by Asahi Denka Kogyo Co., Ltd.) may be used.

  Monomers (other monomers) other than (meth) acrylic acid alkyl ester, hydroxyl group-containing monomer, polyfunctional monomer, and alkylene oxide group-containing reactive monomer may be contained in the monomer component constituting the acrylic polymer. . Examples of other monomers include cyano group-containing monomers, vinyl ester monomers, aromatic vinyl monomers, amide group-containing monomers, imide group-containing monomers, amino group-containing monomers, epoxy group-containing monomers, vinyl ether monomers, and N-acryloylmorpholine. Is mentioned. Among these, a cyano group-containing monomer, a vinyl ester monomer, and an aromatic vinyl monomer are preferable from the viewpoint of improving cohesion and heat resistance. Further, from the viewpoint of improving adhesive force and having a functional group that functions 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-acryloylmorpholine are preferred. Only one type of other monomer may be used, or two or more types may be used.

  Examples of the cyano group-containing monomer include acrylonitrile and methacrylonitrile.

  Examples of the vinyl ester monomer 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 styrene.

  Examples of amide group-containing monomers include acrylamide, methacrylamide, diethyl acrylamide, N-vinyl pyrrolidone, N, N-dimethyl acrylamide, N, N-dimethyl methacrylamide, N, N-diethyl acrylamide, N, N-diethyl methacryl. Examples include amide, N, N′-methylenebisacrylamide, N, N-dimethylaminopropyl acrylamide, N, N-dimethylaminopropyl methacrylamide, and diacetone acrylamide.

  Examples of the imide group-containing monomer include cyclohexylmaleimide, isopropylmaleimide, N-cyclohexylmaleimide, and itaconimide.

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

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

  Examples of the vinyl ether monomer 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, and further preferably 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 monomer does not include a carboxyl group-containing monomer, a sulfo group-containing monomer, a phosphate group-containing monomer, and an acid anhydride group-containing monomer.

  The acrylic polymer can be obtained by polymerizing monomer components constituting the 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 acrylic polymer obtained may be any of a random copolymer, a block copolymer, an alternating copolymer, a graft copolymer, and the like.

  Examples of the solution polymerization method include a method in which a monomer component, a polymerization initiator, and the like are dissolved in a solvent and polymerized by heating to obtain an acrylic polymer solution containing an acrylic polymer.

  Various common solvents can be used as the solvent used in the solution polymerization. Examples of such solvents include 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; One type of solvent may be sufficient and 2 or more types may be sufficient as it.

  The blending ratio of the solvent is, for example, preferably 10 parts by weight to 1000 parts by weight, and 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. .

  Examples of the polymerization initiator used for solution polymerization include a peroxide polymerization initiator and an azo polymerization initiator. Examples of the peroxide polymerization initiator include peroxy carbonate, ketone peroxide, peroxy ketal, hydroperoxide, dialkyl peroxide, diacyl peroxide, peroxy ester, and more specifically, Benzoyl peroxide, t-butyl hydroperoxide, di-t-butyl peroxide, t-butyl peroxybenzoate, dicumyl peroxide, 1,1-bis (t-butylperoxy) -3,3,5- Examples include trimethylcyclohexane and 1,1-bis (t-butylperoxy) cyclododecane. Examples of the azo polymerization initiator include 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. Only one polymerization initiator may be used, or two or more polymerization initiators may be used.

  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 of monomer components (100 parts by weight) constituting the acrylic polymer. ~ 3 parts by weight.

  As heating temperature at the time of superposing | polymerizing by heating by solution polymerization, 50 to 80 degreeC is mentioned, for example. Examples of the heating time include 1 hour to 24 hours.

  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, it is possible to obtain a pressure-sensitive adhesive layer with lighter trigger peel force, lighter 180 degree peel force, and faster wetting rate. In combination with a specific base material layer adopted in the above, a surface protective film that can be easily peeled off from the adherend, can be peeled lightly, and has a higher detection rate of scratches and foreign matter. Can be provided. When the weight average molecular weight is less than 100,000, the cohesive force may be reduced, and adhesive residue is generated on the adherend surface after peeling the surface protective film of the present invention, and the adherend surface after peeling. There is a possibility that the effect of uniform wettability and adhesiveness cannot be obtained. When the weight average molecular weight exceeds 5,000,000, the wettability of the adherend surface after peeling 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 lower, more preferably −10 ° C. or lower. By adjusting the glass transition temperature of the acrylic polymer within the above range, it is possible to obtain a pressure-sensitive adhesive layer with lighter trigger peel force, lighter 180 degree peel force, and faster wetting rate. In combination with a specific base material layer adopted in the above, a surface protective film that can be easily peeled off from the adherend, can be peeled lightly, and has a higher detection rate of scratches and foreign matter. Can be provided. When glass transition temperature is higher than 0 degreeC, the wettability of the to-be-adhered body surface after peeling the surface protection film of this invention may become inadequate. 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 formula, where the glass transition temperature of the homopolymer obtained from each monomer is Tgn (° C.).

  1 / (Tg + 273) = Σ [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 the Represents the type.

The acid value of the acrylic polymer is preferably 15 or less. The acid value is measured using an automatic titration apparatus (Hiranuma Sangyo Co., Ltd., COM-550), and can be calculated from the following equation.
A = {(Y−X) × f × 5.611} / M
A: Acid value Y: Titration volume of sample solution (ml)
X: Titration volume of a solution containing only 50 g of mixed solvent (ml)
f: Factor of titration solution M: 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 obtain a sample solution.
Titration solution: 0.1N, 2-propanol potassium hydroxide solution (manufactured by Wako Pure Chemical Industries, Ltd., 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 improving the wettability of the surface protective film of the present invention.

  Examples of the surfactant include polyoxyalkylene fatty acid esters, polyoxyalkylene sorbitan fatty acid esters, polyoxyalkylene sorbitol fatty acid esters, polyoxyalkylene alkyl ethers, polyoxyalkylene alkyl allyl ethers, and 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, sulfoalkyl succinates such as dialkylsulfosuccinic acid alkali metal salts, higher fatty acid alkali metal salts, poly Anionic surfactants such as xoxyalkylene alkyl ether sulfates, polyoxyalkylene alkyl ether phosphates, polyoxyalkylene alkylphenyl ether sulfates, polyoxyalkylene alkylphenyl ether phosphates, alkylene oxide groups Examples thereof include cationic surfactants and amphoteric surfactants. Moreover, you may have reactive substituents, such as a (meth) acryloyl group and an allyl group, in a molecule | numerator. Only one type of surfactant may be used, or two or more types may be used.

  As the surfactant, an anionic surfactant is preferable in that the effect of the present invention can be sufficiently exhibited. Examples of anionic surfactants that can provide particularly excellent effects include polyoxyalkylene alkylphenyl ether sulfates (especially ammonium polyoxyethylene nonylpropenyl phenyl ether sulfate) and alkali metal dialkylsulfosuccinates (especially sodium dioctylsulfosuccinate). Is 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 (particularly a hydrocarbon group having 10 or 12 carbon atoms), X represents an anionic hydrophilic group, and an average addition mole The number n represents a number from 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 Formula (1) and the compound mentioned by Formula (2), what is represented by Formula (a1)-(a2) is mentioned.

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

  As the anionic surfactant, a general commercial product can be used. For example, trade name “AQUALON HS-10” (Daiichi Kogyo Seiyaku Co., Ltd.), trade name “Neocol P” (Daiichi Kogyo Seiyaku Co., Ltd.) , And trade name “Haitenol N-08” (Daiichi Kogyo Seiyaku Co., Ltd.). In addition, the trade name “Hytenol NF-13” (Daiichi Kogyo Seiyaku Co., Ltd.), the trade name “Hytenol NF-17” (Daiichi Kogyo Seiyaku Co., Ltd.), and the trade name “AQUALON KH-10” (No. 1) Ichi Kogyo Seiyaku Co., Ltd.).

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

  The blending amount of the surfactant is preferably 0.2 to 4 parts by weight, more preferably 0.2 to 3 parts by weight, and still more preferably 100 parts by weight of the acrylic polymer. 0.3 parts by weight to 3 parts by weight. By adjusting the blending amount of the surfactant with respect to 100 parts by weight of the acrylic polymer within the above range, the adhesive peel force is lighter, the 180 ° peel peel force is lighter, and the pressure-sensitive adhesive layer is faster. In combination with a specific base material layer employed in the present invention, it is possible to easily obtain a trigger for peeling from the adherend, and it can be peeled lightly. A higher surface protection film can be provided.

  The acrylic pressure-sensitive adhesive may contain a crosslinking agent from the viewpoint that an appropriate cohesive force can be obtained. Examples of the crosslinking agent include an isocyanate crosslinking agent, an epoxy crosslinking agent, a melamine crosslinking agent, an aziridine crosslinking agent, and a metal chelate crosslinking agent. Among these, an isocyanate type crosslinking agent and an epoxy type crosslinking agent are preferable in that the effects of the present invention can be sufficiently exhibited. One type of crosslinking agent may be sufficient and 2 or more types may be sufficient as it.

  Examples of the isocyanate crosslinking agent include lower aliphatic polyisocyanates such as butylene diisocyanate and hexamethylene diisocyanate, alicyclic isocyanates such as cyclopentylene diisocyanate, cyclohexylene diisocyanate and isophorone diisocyanate, and 2,4-tolylene diene. Isocyanate, aromatic isocyanates such as 4,4′-diphenylmethane diisocyanate, xylylene diisocyanate, trimethylolpropane / tolylene diisocyanate trimer adduct (trade name “Coronate L” manufactured by Nippon Polyurethane Industry Co., Ltd.), trimethylolpropane / Hexamethylene diisocyanate trimer adduct (trade name “Coronate 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 the epoxy crosslinking agent include bisphenol A, epichlorohydrin type epoxy resin, 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-xylenediamine (trade name “TETRAD-X” manufactured by Mitsubishi Gas Chemical Company), 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane (trade name “TETRAD-C” manufactured by Mitsubishi Gas Chemical Co., Inc.).

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

  The blending amount of the crosslinking agent is preferably 0.01 to 15 parts by weight, more preferably 0.5 to 10 parts by weight, and even more preferably 2 parts with respect to 100 parts by weight of the acrylic polymer. Parts by weight to 9 parts by weight, particularly preferably 6 parts by weight to 8 parts by weight. By adjusting the blending amount of the cross-linking agent with respect to 100 parts by weight of the acrylic polymer within the above range, the trigger peel force is lighter, the 180 degree peel strength is lighter, and the pressure-sensitive adhesive layer is faster. By combining with the specific base material layer employed in the present invention, the trigger for peeling from the adherend can be easily obtained, and light peeling can be easily achieved. A high surface protective film can be provided.

  The acrylic pressure-sensitive adhesive may contain a crosslinking catalyst. Examples of the crosslinking catalyst include metal-based crosslinking catalysts (particularly, tin-based crosslinking catalysts) such as tetra-n-butyl titanate, tetraisopropyl titanate, nursem ferric acid, butyltin oxide, and dioctyltin dilaurate. Only one type of crosslinking catalyst may be used, or two or more types may be used.

  The blending 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%, based on the total weight (100% by weight) of the pressure-sensitive adhesive layer. % By weight.

  The amount of the crosslinking catalyst is preferably 0.001 to 0.05 parts by weight, 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 weight part-0.03 weight part. By adjusting the blending amount of the cross-linking catalyst with respect to 100 parts by weight of the acrylic polymer within the above range, an adhesive layer having lighter trigger peel force, lighter 180 degree peel force, and faster wetting rate is obtained. By combining with the specific base material layer employed in the present invention, the trigger for peeling from the adherend can be easily obtained, and light peeling can be easily achieved. A high surface protective film can be provided. Further, by adjusting the blending amount of the cross-linking catalyst with respect to 100 parts by weight of the acrylic polymer within the above range, the cross-linking proceeds rapidly, so that the productivity can be improved.

  The acrylic pressure-sensitive adhesive may contain a crosslinking retarder. Examples of the crosslinking retarder include β-ketoesters such as methyl acetoacetate, ethyl acetoacetate, octyl acetoacetate, oleyl acetoacetate, lauryl acetoacetate, stearyl acetoacetate, acetylacetone, 2,4-hexanedione, benzoylacetone, etc. Β-diketone. Among these, acetylacetone is preferable in that the effects of the present invention can be sufficiently exhibited. Only one type of crosslinking retarder may be used, or two or more types may be used.

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

  The amount of the crosslinking retarder is preferably 0.1 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, and still more preferably 100 parts by weight of the acrylic polymer. 0.1 to 3 parts by weight. By adjusting the blending amount of the crosslinking retarder with respect to 100 parts by weight of the acrylic polymer within the above range, an adhesive layer having lighter trigger peel force, lighter 180 degree peel force, and faster wetting rate is obtained. In combination with a specific base material layer employed in the present invention, it is possible to easily obtain a trigger for peeling from the adherend, and it can be peeled lightly. A higher surface protection film can be provided. Moreover, the pot life 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 colorant (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 by mixing, for example, an acrylic polymer, a crosslinking agent, a crosslinking catalyst, a crosslinking retarder, and other additives.

≪Method for producing surface protective film≫
The surface protective film of the present invention can be produced by any appropriate method.

  The surface protective 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 material for forming an adhesive layer or a hot melt on a base material layer,
(2) According to (1), a method of transferring a pressure-sensitive adhesive layer applied and formed on a separator onto a base material layer,
(3) A method of forming and applying the forming material of the pressure-sensitive adhesive layer onto the base material layer,
(4) A method of extruding a base material layer and an adhesive layer in two layers or multiple layers,
(5) A method of laminating a pressure-sensitive adhesive layer on a base material layer, or a method of laminating two pressure-sensitive adhesive layers together with a laminate layer,
(6) A method of laminating a pressure-sensitive adhesive layer and a base material layer forming material such as a film or a laminate layer in two or multiple layers,
And can be prepared by any suitable method.

≪Usage≫
The surface protective film of the present invention can be easily peeled off from the adherend, can be peeled lightly, and has a high detection rate of scratches and foreign matter, so that the surface protection of optical and electronic members can be achieved. Can be suitably used. That is, the optical member of the present invention has the surface protective film of the present invention attached thereto. The electronic member of the present invention is obtained by attaching the surface protective film of the present invention.

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

<Weight average molecular weight>
A weight average molecular weight means what was obtained by measuring by a gel permeation chromatograph (GPC) method. More specifically, for example, as a GPC measuring device, the product name “HLC-8220GPC” (manufactured by Tosoh Corporation) is used for measurement under the following conditions, and the standard polystyrene equivalent can be calculated.
(Molecular weight measurement conditions)
Sample concentration: 0.2% by weight (tetrahydrofuran solution)
Sample injection volume: 10 μL
Sample column: TSKguardcolumn SuperHZ-H (1) + TSKgel SuperHZM-H (2)
・ Reference column: TSKgel SuperH-RC (1)
・ Eluent: Tetrahydrofuran (THF)
・ Flow rate: 0.6mL / min
・ Detector: Differential refractometer (RI)
Column temperature (measurement temperature): 40 ° C

<Total light transmittance>
The total light transmittance was measured using a haze meter (manufactured by Murakami Color Research Laboratory, model HM-150) according to the method defined in JIS K7361 “Plastic—Testing method for total light transmittance of transparent material”.

<Trigger peeling force at a peeling speed of 0.3 m / min and a peeling angle of 90 degrees with respect to glass>
After pasting the adhesive layer side of the surface protective film, cut to a width of 25 mm and peeled off the separator, onto the surface of a glass plate (manufactured by Matsunami Glass Industry Co., Ltd., trade name: Micro Slide Glass S) using a 2 kg roller , Left at 23 ° C. and 50% RH for 20 minutes, peeled off at a peel angle of 90 degrees and a peel speed of 0.3 m / min, and read the maximum force when the surface protective film began to peel off. It was.

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

<Wetting speed for glass>
(1) A part of the pressure-sensitive adhesive layer surface of a test piece (surface protective film cut to 2.5 cm × 15.0 cm) was adhered to a substrate (glass plate (manufactured by Matsunami Glass Industrial Co., Ltd., trade name: micro slide glass) S)) was held by hand so that the angle was 20 degrees to 30 degrees.
(2) Next, the hand was released from the test piece, and a video camera recorded that the adhesive layer surface of the test piece was in contact with the glass plate and spread in one direction from the contact portion. In the above (1), when a part of the pressure-sensitive adhesive layer surface of the test piece was wet and spread from the part other than the part in contact with the glass plate of the adherend, measurement / recording was not performed.
(3) the test piece was recorded the time until spreads all calculated in wetting rate (cm ² / sec) = Measured area (25 cm ²⁾ / recorded in seconds (sec), wetting rate (cm ² / sec ).
(4) The measurement was performed three times independently, and the average value was adopted. The measurement was performed in a class 10000 clean room (temperature 23 ° C., humidity 50% RH).

<Inspectability>
A glass plate (manufactured by Matsunami Glass Industry Co., Ltd., trade name: Micro Slide Glass S) is cut into a glass plate with a length of about 2 mm, and a surface protective film is applied to the surface opposite to the scratched surface. If the scratch could be easily confirmed by visual observation, it was rated as ◯, and if it was difficult to confirm, it was marked as x.

[Production Example 1]: Production of colored substrate (A) Black ink is applied 5 times or more to one surface of a transparent polyethylene terephthalate film (manufactured by Toray Industries, Inc., Lumirror S10, thickness = 38 μm) by gravure printing. What was processed was made into the colored base material (A).

[Production Example 2]: Production of transparent substrate (B) A transparent polyethylene terephthalate film (manufactured by Toray Industries, Inc., Lumirror S10, thickness = 38 μm) was used as the transparent substrate (B).

[Example 1]
As the polyol, Preminol S3011 (Asahi Glass Co., Ltd., Mn = 10000): 85 parts by weight, Sannix GP3000 (Sanyo Chemical Industries, Mn = 3000): 13 parts by weight, Sannix GP1000 (Sanyo Chemical Industries, Mn = 1000) ) Coronate HX (Nippon Polyurethane Industry Co., Ltd.) which is a polyfunctional alicyclic isocyanate compound as a polyfunctional isocyanate compound using 2 parts by weight: 18 parts by weight, catalyst (manufactured by Nippon Kagaku Sangyo Co., Ltd., trade name: Nasemu Dai) 2 iron): 0.08 parts by weight, Irganox 1010 (manufactured by BASF) as a deterioration inhibitor: 0.5 parts by weight, isopropyl myristate (manufactured by Kao, trade name: Exepar IPM): 30 parts by weight, diluted Mix 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 obtained urethane-based pressure-sensitive adhesive composition was applied to the colored substrate (A) obtained in Production Example 1 so that the thickness after drying with an applicator was 10 μm, and the drying temperature was 130 ° C. and the drying time was 2 minutes. Cure and dry under conditions. Thus, the adhesive layer which consists of a urethane type adhesive (A) on a coloring base material (A) was produced. Next, the surface of the pressure-sensitive adhesive layer was pasted with a silicone-treated surface of a base material made of a polyester resin having a thickness of 25 μm and subjected to silicone treatment on one surface to obtain a surface protective film (1).
The results are shown in Table 1.

[Example 2]
As the polyol, Preminol S3011 (Asahi Glass Co., Ltd., Mn = 10000): 85 parts by weight, Sannix GP3000 (Sanyo Chemical Industries, Mn = 3000): 13 parts by weight, Sannix GP1000 (Sanyo Chemical Industries, Mn = 1000) ) Coronate HX (Nippon Polyurethane Industry Co., Ltd.) which is a polyfunctional alicyclic isocyanate compound as a polyfunctional isocyanate compound using 2 parts by weight: 18 parts by weight, catalyst (manufactured by Nippon Kagaku Sangyo Co., Ltd., trade name: Nasemu Dai) 2 iron): 0.08 part by weight, Irganox 1010 (manufactured by BASF) as a deterioration preventing agent: 0.5 part by weight, isopropyl myristate (manufactured by Kao, trade name: Exepal IPM): 30 parts by weight, charging 1-ethyl-3-methylimidazolium bis (full Rosulfonyl) imide (Daiichi Kogyo Seiyaku, trade name: Elexel AS110): 1.25 parts by weight, modified silicone (manufactured by Shin-Etsu Chemical Co., trade name: KF-6004): 0.01 parts by weight, acetic acid as a diluent solvent Ethyl: 210 parts by weight was blended and stirred with a disper to obtain a urethane-based pressure-sensitive adhesive composition.
The obtained urethane-based pressure-sensitive adhesive composition was applied to the colored substrate (A) obtained in Production Example 1 so that the thickness after drying with an applicator was 10 μm, and the drying temperature was 130 ° C. and the drying time was 2 minutes. Cure and dry under conditions. Thus, the adhesive layer which consists of a urethane type adhesive (B) on the coloring base material (A) was produced. Next, the surface of the pressure-sensitive adhesive layer was pasted with a silicone-treated surface of a base material made of a polyester resin having a thickness of 25 μm and subjected to silicone treatment on one surface to obtain a surface protective film (2).
The results are shown in Table 1.

[Comparative Example 1]
As the polyol, Preminol S3011 (Asahi Glass Co., Ltd., Mn = 10000): 85 parts by weight, Sannix GP3000 (Sanyo Chemical Industries, Mn = 3000): 13 parts by weight, Sannix GP1000 (Sanyo Chemical Industries, Mn = 1000) ) Coronate HX (Nippon Polyurethane Industry Co., Ltd.) which is a polyfunctional alicyclic isocyanate compound as a polyfunctional isocyanate compound using 2 parts by weight: 18 parts by weight, catalyst (manufactured by Nippon Kagaku Sangyo Co., Ltd., trade name: Nasemu Dai) 2 iron): 0.08 parts by weight, Irganox 1010 (manufactured by BASF) as a deterioration inhibitor: 0.5 parts by weight, isopropyl myristate (manufactured by Kao, trade name: Exepar IPM): 30 parts by weight, diluted Mix 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 obtained urethane-based pressure-sensitive adhesive composition was applied to the transparent substrate (B) obtained in Production Example 2 so that the thickness after drying with an applicator was 10 μm, and the drying temperature was 130 ° C. and the drying time was 2 minutes. Cure and dry under conditions. Thus, the adhesive layer which consists of a urethane type adhesive (A) on a transparent base material (B) was produced. Next, the surface of the pressure-sensitive adhesive layer was pasted with the silicone-treated surface of a base material made of a polyester resin having a thickness of 25 μm and subjected to silicone treatment on one surface to obtain a surface protective film (C1).
The results are shown in Table 1.

Example 3
The separator of the surface protective film (1) obtained in Example 1 was peeled off, and the pressure-sensitive adhesive layer side was adhered to a polarizing plate (made by Nitto Denko Corporation, trade name “TEG1465DUHC”) as an optical member for surface protection. An optical member having a film attached thereto was obtained.

Example 4
The separator of the surface protective film (2) obtained in Example 2 was peeled off, and the pressure-sensitive adhesive layer side was attached to a polarizing plate (trade name “TEG1465DUHC” manufactured by Nitto Denko Corporation) as an optical member, and the surface An optical member having a protective film attached thereto was obtained.

Example 5
The separator of the surface protective film (1) obtained in Example 1 was peeled off, and the pressure-sensitive adhesive layer side was attached to an electroconductive film (Nitto Denko Corporation, trade name “Electrista V270L-TFMP”) as an electronic member. An electronic member having a surface protective film adhered thereto was obtained.

Example 6
The separator of the surface protective film (2) obtained in Example 2 was peeled off, and the pressure-sensitive adhesive layer side was attached to an electroconductive film (Nitto Denko Corporation, trade name “Electrista V270L-TFMP”) as an electronic member. An electronic member having a surface protective film adhered thereto was obtained.

  The surface protective film of this invention can be used suitably for the surface protection of an optical member or an electronic member.

DESCRIPTION OF SYMBOLS 1 Base material layer 2 Adhesive layer 3 Separator 10 Surface protection film 11 Colored layer

Claims (5)

A surface protective film having a base material layer mainly composed of a polyester resin and an adhesive layer,
The substrate layer is a colored substrate layer having a colored layer;
The total light transmittance of the surface protective film is 5% or less,
With respect to the glass of the surface protective film, the peeling speed is 0.3 m / min, the trigger peeling force at a peeling angle of 90 degrees is 1 N / 25 mm or less,
With respect to the glass of the surface protective film, the peeling force at a peeling speed of 0.3 m / min and a peeling angle of 180 degrees is 0.1 N / 25 mm or less,
The wetting speed of the surface protective film with respect to glass is 0.05 cm ² / sec or more,
Surface protective 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 pressure-sensitive adhesive and an acrylic pressure-sensitive adhesive.   The surface protective film according to claim 1, wherein the colored layer is a printing layer.   An optical member to which the surface protective film according to claim 1 is attached. An electronic member to which the surface protective film according to claim 1 is attached.

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