JP2017149129A - Optical member with surface protective film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an optical member with a surface protective film, on one surface of which a release liner is stuck via an adhesive layer and on the other surface of which a surface protective film is stuck, and which is inhibited from being peeled together with the release liner from the surface protective film when the release liner is intended to be peeled.SOLUTION: An optical member 1000 with a surface protective film includes a layered body of an optical member 30 and a surface protective film 100, an adhesive layer (2) 20 disposed on a side of the optical member 30, opposite to the surface protective film 100, and a release liner 10 disposed on a side of the adhesive layer (2) 20, opposite to the optical member 30, in the order mentioned above. In the optical member 1000 with a surface protective film, the surface protective film 100 includes a substrate layer 50 and an adhesive layer (1) 40, the adhesive layer (1) 40 of the surface protective film 100 is closer to the optical member 30, and the start peel force P of the optical member 30 from the layered body is greater than the start peel force Q of the release liner 10.SELECTED DRAWING: Figure 1

Description

  The present invention relates to an optical member with a surface protective film. The optical member with a surface protective film of the present invention is a member in which a surface protective film is bonded to the surface of the optical member.

  In the production process of an optical product such as a liquid crystal display device, a release liner is generally attached to one surface of an optical member such as a polarizing plate via an adhesive layer. And when bonding such an optical member to another member (for example, other optical member), a peeling liner is peeled before that, an adhesive layer is exposed, and it sticks to another member ( For example, Patent Document 1).

  On the other hand, a surface protective film is generally attached to the exposed surface side of the optical member in order to prevent scratches on the surface during processing, assembly, inspection, transportation, and the like. Such a surface protective film is peeled from the optical member when the surface protection is no longer necessary.

  That is, in an optical product manufacturing process such as a liquid crystal display device, a release liner is attached to one surface of the optical member via an adhesive layer, and a surface protective film is attached to the other surface. It is common that

  In such an optical member with a surface protective film, when the release liner is to be peeled off as described above, it is important that peeling occurs only at the interface between the release liner and the pressure-sensitive adhesive layer. However, in the conventional optical member with a surface protective film, when the release liner is peeled off as described above, the optical member is peeled off from the surface protective film together with the release liner, that is, optical There is a problem that peeling occurs at the interface between the member and the surface protective film. Such a problem is particularly noticeable when the optical member is thin.

Japanese Patent No. 3972676

  An object of the present invention is an optical member in which a release liner is attached to one surface via an adhesive layer and a surface protective film is attached to the other surface, and the release liner is to be peeled off. In providing an optical member with a surface protective film in which the optical member is hardly peeled off from the surface protective film together with the release liner, that is, hardly peeled off at the interface between the optical member and the surface protective film. is there.

The optical member with a surface protective film of the present invention is
A laminate of an optical member and a surface protective film, an adhesive layer (2) provided on the opposite side of the optical member from the surface protective film, and an adhesive layer (2) provided on the opposite side of the optical member. An optical member with a surface protective film having a release liner in this order,
The surface protective film includes a base material layer and an adhesive layer (1),
The pressure-sensitive adhesive layer (1) of the surface protective film is on the optical member side,
The trigger peel force P of the optical member from the laminate is larger than the trigger peel force Q of the release liner.

  In one embodiment, the thickness of the optical member is 1 μm to 500 μm.

  In one embodiment, the thickness of the surface protective film is 5 μm to 500 μm.

  In one embodiment, the release liner has a thickness of 1 μm to 500 μm.

  In one embodiment, the base material layer is a plastic film.

  In one embodiment, the pressure-sensitive adhesive contained in the pressure-sensitive adhesive layer (1) is at least one selected from a urethane-based pressure-sensitive adhesive, an acrylic pressure-sensitive adhesive, a rubber-based pressure-sensitive adhesive, and a silicone-based pressure-sensitive adhesive.

  In one embodiment, the urethane-based pressure-sensitive adhesive includes a polyurethane-based resin formed from a composition containing a polyol (A) and a polyfunctional isocyanate compound (B).

  In one embodiment, the equivalent ratio of NCO groups to OH groups in the polyol (A) and the polyfunctional isocyanate compound (B) is 2.0 or less as NCO groups / OH groups.

  In one embodiment, the urethane-based pressure-sensitive adhesive includes a polyurethane-based resin formed from a composition containing a urethane prepolymer (C) and a polyfunctional isocyanate compound (B).

  In one embodiment, the equivalent ratio of NCO groups to OH groups in the urethane prepolymer (C) and the polyfunctional isocyanate compound (B) is 2.0 or less as NCO groups / OH groups.

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

  In one embodiment, the acrylic pressure-sensitive adhesive (a) has a (meth) acrylic acid alkyl ester having 4 to 12 carbon atoms in the alkyl group of the alkyl ester moiety, and (b) an (meth) OH group. An acrylic resin formed from a composition containing at least one selected from an acrylic ester and (meth) acrylic acid, and (c) at least one selected from a polyfunctional isocyanate-based crosslinking agent and an epoxy-based crosslinking agent. Including.

In one embodiment, the wetting speed of the surface protective film with respect to the surface of the optical member is 5 cm ² / second or more.

  According to the present invention, an optical member having a release liner attached to one surface via an adhesive layer and a surface protective film attached to the other surface, the release liner being released The optical member is hardly peeled off from the surface protective film together with the release liner, that is, the optical member with the surface protective film is hardly peeled off at the interface between the optical member and the surface protective film. it can.

It is a schematic sectional drawing of the optical member with a surface protection film by one embodiment of this invention. It is a schematic sectional drawing explaining the trigger peeling force P of this optical member from the laminated body of an optical member and a surface protection film. It is a schematic sectional drawing explaining the trigger peeling force Q of a peeling liner.

≪≪Optical member with surface protective film≫≫
The optical member with a surface protective film of the present invention comprises a laminate of an optical member and a surface protective film, a pressure-sensitive adhesive layer (2) provided on the side of the optical member opposite to the surface protective film, and the pressure-sensitive adhesive layer ( 2) a release liner provided on the opposite side of the optical member, and an optical member with a surface protective film in this order, the surface protective film including a base material layer and an adhesive layer (1), The pressure-sensitive adhesive layer (1) of the surface protective film is on the optical member side.

  The optical member with a surface protective film of the present invention comprises a laminate of an optical member and a surface protective film, a pressure-sensitive adhesive layer (2) provided on the side of the optical member opposite to the surface protective film, and the pressure-sensitive adhesive layer ( If it has the release liner provided on the opposite side to the optical member of 2), it may have any other appropriate layer as long as the effects of the present invention are not impaired.

  FIG. 1 is a schematic cross-sectional view of an optical member with a surface protective film according to one embodiment of the present invention. 1, the optical member 1000 with a surface protective film of the present invention includes a release liner 10, an adhesive layer (2) 20, an optical member 30, an adhesive layer (1) 40, a base material layer 50, In this order, the pressure-sensitive adhesive layer (1) 40 and the base material layer 50 constitute the surface protective film 100.

  The thickness of the optical member is preferably 1 μm to 500 μm, more preferably 3 μm to 450 μm, still more preferably 5 μm to 400 μm, and particularly preferably 10 μm to 300 μm. In the optical member with a surface protective film of the present invention, the optical member is peeled off from the surface protective film together with the release liner when the release liner is peeled off even when the thickness of the optical member is thin. That is, it is possible to exhibit an effect that peeling is unlikely to occur at the interface between the optical member and the surface protective film.

  The thickness of the surface protective film is preferably 5 μm to 500 μm, more preferably 10 μm to 450 μm, still more preferably 15 μm to 400 μm, and particularly preferably 20 μm to 300 μm. By adjusting the thickness of the surface protective film within the above range, the optical member with the surface protective film of the present invention can be removed from the surface protective film together with the release liner when the release liner is to be peeled off. The effect that it is hard to peel, ie, it is hard to peel off at the interface of an optical member and a surface protection film can be expressed more.

  The thickness of the release liner is preferably 1 μm to 500 μm, more preferably 3 μm to 450 μm, still more preferably 5 μm to 400 μm, and particularly preferably 10 μm to 300 μm. When the thickness of the release liner is adjusted within the above range, the optical member with a surface protective film of the present invention is peeled from the surface protective film together with the release liner when the release liner is to be peeled off. The effect that it is difficult to be peeled off, that is, it is difficult for peeling to occur at the interface between the optical member and the surface protective film can be exhibited.

  In the optical member with a surface protective film of the present invention, the trigger peeling force P of the optical member from the laminate of the optical member and the surface protective film is larger than the trigger peeling force Q of the release liner. When the trigger peel force P is larger than the trigger peel force Q, the optical member with a surface protective film of the present invention is peeled off from the surface protective film together with the release liner when the release liner is to be peeled off. That is, it is difficult to peel off at the interface between the optical member and the surface protective film.

  The trigger peel force P / the trigger peel force Q is 1 or more.

  When the thickness of the release liner is 38 μm and the release speed is 300 mm / min, the trigger peel force P / the trigger peel force Q is preferably 5 or more, more preferably 5 to 20, and further preferably 6 to 15. Yes, particularly preferably 6-13. If the above-described trigger peeling force P / trigger peeling force Q is within the above range, the optical member with a surface protective film according to the present invention can be used together with the release liner when the release liner is to be peeled off. It is more difficult to peel from the surface protective film, that is, peeling is less likely to occur at the interface between the optical member and the surface protective film.

  When the thickness of the release liner is 38 μm and the release speed is 6 m / min, the trigger peeling force P / the trigger peeling force Q is preferably 2.1 or more, more preferably 2.1 to 20, and further preferably It is 2.3-15, Most preferably, it is 2.5-10. If the above-described trigger peeling force P / trigger peeling force Q is within the above range, the optical member with a surface protective film according to the present invention can be used together with the release liner when the release liner is to be peeled off. It is more difficult to peel from the surface protective film, that is, peeling is less likely to occur at the interface between the optical member and the surface protective film.

  When the thickness of the release liner is 50 μm and the release speed is 300 mm / min, the trigger peel force P / the trigger peel force Q is preferably 1.01 or more, more preferably 1.01 to 10, and still more preferably 1.03 to 5, particularly preferably 1.03 to 3. If the above-described trigger peeling force P / trigger peeling force Q is within the above range, the optical member with a surface protective film according to the present invention can be used together with the release liner when the release liner is to be peeled off. It is more difficult to peel from the surface protective film, that is, peeling is less likely to occur at the interface between the optical member and the surface protective film.

  When the thickness of the release liner is 50 μm and the release speed is 6 m / min, the trigger peel force P / the trigger peel force Q is preferably 1.05 or more, more preferably 1.05 to 10, and still more preferably It is 1.1-5, Most preferably, it is 1.2-3. If the above-described trigger peeling force P / trigger peeling force Q is within the above range, the optical member with a surface protective film according to the present invention can be used together with the release liner when the release liner is to be peeled off. It is more difficult to peel from the surface protective film, that is, peeling is less likely to occur at the interface between the optical member and the surface protective film.

  FIG. 2 is a schematic cross-sectional view for explaining the trigger peeling force P of the optical member from the laminate of the optical member and the surface protective film. As shown in FIG. 2, the trigger peeling force P is a trigger peeling force when peeling the optical member 30 from the laminate of the optical member 30 and the surface protective film 100. A method for measuring the trigger peel force P will be described later.

  FIG. 3 is a schematic cross-sectional view for explaining the trigger peeling force Q of the release liner. As shown in FIG. 3, the trigger peeling force Q is a trigger peeling force when peeling the release liner 10 from the laminate of the release liner 10, the pressure-sensitive adhesive layer (2) 20 and the optical member 30. A method for measuring the trigger peel force Q will be described later.

≪Optical member≫
Any appropriate optical member can be adopted as the optical member as long as the effects of the present invention are not impaired. The optical member may be a single layer or a multilayer. As such an optical member, Preferably, a polarizing plate, a multilayer optical element including a polarizing plate, a phase difference plate, a touch panel using an LCD, an LCD, a color filter used for an LCD, and the like are preferable.

≪Surface protection film≫
The surface protective film includes a base material layer and an adhesive layer (1). As long as the surface protective film includes the base material layer and the pressure-sensitive adhesive layer (1), the surface protective film may have any other appropriate layer as long as the effects of the present invention are not impaired.

The wetting speed of the surface protective film with respect to the surface of the optical member is preferably 5 cm ² / second or more, more preferably 7 cm ² / second or more, further preferably 8 cm ² / second or more, and particularly preferably 8.5 cm. ² / sec or more. If the wetting speed of the surface protective film with respect to the optical member surface is in the above range, the wetting speed of the surface protective film with respect to the optical member surface is excellent. For example, bubbles are unlikely to exist between the optical member surface and the surface protective film.

The surface protective film can be produced by any appropriate method. As such a manufacturing method, for example,
(1) A method of applying a solution or a hot melt of the forming material of the pressure-sensitive adhesive layer (1) on the base material layer,
(2) A method of transferring the pressure-sensitive adhesive layer (1) applied and formed in the form of a separator onto the substrate layer according to the above,
(3) A method for forming and applying the forming material of the pressure-sensitive adhesive layer (1) onto the base material layer,
(4) A method of extruding the base material layer and the pressure-sensitive adhesive layer (1) in two or multiple layers,
(5) A method of laminating the pressure-sensitive adhesive layer (1) on the base material layer or a method of laminating two layers of the pressure-sensitive adhesive layer together with the laminate layer,
(6) A method of laminating two or more layers of the pressure-sensitive adhesive layer (1) and a base material layer forming material such as a film or a laminate layer,
It can be performed according to any appropriate production method.

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

<Base material layer>
Only one layer may be sufficient as a base material layer, and two or more layers may be sufficient as it. The base material layer may be stretched.

  The thickness of the base material layer is preferably 4 μm to 450 μm, more preferably 8 μm to 400 μm, still more preferably 12 μm to 350 μm, and particularly preferably 16 μm to 250 μm. When the thickness of the base material layer is adjusted within the above range, the optical member with a surface protective film of the present invention is separated from the surface protective film together with the release liner when the release liner is to be peeled off. The effect that it is hard to peel, ie, it is hard to peel off at the interface of an optical member and a surface protection film can be expressed more.

  For the purpose of forming a wound body that can be easily rewound, for example, a fatty acid amide, a polyethyleneimine, a long-chain alkyl, It is possible to perform release treatment by adding a system additive or the like, or to provide a coat layer made of any appropriate release agent such as silicone, long-chain alkyl, or fluorine.

  Any appropriate material can be adopted as the material of the base material layer depending on the application. For example, a plastic, paper, a metal film, a nonwoven fabric, etc. are mentioned. Preferably, it is a plastic. That is, the base material layer is preferably a plastic film. The base material layer may be composed of one kind of material or may be composed of two or more kinds of materials. For example, you may be comprised from 2 or more types of plastics.

  Examples of the plastic include a polyester resin, a polyamide resin, and a polyolefin resin. Examples of the polyester resin include polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate. Examples of the polyolefin resin include olefin monomer homopolymers, olefin monomer copolymers, and the like. Specific examples of polyolefin resins include homopolypropylene; block-type, random-type, and graft-type propylene copolymers having an ethylene component as a copolymer component; reactor TPO; low density, high density, linear Low density, ultra-low density, etc. ethylene polymers; ethylene / propylene copolymer, ethylene / vinyl acetate copolymer, ethylene / methyl acrylate copolymer, ethylene / ethyl acrylate copolymer, ethylene / acrylic acid And ethylene copolymers such as butyl copolymer, ethylene / methacrylic acid copolymer, and ethylene / methyl methacrylate copolymer.

  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. In particular, when the material of the base material layer is plastic, it is preferable to contain some of the above additives for the purpose of preventing deterioration. From the viewpoint of improving weather resistance and the like, particularly preferred additives include antioxidants, ultraviolet absorbers, light stabilizers, and fillers.

  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 with respect to the base resin of the base layer (when the base layer is a blend, the blend is the base resin), more preferably It is 0.5 weight% or less, More preferably, it is 0.01 weight%-0.2 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 based on the base resin forming the base layer (when the base layer is a blend, the blend is the base resin), Preferably it is 1 weight% or less, More preferably, it is 0.01 weight%-0.5 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 based on the base resin forming the base layer (when the base layer is a blend, the blend is the base resin). Preferably it is 1 weight% or less, More preferably, it is 0.01 weight%-0.5 weight%.

  Any appropriate filler can be adopted as the filler. Examples of such fillers include inorganic fillers. Specific examples of the inorganic filler include carbon black, titanium oxide, and zinc oxide. The content of the filler is preferably 20% by weight or less with respect to the base resin forming the base layer (when the base layer is a blend, the blend is the base resin), and more preferably Is 10% by weight or less, more preferably 0.01% by weight to 10% by weight.

  Furthermore, as the additive, for the purpose of imparting antistatic properties, inorganic, low molecular weight and high molecular weight antistatic agents such as surfactants, inorganic salts, polyhydric alcohols, metal compounds, carbon and the like are also preferred. In particular, a high molecular weight antistatic agent and carbon are preferable from the viewpoint of contamination and adhesiveness maintenance.

<Adhesive layer (1)>
The pressure-sensitive adhesive layer (1) can be produced by any appropriate production method. Examples of such a production method include a method in which a composition that is a material for forming the pressure-sensitive adhesive layer (1) is applied on the base material layer, and the pressure-sensitive adhesive layer (1) is formed on the base material layer. . Examples of such coating methods include roll coating, gravure coating, reverse coating, roll brushing, spray coating, air knife coating, extrusion coating using a die coater, and the like.

  The thickness of the pressure-sensitive adhesive layer (1) is preferably 1 μm to 150 μm, more preferably 2 μm to 140 μm, still more preferably 3 μm to 130 μm, and particularly preferably 4 μm to 120 μm. By adjusting the thickness of the pressure-sensitive adhesive layer (1) within the above range, the optical member with a surface protective film of the present invention has a surface along with the release liner when the release liner is to be peeled off. The effect that it is difficult to peel from the protective film, that is, peeling hardly occurs at the interface between the optical member and the surface protective film, can be more manifested.

  The content of the pressure-sensitive adhesive in the pressure-sensitive adhesive layer (1) is preferably 50% by weight to 100% by weight, more preferably 60% by weight to 100% by weight, and further preferably 70% by weight to 100% by weight. And particularly preferably 80% to 100% by weight, and most preferably 90% to 100% by weight. By adjusting the content ratio of the pressure-sensitive adhesive in the pressure-sensitive adhesive layer (1) within the above range, the optical member with a surface protective film of the present invention is such that when the release liner is to be peeled off, the optical member becomes the release liner. It is possible to develop an effect that it is difficult to peel off from the surface protective film together with the surface protective film, that is, it is difficult to peel off at the interface between the optical member and the surface protective film.

  The pressure-sensitive adhesive contained in the pressure-sensitive adhesive layer (1) is preferably at least one selected from a urethane-based pressure-sensitive adhesive, an acrylic pressure-sensitive adhesive, a rubber-based pressure-sensitive adhesive, and a silicone-based pressure-sensitive adhesive. In terms of expression, it is more preferably at least one selected from a urethane-based pressure-sensitive adhesive and an acrylic pressure-sensitive adhesive, and more preferably a urethane-based pressure-sensitive adhesive.

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

  The content of the polyurethane-based resin in the urethane-based adhesive is preferably 50% by weight to 100% by weight, more preferably 70% by weight to 100% by weight, and still more preferably 90% by weight to 100% by weight. Particularly preferably 95% to 100% by weight, most preferably 98% to 100% by weight. By adjusting the content ratio of the polyurethane-based resin in the urethane-based pressure-sensitive adhesive within the above range, the optical member with a surface protective film of the present invention has an optical member that is separated from the release liner when the release liner is to be peeled off. The effect that it is difficult to peel together from a surface protection film together, ie, it is hard to peel at the interface of an optical member and a surface protection film, can be expressed more.

  The urethane-based pressure-sensitive adhesive can contain any appropriate other component in addition to the polyurethane-based resin as long as the effects of the present invention are not impaired. Examples of such other components include resin components other than polyurethane resins, tackifiers, inorganic fillers, organic fillers, metal powders, pigments, foils, softeners, anti-aging agents, conductive agents, Examples include ultraviolet absorbers, antioxidants, light stabilizers, surface lubricants, leveling agents, corrosion inhibitors, heat stabilizers, polymerization inhibitors, lubricants, solvents, and catalysts.

  Any appropriate polyurethane resin can be adopted as the polyurethane resin as long as the effects of the present invention are not impaired. The polyurethane resin is preferably a polyurethane resin formed from a composition containing a polyol (A) and a polyfunctional isocyanate compound (B), or a urethane prepolymer (C) and a polyfunctional isocyanate compound (B). It is a polyurethane-type resin formed from the composition containing this. By adopting the above as the polyurethane-based resin, the optical member with a surface protective film of the present invention is peeled off from the surface protective film together with the release liner when the release liner is to be peeled off. The effect that it is difficult to be peeled off, that is, it is difficult for peeling to occur at the interface between the optical member and the surface protective film can be exhibited.

  The polyurethane-based resin can contain any appropriate other component as long as the effects of the present invention are not impaired. Examples of such other components include resin components other than polyurethane resins, tackifiers, inorganic fillers, organic fillers, metal powders, pigments, foils, softeners, anti-aging agents, conductive agents, Examples include ultraviolet absorbers, antioxidants, light stabilizers, surface lubricants, leveling agents, corrosion inhibitors, heat stabilizers, polymerization inhibitors, lubricants, solvents, and catalysts.

  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.

  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 hindered amine light stabilizers include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, and methyl. Examples include 1,2,2,6,6-pentamethyl-4-piperidyl sebacate.

  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 urethane-based pressure-sensitive adhesive may contain a fatty acid ester. 1 type of fatty acid ester may be sufficient and 2 or more types may be sufficient as it.

  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, most preferably 250 to 350. 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, monoglyceride behenate, 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, triglycera 2-ethylhexanoate De, butyl laurate, and the like octyl oleate.

  The blending ratio of the fatty acid ester when preparing the urethane-based pressure-sensitive adhesive is, for example, preferably 5% to 50% by weight, and more preferably 7% to 45% by weight with respect to the polyol (A). More preferably 8 to 40% by weight, particularly preferably 9 to 35% by weight, most preferably 10 to 30% by weight.

  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. Only one type of ionic liquid may be used, or two or more types may be used.

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

  As the ionic liquid, any appropriate ionic liquid can be adopted as long as it does not impair the effects of the present invention as long as it is an ionic liquid containing a fluoro organic anion. 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 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 may 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 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.

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

  The polyol (A) may be only one type or two or more types.

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

  Examples of the polyol (A) preferably include polyester polyol, polyether polyol, polycaprolactone polyol, polycarbonate polyol, and castor oil-based polyol. The polyol (A) is more preferably a polyether polyol.

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

  Examples of the polyol component include ethylene glycol, diethylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 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.

  The number average molecular weight Mn of the polyol (A) is preferably 400 to 20000, more preferably 500 to 17000, still more preferably 600 to 15000, and particularly preferably 800 to 12000. By adjusting the number average molecular weight Mn of the polyol (A) within the above range, the optical member with a surface protective film of the present invention has a surface along with the release liner when the release liner is to be peeled off. The effect that it is difficult to peel from the protective film, that is, peeling hardly occurs at the interface between the optical member and the surface protective film, can be more manifested.

  The polyol (A) preferably contains a polyol (A1) having three OH groups and a number average molecular weight Mn of 8000 to 20000. As for a polyol (A1), only 1 type may be sufficient and 2 or more types may be sufficient.

  The content ratio of the polyol (A1) in the polyol (A) is preferably 70% by weight or more, more preferably 70% by weight to 100% by weight, and further preferably 70% by weight to 90% by weight. By adjusting the content ratio of the polyol (A1) in the polyol (A) within the above range, when the optical member with a surface protective film of the present invention is to release the release liner, the optical member becomes the release liner. It is possible to develop an effect that it is difficult to peel off from the surface protective film together with the surface protective film, that is, it is difficult to peel off at the interface between the optical member and the surface protective film.

  The number average molecular weight Mn of the polyol (A1) is preferably 8000 to 20000, more preferably 8000 to 18000, further preferably 8500 to 17000, further preferably 9000 to 16000, and particularly preferably 9500. -15500, most preferably 10000-15000. By adjusting the number average molecular weight Mn of the polyol (A1) within the above range, the optical member with a surface protective film of the present invention has a surface along with the release liner when the release liner is to be peeled off. The effect that it is difficult to peel from the protective film, that is, peeling hardly occurs at the interface between the optical member and the surface protective film, can be more manifested.

  The polyol (A) may contain a polyol (A2) having 3 or more OH groups and a number average molecular weight Mn of 5000 or less. The polyol (A2) may be only one kind or two or more kinds. The number average molecular weight Mn of the polyol (A2) is preferably 500 to 5000, more preferably 800 to 4500, still more preferably 1000 to 4000, particularly preferably 1000 to 3500, and most preferably 1000. ~ 3000. When the number average molecular weight Mn of the polyol (A2) is out of the above range, the adhesive strength may increase with time, and excellent reworkability may not be exhibited. The polyol (A2) is preferably a polyol (triol) having 3 OH groups, a polyol (tetraol) having 4 OH groups, a polyol (pentaol) having 5 OH groups, and 6 OH groups. The polyol (hexaol) which has is mentioned.

  As the polyol (A2), a total amount of at least one of a polyol having 4 OH groups (tetraol), a polyol having 5 OH groups (pentaol), and a polyol having 6 OH groups (hexaol) is: The content ratio in the polyol (A) is preferably 10% by weight or less, more preferably 7% by weight or less, still more preferably 6% by weight or less, and particularly preferably 5% by weight or less. In the polyol (A), as the polyol (A2), at least of a polyol having 4 OH groups (tetraol), a polyol having 5 OH groups (pentaol), and a polyol having 6 OH groups (hexaol) By adjusting 1 type to the said range, the urethane type adhesive which was further excellent in transparency can be provided.

  The content ratio of the polyol (A2) in the polyol (A) is preferably 30% by weight or less, more preferably 0% by weight to 30% by weight. By adjusting the content ratio of the polyol (A2) in the polyol (A) within the above range, when the optical member with a surface protective film of the present invention is to release the release liner, the optical member becomes the release liner. It is possible to develop an effect that it is difficult to peel off from the surface protective film together with the surface protective film, that is, it is difficult to peel off at the interface between the optical member and the surface protective film.

  In the polyol (A2), the content ratio of the polyol having a number average molecular weight Mn of 5,000 or less having 4 or more OH groups therein is preferably less than 10% by weight, more preferably based on the whole polyol (A). Is 8% by weight or less, more preferably 7% by weight or less, particularly preferably 6% by weight or less, and most preferably 5% by weight or less. When the content ratio of the polyol having a number average molecular weight Mn of 5000 or less and having 4 or more OH groups in the polyol (A2) is 10% by weight or more with respect to the whole polyol (A), the urethane-based pressure-sensitive adhesive is white. There is a risk that transparency will be reduced.

  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 equivalent ratio of NCO groups to OH groups in the polyol (A) and the polyfunctional isocyanate compound (B) is preferably 2.0 or less, more preferably 0.1 to 1.9, as NCO groups / OH groups. More preferably, it is 0.2-1.8, Most preferably, it is 0.3-1.7, Most preferably, it is 0.5-1.6. By adjusting the equivalent ratio of NCO group / OH group within the above range, the optical member with a surface protective film of the present invention can protect the optical member together with the release liner when the release liner is peeled off. The effect that it is hard to peel from a film, ie, it is hard to peel at the interface of an optical member and a surface protection film, can be expressed more.

  The content ratio of the polyfunctional isocyanate compound (B) is preferably 1.0% by weight to 20% by weight, more preferably 1.5% by weight of the polyfunctional isocyanate compound (B) with respect to the polyol (A). % To 19% by weight, more preferably 2.0% to 18% by weight, particularly preferably 2.3% to 17% by weight, and most preferably 2.5% to 16% by weight. It is. By adjusting the content ratio of the polyfunctional isocyanate compound (B) within the above range, the optical member with a surface protective film of the present invention can be used together with the release liner when the release liner is to be peeled off. The effect that it is difficult to peel from the surface protective film, that is, peeling hardly occurs at the interface between the optical member and the surface protective film, can be further exhibited.

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

  The method of curing the composition containing the polyol (A) and the polyfunctional isocyanate compound (B) to form the polyurethane resin includes the effects of the present invention, such as a urethanization reaction method using bulk polymerization or solution polymerization. Any appropriate method can be adopted as long as the above is not impaired.

  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, the optical member with a surface protective film of the present invention is less likely to be peeled from the surface protective film together with the release liner when the release liner is to be peeled off. That is, the effect that peeling hardly occurs at the interface between the optical member and the surface protective film can be further expressed.

  The composition containing the polyol (A) and the polyfunctional isocyanate compound (B) may contain any appropriate other component as long as the effects of the present invention are not impaired. Examples of such other components include resin components other than polyurethane resins, tackifiers, inorganic fillers, organic fillers, metal powders, pigments, foils, softeners, anti-aging agents, conductive agents, Examples include ultraviolet absorbers, antioxidants, light stabilizers, surface lubricants, leveling agents, corrosion inhibitors, heat stabilizers, polymerization inhibitors, lubricants, solvents, and catalysts.

(Polyurethane resin formed from a composition containing urethane prepolymer (C) and polyfunctional isocyanate compound (B))
The polyurethane resin formed from the composition containing the urethane prepolymer (C) and the polyfunctional isocyanate compound (B) may be any polyurethane resin obtained by using a so-called “urethane prepolymer” as a raw material. A suitable polyurethane-based resin can be employed.

  The polyurethane resin formed from the composition containing the urethane prepolymer (C) and the polyfunctional isocyanate compound (B) contains, for example, a polyurethane polyol as the urethane prepolymer (C) and the polyfunctional isocyanate compound (B). And a polyurethane-based resin formed from the composition. Only one type of urethane prepolymer (C) may be used, or two or more types may be used. One type of polyfunctional isocyanate compound (B) may be sufficient, and 2 or more types may be sufficient as it.

  The polyurethane polyol as the urethane prepolymer (C) preferably reacts the polyester polyol (a1) and the polyether polyol (a2) with the organic polyisocyanate compound (a3) in the presence or absence of a catalyst. It is something to be made.

  Any appropriate polyester polyol can be used as the polyester polyol (a1). Examples of such polyester polyol (a1) include polyester polyols obtained by reacting an acid component and a glycol component. Examples of the acid component include terephthalic acid, adipic acid, azelaic acid, sebacic acid, phthalic anhydride, isophthalic acid, trimellitic acid, and the like. Examples of the glycol component include ethylene glycol, propylene glycol, diethylene glycol, butylene glycol, 1,6-hexane glycol, 3-methyl-1,5-pentanediol, 3,3′-dimethylol heptane, polyoxyethylene glycol, Examples of the polyoxypropylene glycol, 1,4-butanediol, neopentyl glycol, butylethylpentanediol, and polyol component include glycerin, trimethylolpropane, and pentaerythritol. Other examples of the polyester polyol (a1) include polyester polyols obtained by ring-opening polymerization of lactones such as polycaprolactone, poly (β-methyl-γ-valerolactone), and polyvalerolactone.

  The molecular weight of the polyester polyol (a1) can be used from a low molecular weight to a high molecular weight. The molecular weight of the polyester polyol (a1) is preferably a number average molecular weight of 500 to 5,000. When the number average molecular weight is less than 500, the reactivity becomes high and the gelation tends to occur. When the number average molecular weight exceeds 5000, the reactivity is lowered, and the cohesive force of the polyurethane polyol itself may be reduced. The amount of the polyester polyol (a1) used is preferably 10 to 90 mol% in the polyol constituting the polyurethane polyol.

  Any appropriate polyether polyol can be used as the polyether polyol (a2). As such a polyether polyol (a2), for example, a low molecular weight polyol such as water, propylene glycol, ethylene glycol, glycerin, trimethylolpropane or the like is used as an initiator, and ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran or the like is used. The polyether polyol obtained by polymerizing an oxirane compound is mentioned. Specific examples of such polyether polyol (a2) include polyether polyols having 2 or more functional groups such as polypropylene glycol, polyethylene glycol, and polytetramethylene glycol.

  The molecular weight of the polyether polyol (a2) can be used from a low molecular weight to a high molecular weight. As a molecular weight of polyether polyol (a2), a number average molecular weight becomes like this. Preferably it is 1000-5000. When the number average molecular weight is less than 1000, the reactivity is high and the gelation tends to occur. When the number average molecular weight exceeds 5000, the reactivity is lowered, and the cohesive force of the polyurethane polyol itself may be reduced. The amount of the polyether polyol (a2) used is preferably 20 mol% to 80 mol% in the polyol constituting the polyurethane polyol.

  A part of the polyether polyol (a2), if necessary, may be glycols such as ethylene glycol, 1,4-butanediol, neopentyl glycol, butylethylpentanediol, glycerin, trimethylolpropane, pentaerythritol, They can be used in combination with polyamines such as ethylenediamine, N-aminoethylethanolamine, isophoronediamine, and xylylenediamine.

  As the polyether polyol (a2), only a bifunctional polyether polyol may be used, or a polyether having a number average molecular weight of 1000 to 5000 and having at least 3 hydroxyl groups in one molecule. A part or all of the polyol may be used. When the polyether polyol (a2) has an average molecular weight of 1000 to 5000 and a part or all of the polyether polyol having at least 3 hydroxyl groups in one molecule, a balance between adhesive force and removability is obtained. Can be good. In such a polyether polyol, if the number average molecular weight is less than 1000, the reactivity becomes high and there is a possibility that gelation tends to occur. Further, in such a polyether polyol, when the number average molecular weight exceeds 5000, the reactivity is lowered, and further, the cohesive force of the polyurethane polyol itself may be reduced. The number average molecular weight of such a polyether polyol is more preferably 2500 to 3500.

  Any appropriate organic polyisocyanate compound can be used as the organic polyisocyanate compound (a3). Examples of such an organic polyisocyanate compound (a3) include aromatic polyisocyanates, aliphatic polyisocyanates, araliphatic polyisocyanates, and alicyclic polyisocyanates.

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

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

  Examples of the araliphatic polyisocyanate include ω, ω′-diisocyanate-1,3-dimethylbenzene, ω, ω′-diisocyanate-1,4-dimethylbenzene, ω, ω′-diisocyanate-1,4-diethylbenzene. 1,4-tetramethylxylylene diisocyanate, 1,3-tetramethylxylylene diisocyanate, and the like.

  Examples of the alicyclic polyisocyanate include 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate, 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, and methyl-2. , 4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), 1,4-bis (isocyanatemethyl) cyclohexane, 1,4-bis (isocyanatemethyl) cyclohexane, etc. It is done.

  As the organic polyisocyanate compound (a3), a trimethylolpropane adduct, a burette reacted with water, a trimer having an isocyanurate ring, and the like can be used in combination.

  Any appropriate catalyst can be used as the catalyst that can be used in obtaining the polyurethane polyol. Examples of such a catalyst include tertiary amine compounds and organometallic compounds.

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

  Examples of organometallic compounds include tin compounds and non-tin compounds.

  Examples of the tin compound include dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin dimaleate, dibutyltin dilaurate (DBTDL), dibutyltin diacetate, dibutyltin sulfide, tributyltin sulfide, tributyltin oxide, tributyl Examples thereof include tin acetate, triethyltin ethoxide, tributyltin ethoxide, dioctyltin oxide, tributyltin chloride, tributyltin trichloroacetate, and tin 2-ethylhexanoate.

  Examples of non-tin compounds include titanium compounds such as dibutyltitanium dichloride, tetrabutyltitanate and butoxytitanium trichloride; lead compounds such as lead oleate, lead 2-ethylhexanoate, lead benzoate and lead naphthenate Iron compounds such as iron 2-ethylhexanoate and iron acetylacetonate; cobalt compounds such as cobalt benzoate and cobalt 2-ethylhexanoate; zinc compounds such as zinc naphthenate and zinc 2-ethylhexanoate; And zirconium-based compounds such as zirconium naphthenate.

  When a catalyst is used in obtaining a polyurethane polyol, in a system in which two types of polyols, a polyester polyol and a polyether polyol, are present, due to the difference in reactivity, in a single catalyst system, gelation or a reaction solution is caused. The problem of becoming cloudy is likely to occur. Therefore, by using two kinds of catalysts when obtaining the polyurethane polyol, the reaction rate, the selectivity of the catalyst and the like can be easily controlled, and these problems can be solved. Examples of such a combination of two types of catalysts include tertiary amine / organometallic, tin / non-tin, and tin / tin, preferably tin / tin, more preferably Is a combination of dibutyltin dilaurate and tin 2-ethylhexanoate. The blending ratio is, by weight ratio, 2-ethylhexanoic acid tin / dibutyltin dilaurate is preferably less than 1, more preferably 0.2 to 0.6. If the blending ratio is 1 or more, gelation tends to occur due to the balance of catalytic activity.

  When a catalyst is used in obtaining the polyurethane polyol, the amount of the catalyst used is preferably 0.01 with respect to the total amount of the polyester polyol (a1), the polyether polyol (a2) and the organic polyisocyanate compound (a3). -1.0 wt%.

  When using a catalyst in obtaining a polyurethane polyol, the reaction temperature is preferably less than 100 ° C, more preferably 85 ° C to 95 ° C. If it is 100 ° C. or higher, it may be difficult to control the reaction rate and the crosslinked structure, and it may be difficult to obtain a polyurethane polyol having a predetermined molecular weight.

  When obtaining a polyurethane polyol, it is not necessary to use a catalyst. In that case, reaction temperature becomes like this. Preferably it is 100 degreeC or more, More preferably, it is 110 degreeC or more. Moreover, when obtaining a polyurethane polyol without a catalyst, it is preferable to make it react for 3 hours or more.

  For example, 1) polyester polyol, polyether polyol, catalyst, and organic polyisocyanate are charged in a flask. 2) polyester polyol, polyether polyol, and catalyst are charged in a flask, and organic polyisocyanate is obtained. The method of adding by dripping is mentioned. As a method for obtaining the polyurethane polyol, the method 2) is preferable in controlling the reaction.

  Any suitable solvent can be used to obtain the polyurethane polyol. Examples of such a solvent include methyl ethyl ketone, ethyl acetate, toluene, xylene, and acetone. Among these solvents, toluene is preferable.

  What was mentioned above can be used as a polyfunctional isocyanate compound (B).

  The composition containing the urethane prepolymer (C) and the polyfunctional isocyanate compound (B) may contain any appropriate other component as long as the effects of the present invention are not impaired. Examples of such other components include resin components other than polyurethane resins, tackifiers, inorganic fillers, organic fillers, metal powders, pigments, foils, softeners, anti-aging agents, conductive agents, Examples include ultraviolet absorbers, antioxidants, light stabilizers, surface lubricants, leveling agents, corrosion inhibitors, heat stabilizers, polymerization inhibitors, lubricants, solvents, and catalysts.

  As a method for producing a polyurethane resin formed from a composition containing a urethane prepolymer (C) and a polyfunctional isocyanate compound (B), a polyurethane resin is produced using a so-called “urethane prepolymer” as a raw material. Any appropriate manufacturing method may be adopted as long as it is a method.

  The number average molecular weight Mn of the urethane prepolymer (C) is preferably 1000 to 100,000.

  In the urethane prepolymer (C) and the polyfunctional isocyanate compound (B), the equivalent ratio of the NCO group to the OH group is preferably 2.0 or less, more preferably 0.1 to 1 as the NCO group / OH group. 0.9, more preferably 0.2 to 1.8, particularly preferably 0.3 to 1.7, and most preferably 0.5 to 1.6. By adjusting the equivalent ratio of NCO group / OH group within the above range, the optical member with a surface protective film of the present invention can protect the optical member together with the release liner when the release liner is peeled off. The effect that it is hard to peel from a film, ie, it is hard to peel at the interface of an optical member and a surface protection film, can be expressed more.

  The content ratio of the polyfunctional isocyanate compound (B) is preferably 1.0% by weight to 10% by weight of the polyfunctional isocyanate compound (B) with respect to the urethane prepolymer (C), more preferably 1. 5 wt% to 9.5 wt%, more preferably 2.0 wt% to 9 wt%, particularly preferably 2.3 wt% to 8.5 wt%, and most preferably 2.5 wt%. % By weight to 8% by weight. By adjusting the content ratio of the polyfunctional isocyanate compound (B) within the above range, the optical member with a surface protective film of the present invention can be used together with the release liner when the release liner is to be peeled off. The effect that it is difficult to peel from the surface protective film, that is, peeling hardly occurs at the interface between the optical member and the surface protective film, can be further exhibited.

[Acrylic adhesive]
The acrylic adhesive contains an acrylic resin.

  The content of the acrylic resin in the acrylic pressure-sensitive adhesive is preferably 50% to 100% by weight, more preferably 70% to 100% by weight, and still more preferably 90% to 100% by weight. Particularly preferably 95% to 100% by weight, most preferably 98% to 100% by weight. By adjusting the content ratio of the acrylic resin in the acrylic pressure-sensitive adhesive within the above range, when the optical member with a surface protective film of the present invention is intended to release the release liner, the optical member is separated from the release liner. The effect that it is difficult to peel together from a surface protection film together, ie, it is hard to peel at the interface of an optical member and a surface protection film, can be expressed more.

  The acrylic pressure-sensitive adhesive may contain any appropriate other component in addition to the acrylic resin as long as the effects of the present invention are not impaired. Examples of such other components include resin components other than acrylic resins, tackifiers, inorganic fillers, organic fillers, metal powders, pigments, foils, softeners, anti-aging agents, conductive agents, Examples include ultraviolet absorbers, antioxidants, light stabilizers, surface lubricants, leveling agents, corrosion inhibitors, heat stabilizers, polymerization inhibitors, lubricants, solvents, and catalysts.

  Any appropriate acrylic resin can be adopted as the acrylic resin as long as the effects of the present invention are not impaired. The acrylic pressure-sensitive adhesive is preferably (a) a (meth) acrylic acid alkyl ester having 4 to 12 carbon atoms in the alkyl group of the alkyl ester moiety, (b) a (meth) acrylic acid ester having an OH group and ( It includes an acrylic resin formed from a composition containing at least one selected from (meth) acrylic acid and (c) at least one selected from a polyfunctional isocyanate-based crosslinking agent and an epoxy-based crosslinking agent.

  The content ratio of the component (a) in the composition forming the acrylic resin is preferably 85% by weight to 99.5% by weight, more preferably 90% by weight to 98.5% by weight, and still more preferably. Is 92.5 wt% to 98 wt%, particularly preferably 95 wt% to 97.5 wt%. By adjusting the content ratio of the component (a) in the composition forming the acrylic resin within the above range, the optical member with a surface protective film of the present invention is an optical member when the release liner is to be peeled off. Can be more difficult to be peeled off from the surface protective film together with the release liner, that is, the effect that peeling does not easily occur at the interface between the optical member and the surface protective film can be exhibited.

  The content ratio of the component (b) in the composition forming the acrylic resin is preferably 0.5% by weight to 15% by weight, more preferably 1.5% by weight to 10% by weight, and still more preferably. Is 2 to 7.5% by weight, particularly preferably 2.5 to 5% by weight. By adjusting the content ratio of the component (b) in the composition forming the acrylic resin within the above range, the optical member with a surface protective film of the present invention is an optical member when the release liner is to be peeled off. Can be more difficult to be peeled off from the surface protective film together with the release liner, that is, the effect that peeling does not easily occur at the interface between the optical member and the surface protective film can be exhibited.

  The content ratio of the component (c) in the composition forming the acrylic resin is preferably 1% by weight to 10% by weight, more preferably 1.5% by weight to 9% by weight, and further preferably 2%. % By weight to 8% by weight, particularly preferably 2.5% by weight to 7% by weight. By adjusting the content ratio of the component (c) in the composition for forming the acrylic resin within the above range, the optical member with a surface protective film of the present invention is an optical member when the release liner is to be peeled off. Can be more difficult to be peeled off from the surface protective film together with the release liner, that is, the effect that peeling does not easily occur at the interface between the optical member and the surface protective film can be exhibited.

  Examples of the (meth) acrylic acid alkyl ester having 4 to 12 carbon atoms in the alkyl ester moiety include n-butyl (meth) acrylate, iso-butyl (meth) acrylate, and t-butyl (meth) acrylate. , N-pentyl (meth) acrylate, iso-pentyl (meth) acrylate, n-hexyl (meth) acrylate, iso-hexyl (meth) acrylate, n-heptyl (meth) acrylate, iso-heptyl (meth) acrylate, 2 -Ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, iso-octyl (meth) acrylate, n-nonyl (meth) acrylate, iso-nonyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate , Kurohekishiru (meth) acrylate one bets and the like. These may be only one kind or two or more kinds.

  The carbon number of the alkyl group in the (meth) acrylic acid alkyl ester having 4 to 12 carbon atoms in the alkyl ester moiety is preferably 4 to 10, and more preferably 4 to 8. The alkyl group may be linear or branched.

  Examples of the (meth) acrylic acid ester having an OH group include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. 3-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 5-hydroxypentyl (meth) acrylate, 3-hydroxy-3-methylbutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 7 -Hydroxyheptyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, (4-hydroxymethylcyclohex Le) - and methyl acrylate. These may be only one kind or two or more kinds.

  Examples of the polyfunctional isocyanate-based crosslinking agent include lower aliphatic polyisocyanates such as butylene diisocyanate and hexamethylene diisocyanate, alicyclic isocyanates such as cyclopentylene diisocyanate, cyclohexylene diisocyanate, and isophorone diisocyanate, 2,4- Aromatic isocyanates such as tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, xylylene diisocyanate, trimethylolpropane / tolylene diisocyanate trimer adduct (trade name “Coronate L” manufactured by Nippon Polyurethane Industry Co., Ltd.) Propane / hexamethylene diisocyanate trimer adduct (trade name “Coronate HL” manufactured by Nippon Polyurethane Industry Co., Ltd.) Cyanurate body (trade name "Coronate HX" manufactured by Nippon Polyurethane Industry Co., Ltd.), and the like isocyanate adducts such as. These may be only one kind or two or more kinds.

  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.). These may be only one kind or two or more kinds.

  The composition forming the acrylic resin may further 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. Such a crosslinking catalyst may be only 1 type, and 2 or more types may be sufficient as it.

  Arbitrary appropriate other monomers may be contained in the composition which forms acrylic resin in the range which does not impair the effect of this invention. Examples of such other monomers include benzyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxymethyl (meth) acrylate, phenoxyethyl (meth) acrylate, (meth) acrylamide, vinyl acetate, and (meth) acrylonitrile. Etc. These may be only one kind or two or more kinds.

  The composition that forms the acrylic resin may contain any appropriate other component as long as the effects of the present invention are not impaired. Examples of such other components include resin components other than acrylic resins, tackifiers, inorganic fillers, organic fillers, metal powders, pigments, foils, softeners, anti-aging agents, conductive agents, Examples include ultraviolet absorbers, antioxidants, light stabilizers, surface lubricants, leveling agents, corrosion inhibitors, heat stabilizers, polymerization inhibitors, lubricants, solvents, and catalysts.

  The weight average molecular weight (Mw) of the acrylic resin is preferably 100,000 or more, more preferably 100,000 to 3,000,000, as measured by a gel permeation chromatograph (GPC) method using a tetrahydrofuran solvent. More preferably, it is 200,000 to 2,000,000, particularly preferably 300,000 to 1,000,000. By adjusting the weight-average molecular weight (Mw) of the acrylic resin within the above range, the optical member with a surface protective film of the present invention can be used together with the release liner when the release liner is peeled off. The effect that it is difficult to peel from the surface protective film, that is, peeling hardly occurs at the interface between the optical member and the surface protective film, can be further exhibited.

  The acrylic resin can be produced by any appropriate method as long as the effects of the present invention are not impaired. An example of such a method is a polymerization reaction of a composition that forms an acrylic resin.

  Specific polymerization methods for the polymerization reaction include, for example, solution polymerization, emulsion polymerization, bulk polymerization, suspension polymerization, and photopolymerization (active energy ray polymerization). In particular, a solution polymerization method is preferable from the viewpoint of cost and productivity. 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 a base polymer solution containing the base polymer.

  Examples of the solvent 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 methylcyclohexane And organic solvents such as alicyclic hydrocarbons such as methyl ketones and methyl ketones. One type of solvent may be sufficient and 2 or more types may be sufficient as it.

  Examples of the polymerization initiator that can be used in the solution polymerization method include a peroxide polymerization initiator and an azo polymerization initiator. Examples of peroxide polymerization initiators 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 [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 content of the polymerization initiator is preferably 0.01 parts by weight to 5 parts by weight, more preferably 0.05 parts by weight to 3 parts by weight with respect to the total amount (100 parts by weight) of monomer components constituting the base polymer. Part.

  In the solution polymerization method, any appropriate heating temperature can be set as the heating temperature for heating and polymerization in a range not impairing the effects of the present invention. The heating temperature is preferably 50 to 80 ° C. In the solution polymerization method, any appropriate heating time can be set as the heating time for heating and polymerization in a range not impairing the effects of the present invention. Such heating time is preferably 1 to 24 hours.

[Rubber adhesive]
As the rubber-based pressure-sensitive adhesive, any appropriate rubber-based pressure-sensitive adhesive such as a known rubber-based pressure-sensitive adhesive described in JP-A-2015-074771 can be employed as long as the effects of the present invention are not impaired. . These may be only one kind or two or more kinds.

[Silicone adhesive]
As the silicone-based pressure-sensitive adhesive, any appropriate silicone-based pressure-sensitive adhesive such as a known silicone-based pressure-sensitive adhesive described in Japanese Patent Application Laid-Open No. 2014-047280 can be adopted as long as the effects of the present invention are not impaired. . These may be only one kind or two or more kinds.

≪Release liner≫
Examples of release liners include release liners in which the surface of a substrate (liner substrate) such as paper or plastic film is treated with silicone, and the surface of a substrate (liner substrate) such as paper or plastic film is made of a polyolefin resin. Examples include a laminated release liner. As a plastic film as a liner substrate, for example, polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate film, polybutylene terephthalate film, Examples thereof include polyurethane films and ethylene-vinyl acetate copolymer films. The plastic film as the liner substrate is preferably a polyethylene film.

≪Adhesive layer (2) ≫
The pressure-sensitive adhesive layer (2) can be produced by any appropriate production method. Examples of such a production method include a method in which a composition that is a material for forming the pressure-sensitive adhesive layer (2) is applied onto a release liner, and the pressure-sensitive adhesive layer (2) is formed on the release liner. Examples of such coating methods include roll coating, gravure coating, reverse coating, roll brushing, spray coating, air knife coating, extrusion coating using a die coater, and the like.

  The thickness of the pressure-sensitive adhesive layer (2) is preferably 1 μm to 500 μm, more preferably 2 μm to 400 μm, still more preferably 5 μm to 350 μm, and particularly preferably 10 μm to 300 μm. When the thickness of the pressure-sensitive adhesive layer (2) is adjusted within the above range, the optical member with a surface protective film of the present invention has a surface along with the release liner when the release liner is peeled off. The effect that it is difficult to peel from the protective film, that is, peeling hardly occurs at the interface between the optical member and the surface protective film, can be more manifested.

  The content of the pressure-sensitive adhesive in the pressure-sensitive adhesive layer (2) is preferably 50% by weight to 100% by weight, more preferably 60% by weight to 100% by weight, and further preferably 70% by weight to 100% by weight. And particularly preferably 80% to 100% by weight, and most preferably 90% to 100% by weight. By adjusting the content ratio of the pressure-sensitive adhesive in the pressure-sensitive adhesive layer (2) within the above range, the optical member with the surface protective film of the present invention is such that when the release liner is to be peeled off, the optical member becomes the release liner. It is possible to develop an effect that it is difficult to peel off from the surface protective film together with the surface protective film, that is, it is difficult to peel off at the interface between the optical member and the surface protective film.

  The pressure-sensitive adhesive contained in the pressure-sensitive adhesive layer (2) is preferably an acrylic pressure-sensitive adhesive.

  The acrylic adhesive contains an acrylic resin.

  The content of the acrylic resin in the acrylic pressure-sensitive adhesive is preferably 50% to 100% by weight, more preferably 70% to 100% by weight, and still more preferably 90% to 100% by weight. Particularly preferably 95% to 100% by weight, most preferably 98% to 100% by weight. By adjusting the content ratio of the acrylic resin in the acrylic pressure-sensitive adhesive within the above range, when the optical member with a surface protective film of the present invention is intended to release the release liner, the optical member is separated from the release liner. The effect that it is difficult to peel together from a surface protection film together, ie, it is hard to peel at the interface of an optical member and a surface protection film, can be expressed more.

  The acrylic pressure-sensitive adhesive may contain any appropriate other component in addition to the acrylic resin as long as the effects of the present invention are not impaired. Examples of such other components include resin components other than acrylic resins, tackifiers, inorganic fillers, organic fillers, metal powders, pigments, foils, softeners, anti-aging agents, conductive agents, Examples include ultraviolet absorbers, antioxidants, light stabilizers, surface lubricants, leveling agents, corrosion inhibitors, heat stabilizers, polymerization inhibitors, lubricants, solvents, and catalysts.

  Any appropriate acrylic resin can be adopted as the acrylic resin as long as the effects of the present invention are not impaired. The acrylic pressure-sensitive adhesive is preferably (a) a (meth) acrylic acid alkyl ester having 4 to 12 carbon atoms in the alkyl group of the alkyl ester moiety, (b) a (meth) acrylic acid ester having an OH group and ( It includes an acrylic resin formed from a composition containing at least one selected from (meth) acrylic acid and (c) at least one selected from a polyfunctional isocyanate-based crosslinking agent and an epoxy-based crosslinking agent.

  The content ratio of the component (a) in the composition forming the acrylic resin is preferably 85% to 99.9% by weight, more preferably 90% to 99.8% by weight, and still more preferably. Is 92.5 wt% to 99.7 wt%, particularly preferably 95 wt% to 99.6 wt%. By adjusting the content ratio of the component (a) in the composition forming the acrylic resin within the above range, the optical member with a surface protective film of the present invention is an optical member when the release liner is to be peeled off. Can be more difficult to be peeled off from the surface protective film together with the release liner, that is, the effect that peeling does not easily occur at the interface between the optical member and the surface protective film can be exhibited.

  The content ratio of the component (b) in the composition forming the acrylic resin is preferably 0.1% by weight to 15% by weight, more preferably 0.2% by weight to 10% by weight, and still more preferably. Is 0.3 wt% to 7.5 wt%, particularly preferably 0.4 wt% to 5 wt%. By adjusting the content ratio of the component (b) in the composition forming the acrylic resin within the above range, the optical member with a surface protective film of the present invention is an optical member when the release liner is to be peeled off. Can be more difficult to be peeled off from the surface protective film together with the release liner, that is, the effect that peeling does not easily occur at the interface between the optical member and the surface protective film can be exhibited.

  The content ratio of the component (c) in the composition forming the acrylic resin is preferably 0.01% by weight to 1.5% by weight, more preferably 0.02% by weight to 1.0% by weight. More preferably 0.03% by weight to 0.8% by weight, and particularly preferably 0.05% by weight to 0.7% by weight. By adjusting the content ratio of the component (c) in the composition for forming the acrylic resin within the above range, the optical member with a surface protective film of the present invention is an optical member when the release liner is to be peeled off. Can be more difficult to be peeled off from the surface protective film together with the release liner, that is, the effect that peeling does not easily occur at the interface between the optical member and the surface protective film can be exhibited.

  Examples of the (meth) acrylic acid alkyl ester having 4 to 12 carbon atoms in the alkyl ester moiety include n-butyl (meth) acrylate, iso-butyl (meth) acrylate, and t-butyl (meth) acrylate. , N-pentyl (meth) acrylate, iso-pentyl (meth) acrylate, n-hexyl (meth) acrylate, iso-hexyl (meth) acrylate, n-heptyl (meth) acrylate, iso-heptyl (meth) acrylate, 2 -Ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, iso-octyl (meth) acrylate, n-nonyl (meth) acrylate, iso-nonyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate , Kurohekishiru (meth) acrylate one bets and the like. These may be only one kind or two or more kinds.

  The carbon number of the alkyl group in the (meth) acrylic acid alkyl ester having 4 to 12 carbon atoms in the alkyl ester moiety is preferably 4 to 10, and more preferably 4 to 8. The alkyl group may be linear or branched.

  Examples of the (meth) acrylic acid ester having an OH group include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. 3-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 5-hydroxypentyl (meth) acrylate, 3-hydroxy-3-methylbutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 7 -Hydroxyheptyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, (4-hydroxymethylcyclohex Le) - and methyl acrylate. These may be only one kind or two or more kinds.

  Examples of the polyfunctional isocyanate-based crosslinking agent include lower aliphatic polyisocyanates such as butylene diisocyanate and hexamethylene diisocyanate, alicyclic isocyanates such as cyclopentylene diisocyanate, cyclohexylene diisocyanate, and isophorone diisocyanate, 2,4- Aromatic isocyanates such as tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, xylylene diisocyanate, trimethylolpropane / tolylene diisocyanate trimer adduct (trade name “Coronate L” manufactured by Nippon Polyurethane Industry Co., Ltd.) Propane / hexamethylene diisocyanate trimer adduct (trade name “Coronate HL” manufactured by Nippon Polyurethane Industry Co., Ltd.) Cyanurate body (trade name "Coronate HX" manufactured by Nippon Polyurethane Industry Co., Ltd.), and the like isocyanate adducts such as. These may be only one kind or two or more kinds.

  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.). These may be only one kind or two or more kinds.

  The composition forming the acrylic resin may further 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. Such a crosslinking catalyst may be only 1 type, and 2 or more types may be sufficient as it.

  Arbitrary appropriate other monomers may be contained in the composition which forms acrylic resin in the range which does not impair the effect of this invention. Examples of such other monomers include benzyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxymethyl (meth) acrylate, phenoxyethyl (meth) acrylate, (meth) acrylamide, vinyl acetate, and (meth) acrylonitrile. Etc. These may be only one kind or two or more kinds.

  The composition that forms the acrylic resin may contain any appropriate other component as long as the effects of the present invention are not impaired. Examples of such other components include resin components other than acrylic resins, tackifiers, inorganic fillers, organic fillers, metal powders, pigments, foils, softeners, anti-aging agents, conductive agents, Examples include ultraviolet absorbers, antioxidants, light stabilizers, surface lubricants, leveling agents, corrosion inhibitors, heat stabilizers, polymerization inhibitors, lubricants, solvents, and catalysts.

  As for the weight average molecular weight (Mw) of the acrylic resin, a value measured by a gel permeation chromatograph (GPC) method using a tetrahydrofuran solvent is preferably 1 million or more, more preferably 1.1 million to 2.5 million. More preferably, it is 1.2 million to 2.3 million, and particularly preferably 1.3 million to 2.1 million. By adjusting the weight-average molecular weight (Mw) of the acrylic resin within the above range, the optical member with a surface protective film of the present invention can be used together with the release liner when the release liner is peeled off. The effect that it is difficult to peel from the surface protective film, that is, peeling hardly occurs at the interface between the optical member and the surface protective film, can be further exhibited.

  The acrylic resin can be produced by any appropriate method as long as the effects of the present invention are not impaired. An example of such a method is a polymerization reaction of a composition that forms an acrylic resin.

  Specific polymerization methods for the polymerization reaction include, for example, solution polymerization, emulsion polymerization, bulk polymerization, suspension polymerization, and photopolymerization (active energy ray polymerization). In particular, a solution polymerization method is preferable from the viewpoint of cost and productivity. 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 a base polymer solution containing the base polymer.

  Examples of the solvent 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 methylcyclohexane And organic solvents such as alicyclic hydrocarbons such as methyl ketones and methyl ketones. One type of solvent may be sufficient and 2 or more types may be sufficient as it.

  Examples of the polymerization initiator that can be used in the solution polymerization method include a peroxide polymerization initiator and an azo polymerization initiator. Examples of peroxide polymerization initiators 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 [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 content of the polymerization initiator is preferably 0.01 parts by weight to 5 parts by weight, more preferably 0.05 parts by weight to 3 parts by weight with respect to the total amount (100 parts by weight) of monomer components constituting the base polymer. Part.

  In the solution polymerization method, any appropriate heating temperature can be set as the heating temperature for heating and polymerization in a range not impairing the effects of the present invention. The heating temperature is preferably 50 to 80 ° C. In the solution polymerization method, any appropriate heating time can be set as the heating time for heating and polymerization in a range not impairing the effects of the present invention. Such heating time is preferably 1 to 24 hours.

≪≪Method for producing optical member with surface protective film≫≫
The method for producing an optical member with a surface protective film of the present invention comprises a laminate of an optical member and a surface protective film, an adhesive layer (2) provided on the opposite side of the optical member to the surface protective film, and the adhesive. A release liner provided on the side opposite to the optical member of the agent layer (2), and an optical member with a surface protective film having the order, and the surface protective film comprises a base material layer and an adhesive layer (1). Any suitable method can be adopted as long as it is a method that can be configured such that the pressure-sensitive adhesive layer (1) of the surface protective film is on the optical member side.

  In the method for producing an optical member with a surface protective film of the present invention, for example, the surface protective film is preferably bonded to the optical member while applying tension to the surface protective film. A tension | tensile_strength can be suitably set according to the structure (for example, thickness, forming material, elastic modulus, tensile elongation, etc.) of a surface protection film. It can be manufactured by the above operation.

  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.

[Production Example 1]: Production of pressure-sensitive adhesive for polarizing plate In a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen gas introduction tube, and a condenser, butyl acrylate (manufactured by Nippon Shokubai Co., Ltd.): 99 parts by weight, 4 -Hydroxybutyl acrylate (Osaka Organic Chemical Co., Ltd.): 1 part by weight, 2,2'-azobisisobutyronitrile (manufactured by Wako Pure Chemical Industries, Ltd.) as a polymerization initiator: 0.1 part by weight, acetic acid Ethyl: 100 parts by weight were charged, nitrogen gas was introduced while gently stirring, and the polymerization temperature was kept at around 55 ° C. for 8 hours to conduct a polymerization reaction, and an acrylic polymer solution having a weight average molecular weight of 1.6 million (50 % By weight) was prepared. The obtained acrylic polymer solution (50% by weight) was diluted with ethyl acetate to 20% by weight. To 100 parts by weight of this solution, Coronate L (manufactured by Nippon Polyurethane Industry Co., Ltd.): 0.1 part by weight was used. In addition, mixing and stirring were performed to prepare an acrylic pressure-sensitive adhesive solution.

[Production Example 2]: Production of polarizing plate (Production of polarizer)
A polyvinyl alcohol film having a polymerization degree of 2400, a saponification degree of 99.9%, and a thickness of 30 μm is immersed in warm water at 30 ° C. and swollen so that the length of the polyvinyl alcohol film becomes 2.0 times the original length. The film was uniaxially stretched. Next, it is immersed in an aqueous solution (dye bath) having a concentration of a mixture of iodine and potassium iodide (weight ratio = 0.5: 8) of 0.3% by weight, and the polyvinyl alcohol film length is 3.0 times the original length. The film was dyed while being uniaxially stretched. Thereafter, the film was stretched so that the length of the polyvinyl alcohol film was 3.7 times the original length while immersed in an aqueous solution (crosslinking bath 1) of 5% by weight boric acid and 3% by weight potassium iodide. In an aqueous solution (crosslinking bath 2) of 4% by weight boric acid and 5% by weight potassium iodide, the polyvinyl alcohol film was stretched so that its length was 6 times the original length. Thereafter, iodine ion impregnation treatment was performed with an aqueous solution (iodine impregnation bath) of 3% by weight of potassium iodide, and then dried in an oven at 60 ° C. for 4 minutes to obtain a polarizer. The thickness of the obtained polarizer was 12 μm.
(Preparation of aqueous adhesive)
A polyvinyl alcohol-based resin containing acetoacetyl groups (average polymerization degree: 1200, saponification degree: 98.5 mol%, acetoacetylation degree: 5 mol%) is dissolved in pure water under a temperature condition of 30 ° C., A water-based adhesive was obtained by adjusting the solid content concentration to 4%.
(Manufacture of polarizing plates)
The above-mentioned aqueous adhesive was applied to a 25 μm thick triacetylcellulose (TAC) so that the thickness of the adhesive layer after drying was 80 nm to obtain a polarizer protective film with an adhesive layer. Next, the polarizer protective film with an adhesive layer was bonded to both sides of the polarizer under a temperature condition of 23 ° C. with a roll machine, and then dried at 55 ° C. for 6 minutes to produce a polarizing plate. Bonding of the polarizer and the polarizer protective film with an adhesive layer was performed such that the polarizer and the adhesive layer of the polarizer protective film with an adhesive layer were in contact with each other. In this way, a polarizing plate was produced.

[Production Example 3]: Manufacture of release liner Silicone-treated surface of a base material made of a polyester resin with a thickness of 38 μm obtained by applying silicone treatment to one side of the pressure-sensitive adhesive for polarizing plate produced in Production Example 1, and a thickness of 50 μm The adhesive layer is applied to the silicone-treated surface of the polyester resin substrate and cured by drying at a drying temperature of 150 ° C. and a drying time of 2 minutes so that the thickness after drying is 20 μm. Formed. In this manner, a laminate of a release liner and a pressure-sensitive adhesive layer having a thickness of 38 μm and a laminate of a release liner and a pressure-sensitive adhesive layer having a thickness of 50 μm were produced.

[Production Example 4]: Production of polarizing plate with laminate of release liner and pressure-sensitive adhesive layer On one side of the polarizing plate obtained in Production Example 2, the release liner obtained in Production Example 3 and the pressure-sensitive adhesive layer The pressure-sensitive adhesive layer side of the laminate was bonded to prepare a polarizing plate with a laminate of a release liner and a pressure-sensitive adhesive layer. The thickness of the polarizing plate with the pressure-sensitive adhesive layer excluding the release liner was 82 μm.

[Production Example 5]: Production of urethane-based pressure-sensitive adhesive composition (U1), which is a material for forming a pressure-sensitive adhesive layer contained in the surface protective film, As a polyol (A), preminol S3011 (polyol having three OH groups) Asahi Glass Co., Ltd., Mn = 10000), Sanniks GP-3000 (manufactured by Sanyo Chemical Co., Ltd., Mn = 3000) which is a polyol having 3 OH groups, Sanniks GP-1000 which is a polyol having 3 OH groups (Manufactured by Sanyo Chemical Co., Ltd., Mn = 1000), coronate HX (manufactured by Nippon Polyurethane Industry Co., Ltd.) which is a polyfunctional alicyclic isocyanate compound as the polyfunctional isocyanate compound (B), catalyst (manufactured by Nippon Chemical Industry Co., Ltd., Product name: Nursem Ferric), Irganox 1010 (made by BASF) as a deterioration inhibitor, fatty acid As esters, isopropyl myristate (trade name: Exepal IPM, Mn = 270, manufactured by Kao Corporation) or cetyl 2-ethylhexanoate (trade name: Saracos 816T, Mn = 368, manufactured by Nisshin Oilio Group Co., Ltd.), 1- Ethyl-3-methylimidazolium bis (fluoromethanesulfonyl) imide (Daiichi Kogyo Seiyaku Co., Ltd., trade name: AS110), double-ended polyether-modified silicone oil (Shin-Etsu Chemical Co., Ltd., trade name: KF) -6004), ethyl acetate was added as a diluting solvent and mixed and stirred to produce a urethane-based pressure-sensitive adhesive composition. The number of blending parts is shown in Table 1.

[Production Example 6]: Production of urethane-based pressure-sensitive adhesive composition (U2), which is a material for forming a pressure-sensitive adhesive layer contained in a surface protective film, as urethane prepolymer (C), Siavine SH-109 (manufactured by Toyochem Co., Ltd.) Coronate HX (manufactured by Nippon Polyurethane Industry Co., Ltd.), which is a polyfunctional alicyclic isocyanate compound, is added as the polyfunctional isocyanate compound (B), and toluene is added as a diluent solvent, followed by mixing and stirring, and a urethane pressure-sensitive adhesive composition (U2 ) Was adjusted. The number of blending parts is shown in Table 1. In addition, all the compounding parts of each material except toluene become solid content conversion, and the part of toluene points out the amount of all the solvents contained in an adhesive.

[Production Example 7]: Production of acrylic pressure-sensitive adhesive composition (Ac1), which is a material for forming the pressure-sensitive adhesive layer contained in the surface protective film, four equipped with a stirring blade, a thermometer, a nitrogen gas introduction pipe, and a cooler In the neck flask, 2-ethylhexyl acrylate (manufactured by Nippon Shokubai Co., Ltd.): 100 parts by weight, 2-hydroxyethyl acrylate (manufactured by Toagosei Co., Ltd.): 4 parts by weight, 2,2′-azobisisobuty as a polymerization initiator Ronitrile (manufactured by Wako Pure Chemical Industries, Ltd.): 0.2 parts by weight, ethyl acetate: 156 parts by weight, nitrogen gas was introduced while gently stirring, and the liquid temperature in the flask was kept at around 65 ° C. A polymerization reaction was carried out for 6 hours to prepare a solution (40% by weight) of an acrylic polymer (Ac1P) having a weight average molecular weight of 550,000. Coronate HX (manufactured by Nippon Polyurethane Industry Co., Ltd.), catalyst (manufactured by Nippon Chemical Industry Co., Ltd., trade name) as a crosslinking agent for the obtained acrylic polymer solution (Ac1P) (40 wt%) having a weight average molecular weight of 550,000 : Nacem Ferric), ethyl acetate as a diluent solvent was added and mixed and stirred to produce an acrylic pressure-sensitive adhesive composition (Ac1). The number of blending parts is shown in Table 1. In addition, all the compounding parts of each material except ethyl acetate become solid content conversion, and the number of parts of ethyl acetate points out the amount of all the solvents contained in an adhesive.

[Production Example 8]: Production of acrylic pressure-sensitive adhesive composition (Ac2), which is a material for forming the pressure-sensitive adhesive layer contained in the surface protective film, four equipped with a stirring blade, a thermometer, a nitrogen gas introduction pipe, and a cooler In a neck flask, 95 parts by weight of butyl acrylate (manufactured by Nippon Shokubai Co., Ltd.), 5 parts by weight of acrylic acid (manufactured by Toagosei Co., Ltd.), 2,2′-azobisisobutyronitrile (as a polymerization initiator) Yakuhin Kogyo Co., Ltd.): 0.2 parts by weight, ethyl acetate: 186 parts by weight, nitrogen gas was introduced while gently stirring, and the temperature of the liquid in the flask was kept at around 63 ° C. for 10 hours. Then, a solution (35% by weight) of an acrylic polymer (Ac2P) having a weight average molecular weight of 500,000 was prepared. Tetrad C (manufactured by Mitsubishi Gas Chemical Co., Ltd.), catalyst (manufactured by Nippon Chemical Industry Co., Ltd.) Name: Nursem Ferric) and ethyl acetate as a diluent solvent were added and mixed and stirred to produce an acrylic pressure-sensitive adhesive composition (Ac2). The number of blending parts is shown in Table 1. In addition, all the compounding parts of each material except ethyl acetate become solid content conversion, and the number of parts of ethyl acetate points out the amount of all the solvents contained in an adhesive.

[Production Example 9]: Production of rubber-based pressure-sensitive adhesive composition (G), which is a material for forming a pressure-sensitive adhesive layer contained in a surface protective film. Hibler 5127 (manufactured by Kuraray Co., Ltd.): 100 parts by weight of toluene as a diluent solvent Was mixed and stirred to produce a rubber-based pressure-sensitive adhesive composition (G). The number of blending parts is shown in Table 1.

[Production Example 10]: Production of silicone-based pressure-sensitive adhesive composition (S), which is a material for forming the pressure-sensitive adhesive layer contained in the surface protective film. Addition-reaction type silicone-based pressure-sensitive adhesive (trade name: X-40-3306, Shin-Etsu) Chemical Industry Co., Ltd.) and a platinum-based catalyst (trade name: CAT-PL-50T, manufactured by Shin-Etsu Chemical Co., Ltd.) were mixed to produce a silicone-based pressure-sensitive adhesive composition (S). The number of blending parts is shown in Table 1.

[Production Example 11]: Production of surface protective film with separator The obtained adhesive compositions were dried on a base material "Lumirror S10" (thickness 38 µm, manufactured by Toray Industries, Inc.) made of a polyester resin, with a fountain roll. Was coated to a thickness of 10 μm, and cured by drying under conditions of a drying temperature of 130 ° C. and a drying time of 30 seconds. Thus, the adhesive layer was produced on the base material. Next, the surface of the pressure-sensitive adhesive layer was pasted with a silicone-treated surface of a base material (separator) 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 with a separator.

<Measurement of trigger peeling force P of optical member>
A surface protective film is bonded to the surface opposite to the release liner of the polarizing plate having a laminate of the release liner and the pressure-sensitive adhesive layer produced in Production Example 4 to protect the surface. A polarizing plate with a film was prepared. The produced polarizing plate with a surface protective film was cut into a size of 25 mm in width and 80 mm in length. In addition, as a method of cutting the polarizing plate with a surface protective film, a cutting machine was used, but cutting with a super cutter may be performed. After being left in an environment of 23 ° C. × 50% RH for 24 hours, the release liner of the polarizing plate with a surface protective film was peeled off, and the single-sided adhesive tape cut to a size of 25 mm width and 50 mm length (made by Nichiban Co., Ltd., trade name “ Cellotape (registered trademark) ”was pressure-bonded to the pressure-sensitive adhesive layer side of the polarizing plate with a surface protective film so that the end face was 1 mm, and left for 10 seconds. Thereafter, the single-sided adhesive tape was peeled off at a peeling speed of 300 mm / min and 6.0 m / min at a peeling angle of 180 ° using a universal tensile testing machine (product name: TCM-1kNB, manufactured by Minebea Co., Ltd.). At that time, the maximum stress applied at the beginning of peeling was used as the peeling force (N / 25 mm). The measurement was performed in an environment of 23 ° C. × 50% RH.

<Measurement of trigger peel strength Q of release liner>
A surface protective film is bonded to the surface opposite to the release liner of the polarizing plate having a laminate of the release liner and the pressure-sensitive adhesive layer produced in Production Example 4 to protect the surface. A polarizing plate with a film was prepared. The produced polarizing plate with a surface protective film was cut into a size of 25 mm in width and 80 mm in length. In addition, as a method of cutting the polarizing plate with a surface protective film, a cutting machine was used, but cutting with a super cutter may be performed. One-sided adhesive tape (made by Nichiban Co., Ltd., trade name “Cellotape (registered trademark)”) cut at a size of 25 mm in width and 50 mm in length after being left in an environment of 23 ° C. × 50% RH for 24 hours, has an end face of 1 mm. It was pressed against the release liner side of the polarizing plate with a surface protective film so as to come out, and left for 10 seconds. Thereafter, the single-sided adhesive tape was peeled off at a peeling speed of 300 mm / min and 6.0 m / min at a peeling angle of 180 ° using a universal tensile testing machine (product name: TCM-1kNB, manufactured by Minebea Co., Ltd.). At that time, the maximum stress applied at the beginning of peeling was used as the peeling force (N / 25 mm). The measurement was performed in an environment of 23 ° C. × 50% RH.
When the thickness of the release liner was 38 μm and the release rate was 300 mm / min, the trigger release force Q was 0.40 N / 25 mm.
When the thickness of the release liner was 38 μm and the release rate was 6 m / min, the trigger release force Q was 1.23 N / 25 mm.
When the thickness of the release liner was 50 μm and the release rate was 300 mm / min, the trigger release force Q was 1.99 N / 25 mm.
When the thickness of the release liner was 50 μm and the release speed was 6 m / min, the trigger release force Q was 2.60 N / 25 mm.

<Measurement of initial adhesive strength of surface protective film>
The surface protective film with a separator obtained in Production Example 11 was cut into a size having a width of 25 mm and a length of 80 mm, and the separator was peeled off. Thereafter, the polarizing plate with the laminate of the release liner and the pressure-sensitive adhesive layer obtained in Production Example 4 was cut into a width of 70 mm and a length of 100 mm, and the surface protective film was adhered to the surface opposite to the release liner. The agent layer surface was laminated at a pressure of 0.25 MPa to prepare an evaluation sample. After laminating, it is left in an environment of 23 ° C. × 50% RH for 30 minutes, using a universal tensile tester (Minebea Co., Ltd., product name: TCM-1kNB) at a peeling speed of 300 mm / min and a peeling angle of 180 degrees. When the surface protective film was peeled off, the adhesive strength in the region where the value was stabilized was measured. The measurement was performed in an environment of 23 ° C. × 50% RH.

<Measurement of wetting speed of surface protective film>
The separator-coated surface protective film obtained in Production Example 11 was cut into a width of 2.5 cm and a length of 10 cm to obtain an evaluation sample. As an adherend, a polarizing plate provided with a laminate of the release liner obtained in Production Example 4 and an adhesive layer was used. On the surface of the adherend opposite to the release liner, fix one end of the width side of the adhesive layer side of the evaluation sample from which the separator has been peeled off, lift the unfixed width side end, and The time from release until 100 mm wet spreading was measured. (Unit: seconds / 2.5 cm × 10 cm). The wetting rate (unit: cm ² / sec) was calculated from the time taken.

<Measurement of weight average molecular weight>
The weight average molecular weight (Mw) of the acrylic polymers obtained in Production Examples 7 and 8 was measured using a GPC device (HLC-8220 GPC, manufactured by Tosoh Corporation). The measurement conditions are as follows. The weight average molecular weight was determined in terms of polystyrene.
Sample concentration: 0.2% by weight (THF solution)
Sample injection volume: 10 μl eluent THF flow rate: 0.6 ml / min
Measurement temperature: 40 ° C
Sample column: TSKguardcolumn SuperHZ-H (1) + TSKgel SuperHZM-H (2)
Reference column: TSKgel SuperH-RC (1)
Detector: Differential refractometer (RI)

[Examples 1-15, Comparative Examples 1-3]
The surface protective film with a separator obtained in Production Example 11 along the number of parts shown in Table 1 was cut into a size of 25 mm in width and 80 mm in length, and the separator was peeled off. Thereafter, the polarizing plate with the laminate of the release liner and the pressure-sensitive adhesive layer obtained in Production Example 4 was cut into a width of 70 mm and a length of 100 mm, and the surface protective film was adhered to the surface opposite to the release liner. The surface of the adhesive layer is laminated at a pressure of 0.25 MPa, and optical members (1) to (15) with a surface protective film having a configuration of release liner / adhesive layer / optical member / surface protective film (adhesive layer / base material layer) , (C1) to (C3) were obtained.
The results are shown in Table 1.

  The optical member with a surface protective film of the present invention can be used for any appropriate application. Preferably, the optical member with a surface protective film of the present invention is preferably used in the fields of optical members and electronic members.

10 Release liner 20 Adhesive layer (2)
30 Optical member 40 Adhesive layer (1)
50 Base material layer 100 Surface protective film 1000 Optical member with surface protective film

Claims (13)

A laminate of an optical member and a surface protective film, an adhesive layer (2) provided on the opposite side of the optical member from the surface protective film, and an adhesive layer (2) provided on the opposite side of the optical member. An optical member with a surface protective film having a release liner in this order,
The surface protective film includes a base material layer and an adhesive layer (1),
The pressure-sensitive adhesive layer (1) of the surface protective film is on the optical member side,
The trigger peeling force P of the optical member from the laminate is larger than the trigger peeling force Q of the release liner.
Optical member with surface protective film.   The optical member with a surface protective film according to claim 1, wherein the optical member has a thickness of 1 μm to 500 μm.   The optical member with a surface protective film according to claim 1 or 2, wherein the surface protective film has a thickness of 5 µm to 500 µm.   The optical member with a surface protective film according to claim 1, wherein the release liner has a thickness of 1 μm to 500 μm.   The optical member with a surface protective film according to any one of claims 1 to 4, wherein the base material layer is a plastic film.   The pressure-sensitive adhesive contained in the pressure-sensitive adhesive layer (1) is at least one selected from urethane-based pressure-sensitive adhesives, acrylic pressure-sensitive adhesives, rubber-based pressure-sensitive adhesives, and silicone-based pressure-sensitive adhesives. An optical member with a surface protective film as described in 1.   The optical member with a surface protective film according to claim 6, wherein the urethane-based pressure-sensitive adhesive contains a polyurethane-based resin formed from a composition containing a polyol (A) and a polyfunctional isocyanate compound (B).   The optical with surface protective film according to claim 7, wherein an equivalent ratio of NCO groups to OH groups in the polyol (A) and the polyfunctional isocyanate compound (B) is 2.0 or less as NCO groups / OH groups. Element.   The optical member with a surface protective film according to claim 6, wherein the urethane-based pressure-sensitive adhesive includes a polyurethane-based resin formed from a composition containing a urethane prepolymer (C) and a polyfunctional isocyanate compound (B).   The surface protection film according to claim 9, wherein an equivalent ratio of NCO groups to OH groups in the urethane prepolymer (C) and the polyfunctional isocyanate compound (B) is 2.0 or less as NCO groups / OH groups. Attached optical member.   The optical member with a surface protective film according to any one of claims 7 to 10, wherein the urethane-based pressure-sensitive adhesive contains a fatty acid ester.   The acrylic pressure-sensitive adhesive (a) (meth) acrylic acid alkyl ester having 4 to 12 carbon atoms in the alkyl group of the alkyl ester moiety, (b) (meth) acrylic acid ester having an OH group, and (meth) The acrylic resin formed from the composition containing the at least 1 sort (s) chosen from acrylic acid and the (c) at least 1 sort (s) chosen from a polyfunctional isocyanate type crosslinking agent and an epoxy type crosslinking agent is included. Optical member with surface protective film. The wetting speed of the surface protective film to the optical member surface is 5 cm 2 ^/ sec or more, a surface protective film attached optical member according to any one of claims 1 to 12.

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