JP7154733B2 - Optical components with surface protection film - Google Patents

Description

TECHNICAL FIELD 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 attached to the surface of an optical member.

In the manufacturing process of optical products such as liquid crystal display devices, it is common to attach a release liner to one surface of an optical member such as a polarizing plate via an adhesive layer. When such an optical member is attached to another member (for example, another optical member), the release liner is peeled off before that, the pressure-sensitive adhesive layer is exposed, and the adhesive layer is attached to the other member ( For example, Patent Document 1).

On the other hand, an optical member generally has a surface protective film adhered to its exposed surface in order to prevent the surface from being damaged during processing, assembly, inspection, transportation, and the like. Such a surface protection film is peeled off from the optical member when the surface protection is no longer required.

That is, in the manufacturing process of optical products such as liquid crystal display devices, a release liner is attached to one surface of an 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 released as described above, it is important that the release occurs only at the interface between the release liner and the pressure-sensitive adhesive layer. However, in a conventional optical member with a surface protective film, when the release liner is to be peeled off as described above, the optical member is peeled off from the surface protective film together with the release liner. There is a problem that peeling occurs at the interface between the member and the surface protection film. Such a problem is particularly noticeable when the optical member is thin.

Japanese Patent No. 3972676

An object of the present invention is to provide an optical member having a release liner adhered to one surface via an adhesive layer and a surface protective film adhered to the other surface, wherein the release liner is peeled off. To provide 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, peeling hardly occurs at the interface between the optical member and the surface protective film. be.

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

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

In one embodiment, the surface protective film has a thickness of 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 layer is a plastic film.

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

In one embodiment, 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).

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 pressure-sensitive adhesive contains a polyurethane 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 comprises (a) a (meth)acrylic acid alkyl ester in which the alkyl group of the alkyl ester portion has 4 to 12 carbon atoms, and (b) a (meth)acrylic acid having an OH group. An acrylic resin formed from a composition containing at least one selected from acrylic acid esters and (meth)acrylic acid, and (c) at least one selected from polyfunctional isocyanate cross-linking agents and epoxy cross-linking agents. include.

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, the optical member has a release liner adhered to one surface via an adhesive layer and a surface protective film adhered to the other surface, and the release liner is peeled off. It is possible to provide an optical member with a surface protective film in which the optical member is difficult to be peeled off from the surface protective film together with the release liner, that is, peeling is unlikely to occur at the interface between the optical member and the surface protective film. can.

1 is a schematic cross-sectional view of an optical member with a surface protective film according to one embodiment of the present invention; FIG. FIG. 3 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 protection film. FIG. 4 is a schematic cross-sectional view for explaining the trigger release force Q of the release liner;

≪≪Optical member with surface protection 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) An optical member with a surface protective film comprising, in this order, the optical member of 2) and a release liner provided on the opposite side, the surface protective film comprising a substrate layer and an adhesive layer (1), The pressure-sensitive adhesive layer (1) of the surface protection 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 ( As long as it has the release liner provided on the opposite side of the optical member of 2), it may have any appropriate other layer within a range that does not impair the effects of the present invention.

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

The thickness of the optical member is preferably 1 μm to 500 μm, more preferably 3 μm to 450 μm, even more preferably 5 μm to 400 μm, particularly preferably 10 μm to 300 μm. In the optical member with a surface protective film of the present invention, even when the thickness of the optical member is so thin, when the release liner is to be peeled off, the optical member is peeled off from the surface protective film together with the release liner. In other words, the effect that peeling at the interface between the optical member and the surface protective film is difficult to occur can be exhibited.

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 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 difficult to peel, that is, it is difficult for peeling to occur at the interface between the optical member and the surface protection film, can be further exhibited.

The thickness of the release liner is preferably 1 μm to 500 μm, more preferably 3 μm to 450 μm, even more preferably 5 μm to 400 μm, particularly preferably 10 μm to 300 μm. By adjusting the thickness of the release liner within the above range, the optical member with a surface protective film of the present invention can be peeled off from the surface protective film together with the release liner when the release liner is to be peeled off. In other words, the effect that peeling hardly occurs at the interface between the optical member and the surface protective film can be further exhibited.

In the optical member with a surface protective film of the present invention, the initial peel force P of the optical member from the laminate of the optical member and the surface protective film is greater than the initial peel force Q of the release liner. Since the trigger release force P is greater than the trigger release force Q, the optical member with the 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. In other words, peeling hardly occurs at the interface between the optical member and the surface protective film.

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

When the thickness of the release liner is 38 μm and the peel 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 still more preferably 6 to 15. Yes, particularly preferably 6 to 13. If the trigger release force P/the trigger release force Q is within the above range, the optical member with the surface protective film of 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 off from the surface protective film, that is, peeling is more difficult 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 peel speed is 6 m/min, the trigger release force P/the trigger release force Q is preferably 2.1 or more, more preferably 2.1 to 20, and still more preferably 2.3 to 15, particularly preferably 2.5 to 10. If the trigger release force P/the trigger release force Q is within the above range, the optical member with the surface protective film of 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 off from the surface protective film, that is, peeling is more difficult 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 peel 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 trigger release force P/the trigger release force Q is within the above range, the optical member with the surface protective film of 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 off from the surface protective film, that is, peeling is more difficult 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 peel 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 1.1 to 5, particularly preferably 1.2 to 3. If the trigger release force P/the trigger release force Q is within the above range, the optical member with the surface protective film of 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 off from the surface protective film, that is, peeling is more difficult 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 protection film. As shown in FIG. 2 , the trigger peel force P is the trigger peel force when the optical member 30 is peeled off 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 release force Q of the release liner. As shown in FIG. 3 , the trigger release force Q is the trigger release force when peeling the release liner 10 from the laminate of the release liner 10 , the adhesive layer ( 2 ) 20 and the optical member 30 . A method for measuring the trigger peel force Q will be described later.

≪Optical components≫
As the optical member, any appropriate optical member can be adopted as long as the effects of the present invention are not impaired. The optical member may be of one layer or of multiple layers. Such an optical member preferably includes a polarizing plate, a multilayer optical element including a polarizing plate, a retardation plate, an LCD, a touch panel using an LCD, a color filter used in an LCD, and the like.

≪Surface protection film≫
A surface protection film contains a base material layer and an adhesive layer (1). As long as the surface protection film includes the substrate layer and the pressure-sensitive adhesive layer (1), it may have any appropriate other layers within a range that does not impair the effects of the present invention.

The wetting speed of the surface protective film with respect to the surface of the optical member is preferably 5 cm ² /sec or more, more preferably 7 cm ² /sec or more, still more preferably 8 cm ² /sec 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 surface of the optical member is within the above range, the wetting speed of the surface protective film with respect to the surface of the optical member is excellent and, for example, air bubbles are less likely to exist between the surface of the optical member and the surface protective film.

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

Examples of coating methods that can be used include a roll coater method, a comma coater method, a die coater method, a reverse coater method, a silk screen method, and a gravure coater method.

<Base material layer>
The base material layer may consist of only one layer, or may consist of two or more layers. The substrate layer may be stretched.

The thickness of the substrate layer is preferably 4 μm to 450 μm, more preferably 8 μm to 400 μm, even more preferably 12 μm to 350 μm, and particularly preferably 16 μm to 250 μm. By adjusting the thickness of the substrate layer within the above range, the optical member with a surface protective film of the present invention can be 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 difficult to peel, that is, it is difficult for peeling to occur at the interface between the optical member and the surface protection film, can be further exhibited.

For example, fatty acid amide, polyethyleneimine, long-chain alkyl Release treatment can be performed by adding a system additive or the like, or a coat layer made of any suitable release agent such as a silicone-based, long-chain alkyl-based, or fluorine-based release agent can be provided.

Any appropriate material can be adopted as the material of the base material layer depending on the application. Examples include plastics, paper, metal films, and non-woven fabrics. Preferably, it is plastic. That is, the substrate 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, it may be composed of two or more types of plastics.

Examples of the plastics include polyester-based resins, polyamide-based resins, and polyolefin-based resins. Polyester-based resins include, for example, polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate. Examples of polyolefin-based resins include homopolymers of olefin monomers and copolymers of olefin monomers. Specific examples of polyolefin-based resins include, for example, homopolypropylene; block-, random-, and graft-based propylene-based copolymers having an ethylene component as a copolymerization component; reactor TPO; low-density, high-density, linear Ethylene-based polymers with low density, ultra-low density, etc.; ethylene/propylene copolymer, ethylene/vinyl acetate copolymer, ethylene/methyl acrylate copolymer, ethylene/ethyl acrylate copolymer, ethylene/acrylic acid ethylene-based copolymers such as butyl copolymers, ethylene/methacrylic acid copolymers, and ethylene/methyl methacrylate copolymers;

The base material layer may contain any appropriate additive as needed. Examples of additives that can be contained in the base material layer include antioxidants, ultraviolet absorbers, light stabilizers, antistatic agents, fillers, pigments, and the like. The type, number, and amount of additives that can be contained in the base material layer can be appropriately set according to the purpose. In particular, when the material of the substrate 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, particularly preferred additives include antioxidants, ultraviolet absorbers, light stabilizers, and fillers.

Any appropriate antioxidant can be employed as the antioxidant. Examples of such antioxidants include phenol-based antioxidants, phosphorus-based processing heat stabilizers, lactone-based processing heat stabilizers, sulfur-based heat-resistant stabilizers, and phenol/phosphorus-based antioxidants. The content of the antioxidant is preferably 1% by weight or less, more preferably 1% by weight or less, relative to the base resin of the base layer (when the base layer is a blend, the blend is the base resin). It is 0.5 wt % or less, more preferably 0.01 wt % to 0.2 wt %.

Any appropriate UV absorber can be adopted as the UV absorber. Examples of such ultraviolet absorbers include benzotriazole-based ultraviolet absorbers, triazine-based ultraviolet absorbers, and benzophenone-based ultraviolet absorbers. The content of the ultraviolet absorber is preferably 2% 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 It is preferably 1 wt % or less, more preferably 0.01 wt % to 0.5 wt %.

Any suitable light stabilizer can be employed as the light stabilizer. Examples of such light stabilizers include hindered amine light stabilizers and benzoate light stabilizers. The content of the light stabilizer is preferably 2% 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 It is preferably 1 wt % or less, more preferably 0.01 wt % to 0.5 wt %.

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

Further, the additive preferably includes inorganic, low-molecular-weight, and high-molecular-weight antistatic agents such as surfactants, inorganic salts, polyhydric alcohols, metal compounds, and carbon for the purpose of imparting antistatic properties. In particular, high-molecular-weight antistatic agents and carbon are preferred from the viewpoint of contamination and maintenance of adhesiveness.

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

The thickness of the adhesive layer (1) is preferably 1 μm to 150 μm, more preferably 2 μm to 140 μm, even 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 surface protective film-attached optical member of the present invention allows the optical member to adhere to the surface together with the release liner when the release liner is to be peeled off. The effect that it is difficult to peel off from the protective film, that is, the effect that peeling hardly occurs at the interface between the optical member and the surface protective film can be exhibited.

The content of the adhesive in the adhesive layer (1) is preferably 50 wt% to 100 wt%, more preferably 60 wt% to 100 wt%, still more preferably 70 wt% to 100 wt%. , particularly preferably 80% to 100% by weight, most preferably 90% to 100% by weight. By adjusting the content of the pressure-sensitive adhesive in the pressure-sensitive adhesive layer (1) within the above range, the surface protective film-attached optical member of the present invention is such that when the release liner is to be peeled off, the optical member can be easily removed from the release liner. Together with this, it is difficult to peel off from the surface protective film, that is, the effect that peeling hardly occurs at the interface between the optical member and the surface protective film can be further exhibited.

The adhesive contained in the adhesive layer (1) is preferably at least one selected from urethane-based adhesives, acrylic-based adhesives, rubber-based adhesives, and silicone-based adhesives. At least one selected from a urethane-based pressure-sensitive adhesive and an acrylic pressure-sensitive adhesive is more preferable, and a urethane-based pressure-sensitive adhesive is even more preferable in that it can be expressed.

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

The content of the polyurethane-based resin in the urethane-based 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 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, when the release liner is about to be peeled off, can be easily separated from the release liner. Together, it is difficult to peel off from the surface protective film, that is, the effect that peeling hardly occurs at the interface between the optical member and the surface protective film can be further exhibited.

The urethane-based pressure-sensitive adhesive may contain any appropriate other component in addition to the polyurethane-based resin within a range that does not impair the effects of the present invention. Such other components include, for example, resin components other than polyurethane resins, tackifiers, inorganic fillers, organic fillers, metal powders, pigments, foils, softeners, anti-aging agents, conductive agents, UV absorbers, antioxidants, light stabilizers, surface lubricants, leveling agents, corrosion inhibitors, heat stabilizers, polymerization inhibitors, lubricants, solvents, catalysts and the like.

As the polyurethane-based resin, any appropriate polyurethane-based resin can be adopted as long as the effects of the present invention are not impaired. The polyurethane-based resin is preferably a polyurethane-based 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 resin formed from a composition containing By employing such a polyurethane resin as described above, the optical member with a surface protective film of the present invention can be peeled off from the surface protective film together with the release liner when the release liner is to be peeled off. In other words, the effect that peeling hardly occurs at the interface between the optical member and the surface protective film can be further exhibited.

The polyurethane-based resin may contain any appropriate other component within a range that does not impair the effects of the present invention. Such other components include, for example, resin components other than polyurethane resins, tackifiers, inorganic fillers, organic fillers, metal powders, pigments, foils, softeners, anti-aging agents, conductive agents, UV absorbers, antioxidants, light stabilizers, surface lubricants, leveling agents, corrosion inhibitors, heat stabilizers, polymerization inhibitors, lubricants, solvents, catalysts and the like.

The polyurethane-based resin preferably contains anti-deterioration agents such as antioxidants, ultraviolet absorbers, and light stabilizers. By including a deterioration inhibitor in the polyurethane-based resin, it is possible to have excellent adhesive residue prevention properties, such as less adhesive residue on the adherend even when stored in a heated state after being attached to the adherend. Only one kind of anti-degradation agent may be used, or two or more kinds thereof may be used. Antioxidants are particularly preferred as deterioration inhibitors.

Antioxidants include, for example, radical chain inhibitors and peroxide decomposers.

Examples of radical chain inhibitors include phenol antioxidants and amine antioxidants.

Examples of peroxide decomposers include sulfur-based antioxidants and phosphorus-based antioxidants.

Examples of phenolic antioxidants include monophenolic antioxidants, bisphenolic antioxidants, polymeric phenolic antioxidants, and the like.

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

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

Examples of polymeric phenolic antioxidants include 1,1,3-tris(2-methyl-4-hydroxy-5-t-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, tocopherol and the like.

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

Phosphorus antioxidants include, for example, triphenylphosphite, diphenylisodecylphosphite, and phenyldiisodecylphosphite.

Examples of ultraviolet absorbers include benzophenone-based ultraviolet absorbers, benzotriazole-based ultraviolet absorbers, salicylic acid-based ultraviolet absorbers, oxalic acid anilide-based ultraviolet absorbers, cyanoacrylate-based ultraviolet absorbers, and triazine-based ultraviolet absorbers. be done.

Benzophenone-based UV absorbers include, for example, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2,2' -dihydroxy-4-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone, bis(2-methoxy-4-hydroxy-5-benzoylphenyl ) methane and the like.

Benzotriazole-based UV absorbers include, for example, 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 cyanoacrylate ultraviolet absorbers include 2-ethylhexyl-2-cyano-3,3'-diphenyl acrylate and ethyl-2-cyano-3,3'-diphenyl acrylate.

Examples of light stabilizers include hindered amine light stabilizers and ultraviolet 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, methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacate and the like can be mentioned.

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

The urethane pressure-sensitive adhesive may contain a fatty acid ester. Only one kind of fatty acid ester may be used, or two or more kinds thereof may be used.

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. is. By adjusting the number average molecular weight Mn of the fatty acid ester within the above range, the wetting speed can be further improved. If the number average molecular weight Mn of the fatty acid ester is too small, the wetting speed may not improve even if the number of parts added is large. If the number average molecular weight Mn of the fatty acid ester is too large, the curability of the pressure-sensitive adhesive during drying may deteriorate, which may adversely affect not only wettability but also other pressure-sensitive adhesive properties.

As the fatty acid ester, any suitable fatty acid ester can be adopted as long as it does not impair the effects of the present invention. Examples of such fatty acid esters include polyoxyethylene bisphenol A laurate, butyl stearate, 2-ethylhexyl palmitate, 2-ethylhexyl stearate, monoglyceride behenate, cetyl 2-ethylhexanoate, and myristic acid. Isopropyl, isopropyl palmitate, cholesteryl isostearate, lauryl methacrylate, methyl cocoate, methyl laurate, methyl oleate, methyl stearate, myristyl myristate, octyldodecyl myristate, pentaerythritol monooleate, pentaerythritol monostearate , pentaerythritol tetrapalmitate, stearyl stearate, isotridecyl stearate, 2-ethylhexanoic acid triglyceride, butyl laurate, octyl oleate and the like.

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

The urethane pressure-sensitive adhesive may contain an ionic liquid containing a fluoroorganic anion. By including an ionic liquid containing a fluoroorganic anion in the urethane-based pressure-sensitive adhesive, it is possible to provide a urethane-based pressure-sensitive adhesive with extremely excellent antistatic properties. 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 exhibits a liquid state at 25°C.

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

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

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

In general formula (1), Ra represents a hydrocarbon group having 4 to 20 carbon atoms and may contain a heteroatom; It represents a hydrogen group and may contain a heteroatom. However, when the nitrogen atom contains a double bond, there is no Rc.

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

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

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

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

Specific examples of the cation represented by formula (1) include 1-ethylpyridinium cation, 1-butylpyridinium cation, 1-hexylpyridinium cation, 1-ethyl-3-methylpyridinium cation, 1-butyl -3-methylpyridinium cation, 1-hexyl-3-methylpyridinium cation, 1-butyl-4-methylpyridinium cation, 1-octyl-4-methylpyridinium cation, 1-butyl-3,4-dimethylpyridinium cation, pyridinium cations such as 1,1-dimethylpyrrolidinium cation; 1-ethyl-1-methylpyrrolidinium cation, 1-methyl-1-propylpyrrolidinium cation, 1-methyl-1-butylpyrrolidinium cation, 1-methyl-1-pentylpyrrolidinium cation, 1-methyl-1-hexylpyrrolidinium cation, 1-methyl-1-heptylpyrrolidinium cation, 1-ethyl-1-propylpyrrolidinium cation, 1 -ethyl-1-butylpyrrolidinium cation, 1-ethyl-1-pentylpyrrolidinium cation, 1-ethyl-1-hexylpyrrolidinium cation, 1-ethyl-1-heptylpyrrolidinium cation, 1 , 1-dipropylpyrrolidinium cation, 1-propyl-1-butylpyrrolidinium cation, 1,1-dibutylpyrrolidinium cation and other pyrrolidinium cations; 1-propylpiperidinium cation, 1-pentylpi peridinium 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 cation , 1-ethyl-1-pentylpiperidinium cation, 1-ethyl-1-hexylpiperidinium cation, 1-ethyl-1-heptylpiperidinium cation, 1-propyl-1-butylpiperidinium cation, Piperidinium cations such as 1,1-dimethylpiperidinium cation, 1,1-dipropylpiperidinium cation, 1,1-dibutylpiperidinium cation; 2-methyl-1-pyrroline cation; 1,2-dimethylindole cation; 1-ethylcarbazole cation; and the like.

Among these, 1-ethylpyridinium cation, 1-butylpyridinium cation, 1-hexylpyridinium cation, 1-ethyl-3-methylpyridinium cation, 1 -pyridinium cations such as butyl-3-methylpyridinium cation, 1-hexyl-3-methylpyridinium cation, 1-butyl-4-methylpyridinium cation, 1-octyl-4-methylpyridinium cation; 1-ethyl-1- methylpyrrolidinium cation, 1-methyl-1-propylpyrrolidinium cation, 1-methyl-1-butylpyrrolidinium cation, 1-methyl-1-pentylpyrrolidinium cation, 1-methyl-1-hexyl pyrrolidinium cation, 1-methyl-1-heptylpyrrolidinium cation, 1-ethyl-1-propylpyrrolidinium cation, 1-ethyl-1-butylpyrrolidinium cation, 1-ethyl-1-pentylpyrrolidinium cation cation, 1-ethyl-1-hexylpyrrolidinium cation, 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 cation, 1-ethyl-1-pentylpiperidinium cation, 1-ethyl-1- piperidinium cations such as hexylpiperidinium cation, 1-ethyl-1-heptylpiperidinium cation, 1-propyl-1-butylpiperidinium cation; and the like, more preferably 1-hexyl pyridinium cation, 1-ethyl-3-methylpyridinium cation, 1-butyl-3-methylpyridinium cation, 1-octyl-4-methylpyridinium cation, 1-methyl-1-propylpyrrolidinium cation, 1-methyl-1 - is a propylpiperidinium cation.

Examples of cations represented by general formula (2) include imidazolium cations, tetrahydropyrimidinium cations, and dihydropyrimidinium cations.

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

Among these, 1,3-dimethylimidazolium cation, 1,3-diethylimidazolium cation, 1-ethyl-3-methylimidazolium cation, 1 -butyl-3-methylimidazolium cation, 1-hexyl-3-methylimidazolium cation, 1-octyl-3-methylimidazolium cation, 1-decyl-3-methylimidazolium cation, 1-dodecyl-3- imidazolium cations such as methylimidazolium cations and 1-tetradecyl-3-methylimidazolium cations, more preferably 1-ethyl-3-methylimidazolium cations and 1-hexyl-3-methylimidazolium cations; be.

Examples of the cation represented by formula (3) include pyrazolium cation and 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; pyrazolinium cation 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 cations represented by general formula (4) include tetraalkylammonium cations, trialkylsulfonium cations, tetraalkylphosphonium cations, and some of the above alkyl groups are substituted with alkenyl groups, alkoxyl groups, and epoxy groups. and the like.

Specific examples of the cation represented by formula (4) include tetramethylammonium cation, tetraethylammonium cation, tetrabutylammonium cation, tetrapentylammonium cation, tetrahexylammonium cation, tetraheptylammonium cation, and triethylmethylammonium. cations, 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, triethyl Examples include methylphosphonium cation, tributylethylphosphonium cation, trimethyldecylphosphonium cation, and diallyldimethylammonium cation.

Among these, triethylmethylammonium cation, tributylethylammonium cation, trimethyldecylammonium cation, diethylmethylsulfonium cation, dibutylethylsulfonium cation, dimethyldecylsulfonium cation, and Asymmetric tetraalkylammonium cations, trialkylsulfonium cations, tetraalkylphosphonium cations such as triethylmethylphosphonium cation, tributylethylphosphonium cation, trimethyldecylphosphonium cation, and N,N-diethyl-N-methyl-N-(2-methoxy ethyl)ammonium cation, glycidyltrimethylammonium cation, diallyldimethylammonium cation, N,N-dimethyl-N-ethyl-N-propylammonium cation, N,N-dimethyl-N-ethyl-N-butylammonium cation, N,N -dimethyl-N-ethyl-N-pentylammonium cation, N,N-dimethyl-N-ethyl-N-hexylammonium cation, N,N-dimethyl-N-ethyl-N-heptylammonium cation, N,N-dimethyl -N-ethyl-N-nonylammonium cation, N,N-dimethyl-N,N-dipropylammonium cation, N,N-diethyl-N-propyl-N-butylammonium cation, N,N-dimethyl-N- Propyl-N-pentylammonium cation, N,N-dimethyl-N-propyl-N-hexylammonium cation, N,N-dimethyl-N-propyl-N-heptylammonium cation, N,N-dimethyl-N-butyl- N-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 cations, 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 cations, 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 more preferably trimethylpropylammonium cation.

As the fluoroorganic anion that can constitute the ionic liquid, any suitable fluoroorganic anion can be adopted as long as the effects of the present invention are not impaired. Such fluoroorganic anions may be fully fluorinated (perfluorinated) or partially fluorinated.

Such fluoroorganic anions include, for example, fluorinated arylsulfonates, perfluoroalkanesulfonates, bis(fluorosulfonyl)imides, bis(perfluoroalkanesulfonyl)imides, cyanoperfluoroalkanesulfonylamides, bis(cyano) perfluoroalkanesulfonylmethide, cyano-bis-(perfluoroalkanesulfonyl)methide, tris(perfluoroalkanesulfonyl)methide, trifluoroacetate, perfluoroalkylate, tris(perfluoroalkanesulfonyl)methide, (perfluoroalkane sulfonyl)trifluoroacetamide and the like.

Among these fluoroorganic anions, more preferred are perfluoroalkylsulfonate, bis(fluorosulfonyl)imide and bis(perfluoroalkanesulfonyl)imide, more specifically trifluoromethanesulfonate, pentafluoroethane sulfonate, heptafluoropropanesulfonate, nonafluorobutanesulfonate, bis(fluorosulfonyl)imide, bis(trifluoromethanesulfonyl)imide.

Specific examples of the ionic liquid may be appropriately selected from combinations of the above cationic components and the above anionic components. Specific examples of such ionic liquids include 1-hexylpyridinium bis(fluorosulfonyl)imide, 1-ethyl-3-methylpyridinium trifluoromethanesulfonate, 1-ethyl-3-methylpyridinium pentafluoroethanesulfonate, 1-ethyl-3-methylpyridinium heptafluoropropanesulfonate, 1-ethyl-3-methylpyridinium nonafluorobutanesulfonate, 1-butyl-3-methylpyridinium trifluoromethanesulfonate, 1-butyl-3-methylpyridinium bis(trifluoromethane sulfonyl)imide, 1-butyl-3-methylpyridinium bis(pentafluoroethanesulfonyl)imide, 1-octyl-4-methylpyridinium bis(fluorosulfonyl)imide, 1,1-dimethylpyrrolidinium bis(trifluoromethanesulfonyl)imide 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-hexylpyrroli Dinium bis(trifluoromethanesulfonyl)imide, 1-methyl-1-heptylpyrrolidinium bis(trifluoromethanesulfonyl)imide, 1-ethyl-1-propylpyrrolidinium bis(trifluoromethanesulfonyl)imide, 1-ethyl -1-butylpyrrolidinium bis(trifluoromethanesulfonyl)imide, 1-ethyl-1-pentylpyrrolidinium bis(trifluoromethanesulfonyl)imide, 1-ethyl-1-hexylpyrrolidinium bis(trifluoromethanesulfonyl)imide 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)imide phonyl)imide, 1-pentylpiperidinium bis(trifluoromethanesulfonyl)imide, 1,1-dimethylpiperidinium bis(trifluoromethanesulfonyl)imide, 1-methyl-1-ethylpiperidinium bis(trifluoromethanesulfonyl)imide imide, 1-methyl-1-propylpiperidinium bis(trifluoromethanesulfonyl)imide, 1-methyl-1-propylpiperidinium bis(fluorosulfonyl)imide, 1-methyl-1-butylpiperidinium bis(trifluoro methanesulfonyl)imide, 1-methyl-1-pentylpiperidinium bis(trifluoromethanesulfonyl)imide, 1-methyl-1-hexylpiperidinium bis(trifluoromethanesulfonyl)imide, 1-methyl-1-heptyl Lupiperidinium 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 ) imide, 1,1-dipropylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-propyl-1-butylpiperidinium bis (trifluoromethanesulfonyl) imide, 1,1-dibutylpiperidinium bis (trifluoromethane sulfonyl)imide, 1,1-dimethylpyrrolidinium bis(pentafluoroethanesulfonyl)imide, 1-methyl-1-ethylpyrrolidinium bis(pentafluoroethanesulfonyl)imide, 1-methyl-1-propylpyrrolidinium Bis(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(pentafluoroethanesulfonyl)imide Fluoroethane 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 imide, 1-methyl-1-propylpiperidinium bis(pentafluoroethanesulfonyl)imide, 1-methyl-1-butylpiperidinium bis(pentafluoroethanesulfonyl)imide, 1-methyl-1-pentylpiperidinium bis(pentafluoroethanesulfonyl)imide, 1-methyl-1-hexylpiperidinium bis(pentafluoroethanesulfonyl)imide, 1-methyl-1-heptylpiperidinium bis(pentafluoroethanesulfonyl)imide, 1 -ethyl-1-propylpiperidinium bis(pentafluoroethanesulfonyl)imide, 1-ethyl-1-butylpiperidinium bis(pentafluoroethanesulfonyl)imide, 1-ethyl-1-pentylpiperidinium bis(pentafluoroethanesulfonyl)imide fluoroethanesulfonyl)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-methylimidazoly um trifluoroacetate, 1-ethyl-3-methylimidazolium heptafluorobutyrate, 1-ethyl-3-methylimidazolium trifluoromethanesulfonate, 1-ethyl-3-methylimidazolium heptafluoropropanesulfonate, 1-ethyl- 3-methylimidazolium nonafluorobutanesulfonate, 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, 1-ethyl-3-methylimidazolium bis(fluorosulfonyl)imide, 1-ethyl-3-methyl imidazolium 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-methylimidazolium bis(trifluoromethanesulfonyl)imide, 1 -hexyl-3-methylimidazolium trifluoromethanesulfonate, 1-hexyl-3-methylimidazolium bis(fluorosulfonyl)imide, 1,2-dimethyl-3-propylimidazolium bis(trifluoromethanesulfonyl)imide, 1- ethyl-2,3,5-trimethylpyrazolium bis(trifluoromethanesulfonyl)imide, 1-propyl-2,3,5-trimethylpyrazolium bis(trifluoromethanesulfonyl)imide, 1-butyl-2,3, 5-trimethylpyrazolium bis(trifluoromethanesulfonyl)imide, 1-ethyl-2,3,5-trimethylpyrazolium bis(pentafluoroethanesulfonyl)imide, 1-propyl-2,3,5-trimethylpyrazo lithium bis(pentafluoroethanesulfonyl)imide, 1-butyl-2,3,5-trimethylpyrazolium bis(pentafluoroethanesulfonyl)imide, 1-ethyl-2,3,5-trimethylpyrazolium (trifluoromethane sulfonyl)trifluoroacetamide, 1-propyl-2,3,5-trimethylpyrazolium (trifluoromethanesulfonyl)trifluoroacetamide, 1-butyl-2,3,5-trimethylpyrazolium (trifluoro methanesulfonyl)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(trifluoromethanesulfonyl)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-heptyl ammonium bis(trifluoromethanesulfonyl)imide, N,N-dimethyl-N-butyl-N-hexylammonium bis(trifluoromethanesulfonyl)imide, N,N-dimethyl-N-butyl-N-heptylammonium 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(trifluoromethanesulfonyl)imide, N,N-diethyl-N-methyl-N,N-heptylammonium bis(trifluoromethanesulfonyl)imide, N,N-diethyl-N-propyl-N-pentylane monium 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-methylpyridinium (trifluoromethanesulfonyl) trifluoroacetamide, 1-ethyl-3-methylimidazolium (trifluoromethanesulfonyl) ) trifluoroacetamide, tetrahexylammonium bis(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 nium bis(trifluoromethanesulfonyl)imide, glycidyltrimethylammonium bis(pentafluoroethanesulfonyl)imide, diallyldimethylammonium bis(trifluoromethanesulfonyl)imide, diallyldimethylbis(pentafluoroethanetansulfonyl)imide, lithium bis(trifluoromethanesulfonyl)imide imide, lithium bis(fluorosulfonyl)imide, and the like.

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

A commercially available ionic liquid may be used, but it is also possible to synthesize it as follows. The method for synthesizing the ionic liquid is not particularly limited as long as the desired ionic liquid can be obtained. Publishing), the halide method, the hydroxide method, the acid ester method, the complexation method, and the neutralization method are used.

The synthesis methods of the halide method, the hydroxide method, the acid ester method, the complex formation method, and the neutralization method are shown below using nitrogen-containing onium salts as examples, but other sulfur-containing onium salts and phosphorus-containing onium salts and other ionic liquids can be obtained by the same method.

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

The obtained halide is an acid (HA) or salt having an anion structure (A ⁻ ) of the target ionic liquid (MA, M are cations that form a salt with the target anion such as ammonium, lithium, sodium, potassium, etc. ) to obtain the desired ionic liquid (R ₄ NA).

The hydroxide method is a method carried out by reactions shown in reaction formulas (4) to (8). First, a halide (R ₄ NX) is electrolyzed by an ion-exchange membrane method (reaction formula (4)), an OH-type ion-exchange resin method (reaction formula (5)), or a reaction with silver oxide (Ag ₂ O) (reaction formula ( A hydroxide (R ₄ NOH) is obtained in 6)) (chlorine, bromine, and iodine are used as halogens).

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

The acid ester method is a method carried out by reactions 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 (reaction formula (9)). Esters and esters of organic acids such as methanesulfonic acid, methylphosphonic acid and formic acid are used).

The target ionic liquid (R ₄ NA) can be obtained by subjecting the obtained acid ester to the reactions of reaction formulas (10) to (11) in the same manner as in the above halogenation method. Alternatively, the ionic liquid can be obtained directly by using methyltrifluoromethanesulfonate, methyltrifluoroacetate, or the like as the acid ester.

The neutralization method is a method carried out by the reaction shown in reaction formula (12). reacting a tertiary amine with an organic _acid such as _{CF3COOH , CF3SO3H} , _{( CF3SO2} ) _2NH , _{( CF3SO2} ) _3CH , _{( C2F5SO2} ) _2NH ; can be obtained by

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

The amount of the ionic liquid to be blended varies depending on the compatibility between the polymer and the ionic liquid used, and cannot be generally defined. 001 parts by weight to 50 parts by weight, more preferably 0.01 parts by weight to 40 parts by weight, still more preferably 0.01 parts by weight to 30 parts by weight, and particularly preferably 0.01 parts by weight to 20 parts by weight. parts by weight, most preferably 0.01 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 extremely excellent antistatic properties. If the amount of the ionic liquid is less than 0.01 part by weight, it may not be possible to obtain sufficient antistatic properties. If the amount of the ionic liquid exceeds 50 parts by weight, contamination of the adherend tends to increase.

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

When the urethane pressure-sensitive adhesive contains modified silicone oil, the content is preferably 0.001 to 50 parts by weight, more preferably 0.01 to 50 parts by weight, relative 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, most preferably 0.01 to 10 parts by weight . By adjusting the content of the modified silicone oil within the above range, the effects of the present invention can be exhibited even more effectively.

As the modified silicone oil, any appropriate modified silicone oil can be adopted as long as the effects of the present invention are not impaired. Examples of such modified silicone oils include modified silicone oils 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 exhibited even more effectively.

Examples of the polyether-modified silicone oil include side-chain-type polyether-modified silicone oil and both-ends-type polyether-modified silicone oil. Among these, double-ended polyether-modified silicone oil is preferable in that the effects of the present invention can be sufficiently and more effectively exhibited.

(Polyurethane resin formed from composition containing polyol (A) and 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 an object.

Only one kind of polyol (A) may be used, or two or more kinds thereof may be used.

The number of polyfunctional isocyanate compounds (B) may be one, or two or more.

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

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

Polyol components include, for example, ethylene glycol, diethylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2-butyl-2-ethyl-1 ,3-propanediol, 2,4-diethyl-1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 2-methyl -1,8-octanediol, 1,8-decanediol, octadecanediol, glycerin, trimethylolpropane, pentaerythritol, hexanetriol, polypropylene glycol and the like. Examples of acid components include succinic acid, methylsuccinic 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 , acid anhydrides thereof, and the like.

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

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

Polycarbonate polyols include, for example, polycarbonate polyols obtained by subjecting the above polyol component and phosgene to a polycondensation reaction; Polycarbonate polyols obtained by transesterification condensation with carbonic acid diesters such as propylene carbonate, diphenyl carbonate, and dibenzyl carbonate; Copolycarbonate polyols obtained by using two or more of the above polyol components in combination; Various polycarbonate polyols above and carboxyl group-containing polyols Polycarbonate polyol obtained by esterifying a compound; Polycarbonate polyol obtained by etherifying the above various polycarbonate polyols and a hydroxyl group-containing compound; Obtained by transesterifying the above various polycarbonate polyols and an ester compound. Polycarbonate polyols; Polycarbonate polyols obtained by transesterification of various polycarbonate polyols and hydroxyl group-containing compounds; Polyester-based polycarbonate polyols obtained by polycondensation reaction of various polycarbonate polyols and dicarboxylic acid compounds; Various polycarbonate polyols and a copolymerized polyether-based polycarbonate polyol obtained by copolymerizing alkylene oxide; and the like.

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

The number average molecular weight Mn of the polyol (A) is preferably 400-20,000, more preferably 500-17,000, even more preferably 600-15,000, and particularly preferably 800-12,000. 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, when the release liner is to be peeled off, the optical member adheres to the surface of the release liner together with the release liner. The effect that it is difficult to peel off from the protective film, that is, the effect that peeling hardly occurs at the interface between the optical member and the surface protective film can be exhibited.

The polyol (A) preferably contains a polyol (A1) having three OH groups and a number average molecular weight Mn of 8,000 to 20,000. Only one kind of polyol (A1) may be used, or two or more kinds thereof may be used.

The content of polyol (A1) in polyol (A) is preferably 70% by weight or more, more preferably 70% to 100% by weight, still more preferably 70% to 90% by weight. By adjusting the content ratio of the polyol (A1) in the polyol (A) 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 can be easily removed from the release liner. Together with this, it is difficult to peel off from the surface protective film, that is, the effect that peeling hardly occurs at the interface between the optical member and the surface protective film can be further exhibited.

The number average molecular weight Mn of the polyol (A1) is preferably 8,000 to 20,000, more preferably 8,000 to 18,000, even more preferably 8,500 to 17,000, still more preferably 9,000 to 16,000, and particularly preferably 9,500. ~15,500, most preferably 10,000-15,000. 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, when the release liner is to be peeled off, the optical member adheres to the surface of the release liner together with the release liner. The effect that it is difficult to peel off from the protective film, that is, the effect that peeling hardly occurs at the interface between the optical member and the surface protective film can be exhibited.

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. Only one kind of polyol (A2) may be used, or two or more kinds thereof may be used. 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, most preferably 1000. ~3000. If the number-average molecular weight Mn of the polyol (A2) is out of the above range, the adhesive strength may increase over time, and excellent reworkability may not be achieved. The polyol (A2) is preferably a polyol having 3 OH groups (triol), a polyol having 4 OH groups (tetraol), a polyol having 5 OH groups (pentaol), or 6 OH groups. polyols (hexaols) having

As the polyol (A2), the 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 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. At least a polyol (tetraol) having 4 OH groups, a polyol having 5 OH groups (pentaol), and a polyol having 6 OH groups (hexaol) as the polyol (A2) in the polyol (A) By adjusting one type to the above range, it is possible to provide a urethane-based pressure-sensitive adhesive with even more excellent transparency.

The content of polyol (A2) in polyol (A) is preferably 30% by weight or less, more preferably 0% to 30% by weight. By adjusting the content ratio of the polyol (A2) in the polyol (A) 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 can be removed from the release liner. Together with this, it is difficult to peel off from the surface protective film, that is, the effect that peeling hardly occurs at the interface between the optical member and the surface protective film can be further exhibited.

In the polyol (A2), the content of polyols having 4 or more OH groups and a number average molecular weight Mn of 5000 or less is preferably less than 10% by weight, more preferably less than 10% by weight, based on the total 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 of the polyol having 4 or more OH groups and a number average molecular weight Mn of 5000 or less in the polyol (A2) is 10% by weight or more relative to the total polyol (A), the urethane pressure-sensitive adhesive becomes white. There is a possibility that it will become easy to change and the transparency will decrease.

The number of polyfunctional isocyanate compounds (B) may be one, or two or more.

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

Polyfunctional aliphatic isocyanate compounds include, for example, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, 2,4, 4-trimethylhexamethylene diisocyanate and the like.

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

Polyfunctional aromatic diisocyanate compounds include, for example, phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,2′-diphenylmethane diisocyanate, 4,4′-diphenylmethane diisocyanate, 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 such as those described above, water-reacted biuret forms, trimers having an isocyanurate ring, and the like. Moreover, you may use these together.

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 0.2 to 1.8, particularly preferably 0.3 to 1.7, and most preferably 0.5 to 1.6. By adjusting the NCO group/OH group equivalent ratio within the above range, the optical member with a surface protective film of the present invention can protect the surface of the optical member together with the release liner when the release liner is to be peeled off. The effect that it is difficult to peel off from the film, that is, the effect that peeling hardly occurs at the interface between the optical member and the surface protection film can be further exhibited.

The content of the polyfunctional isocyanate compound (B) is preferably 1.0% by weight to 20% by weight, more preferably 1.5% by weight, based on 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. is. By adjusting the content of the polyfunctional isocyanate compound (B) within the above range, the surface protective film-attached optical member of the present invention is such that when the release liner is to be peeled off, the optical member can be removed together with the release liner. The effect that it is difficult to peel off from the surface protective film, that is, the effect that peeling hardly occurs at the interface between the optical member and the surface protective film can be exhibited.

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

As a method for forming a polyurethane-based resin by curing a composition containing a polyol (A) and a polyfunctional isocyanate compound (B), effects of the present invention, such as a urethanization reaction method using bulk polymerization or solution polymerization, etc. Any appropriate method can be adopted as long as it does not impair the

A catalyst is preferably used to cure the composition containing the polyol (A) and the polyfunctional isocyanate compound (B). Examples of such catalysts include organometallic compounds and tertiary amine compounds.

Examples of organometallic compounds include iron-based compounds, tin-based compounds, titanium-based compounds, zirconium-based compounds, lead-based compounds, cobalt-based compounds, and zinc-based compounds. Among these, iron-based compounds and tin-based compounds are preferable in terms of reaction speed 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, tributyltin ethoxide, dioctyltin oxide, dioctyltin dilaurate, tributyltin chloride, tributyltin trichloroacetate, tin 2-ethylhexanoate and the like.

Titanium compounds include, for example, dibutyltitanium dichloride, tetrabutyltitanate, butoxytitanium trichloride and the like.

Zirconium-based compounds include, for example, zirconium naphthenate and zirconium acetylacetonate.

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

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

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

Tertiary amine compounds include, for example, triethylamine, triethylenediamine, 1,8-diazabisic-(5,4,0)-undecene-7 and the like.

Only one kind of catalyst may be used, or two or more kinds thereof may be used. Moreover, a catalyst and a cross-linking retarder may be used in combination. The amount of the catalyst is preferably 0.02% to 0.10% by weight, more preferably 0.02% to 0.08% by weight, more preferably 0% by weight, relative to the polyol (A). 0.02% to 0.06% by weight, particularly preferably 0.02% to 0.05% by weight. 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 off from the surface protective film together with the release liner when the release liner is to be peeled off. In other words, the effect that peeling hardly occurs at the interface between the optical member and the surface protective film can be further exhibited.

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. Such other components include, for example, resin components other than polyurethane resins, tackifiers, inorganic fillers, organic fillers, metal powders, pigments, foils, softeners, anti-aging agents, conductive agents, UV absorbers, antioxidants, light stabilizers, surface lubricants, leveling agents, corrosion inhibitors, heat stabilizers, polymerization inhibitors, lubricants, solvents, catalysts and the like.

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

A polyurethane resin formed from a composition containing a urethane prepolymer (C) and a polyfunctional isocyanate compound (B) contains, for example, a polyurethane polyol as the urethane prepolymer (C) and a polyfunctional isocyanate compound (B). Polyurethane-based resins formed from compositions that The urethane prepolymer (C) may be of only one type, or may be of two or more types. The number of polyfunctional isocyanate compounds (B) may be one, or two or more.

The polyurethane polyol as the urethane prepolymer (C) is preferably obtained by reacting 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 that is made possible.

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

As the molecular weight of the polyester polyol (a1), it is possible to use from low molecular weight to high molecular weight. As for the molecular weight of the polyester polyol (a1), the number average molecular weight is preferably 500 to 5,000. If the number average molecular weight is less than 500, the reactivity becomes high and gelation may easily occur. If the number-average molecular weight exceeds 5,000, the reactivity may become low, and the cohesive strength of the polyurethane polyol itself may become small. The amount of the polyester polyol (a1) used is preferably 10 to 90 mol % of the polyols constituting the polyurethane polyol.

Any appropriate polyether polyol can be used as the polyether polyol (a2). Examples of such polyether polyols (a2) include water, propylene glycol, ethylene glycol, glycerin, trimethylolpropane, and other low-molecular-weight polyols as initiators, and ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, and the like. Examples include polyether polyols obtained by polymerizing oxirane compounds. Specific examples of such polyether polyols (a2) include polyether polyols having two or more functional groups, such as polypropylene glycol, polyethylene glycol, and polytetramethylene glycol.

As the molecular weight of the polyether polyol (a2), it is possible to use from low molecular weight to high molecular weight. As for the molecular weight of the polyether polyol (a2), the number average molecular weight is preferably 1,000 to 5,000. If the number average molecular weight is less than 1,000, the reactivity becomes high and gelation may easily occur. If the number-average molecular weight exceeds 5,000, the reactivity may become low, and the cohesive strength of the polyurethane polyol itself may become small. The amount of the polyether polyol (a2) used is preferably 20 mol % to 80 mol % of the polyol constituting the polyurethane polyol.

Part of the polyether polyol (a2), if necessary, glycols such as ethylene glycol, 1,4-butanediol, neopentyl glycol, butylethylpentanediol, glycerin, trimethylolpropane, pentaerythritol, It can be used in combination with polyvalent amines such as ethylenediamine, N-aminoethylethanolamine, isophoronediamine, xylylenediamine, and the like.

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 at least 3 or more hydroxyl groups in one molecule. Part or all of the polyol may be used. As the polyether polyol (a2), a polyether polyol having an average molecular weight of 1000 to 5000 and having at least 3 or more hydroxyl groups in one molecule is partially or wholly used. 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 is likely to occur. Moreover, in such a polyether polyol, if the number average molecular weight exceeds 5,000, the reactivity may be lowered, and the cohesive strength of the polyurethane polyol itself may be lowered. The number average molecular weight of such polyether polyols is more preferably 2500-3500.

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

Examples of aromatic polyisocyanates include 1,3-phenylene diisocyanate, 4,4'-diphenyldiisocyanate, 1,4-phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6 - tolylene diisocyanate, 4,4'-toluidine diisocyanate, 2,4,6-triisocyanatotoluene, 1,3,5-triisocyanatobenzene, dianisidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4', 4″-triphenylmethane triisocyanate and the like.

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

Examples of araliphatic polyisocyanates 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 alicyclic polyisocyanates include 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate, 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, methyl-2 ,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4′-methylenebis(cyclohexyl isocyanate), 1,4-bis(isocyanatomethyl)cyclohexane, 1,4-bis(isocyanatomethyl)cyclohexane and the like. be done.

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

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

Tertiary amine compounds include, for example, triethylamine, triethylenediamine, 1,8-diazabicyclo(5,4,0)-undecene-7 (DBU) and the like.

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

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

Examples of non-tin compounds include titanium compounds such as dibutyl titanium dichloride, tetrabutyl titanate, and butoxy titanium trichloride; lead compounds such as lead oleate, lead 2-ethylhexanoate, lead benzoate, and lead naphthenate. iron-based compounds such as iron 2-ethylhexanoate and iron acetylacetonate; cobalt-based compounds such as cobalt benzoate and cobalt 2-ethylhexanoate; zinc-based compounds such as zinc naphthenate and zinc 2-ethylhexanoate; zirconium-based compounds such as zirconium naphthenate;

When a catalyst is used to obtain a polyurethane polyol, in a system in which two kinds of polyols, a polyester polyol and a polyether polyol, are present, gelation or a reaction solution may occur in a single catalyst system due to the difference in reactivity. The problem of turbidity is likely to occur. Therefore, by using two kinds of catalysts when obtaining a polyurethane polyol, the reaction rate, the selectivity of the catalyst, etc. can be easily controlled, and these problems can be solved. Combinations of such two types of catalysts include, for example, tertiary amine/organometallic, tin/non-tin, and tin/tin, preferably tin/tin, and more preferably. is a combination of dibutyltin dilaurate and tin 2-ethylhexanoate. The weight ratio of tin 2-ethylhexanoate/dibutyltin dilaurate is preferably less than 1, more preferably 0.2 to 0.6. If the compounding ratio is 1 or more, gelation may tend 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% by weight.

If a catalyst is used in obtaining the polyurethane polyol, the reaction temperature is preferably below 100°C, more preferably between 85°C and 95°C. If the temperature is 100° C. or higher, it may become difficult to control the reaction rate and the crosslinked structure, and it may become 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, the reaction temperature is preferably 100° C. or higher, more preferably 110° C. or higher. Moreover, when obtaining a polyurethane polyol under no catalyst, it is preferable to carry out reaction for 3 hours or more.

Methods for obtaining polyurethane polyol include, for example, 1) a method of charging a polyester polyol, a polyether polyol, a catalyst, and an organic polyisocyanate into a volumetric flask, and 2) a method of charging a polyester polyol, a polyether polyol, and a catalyst into a flask to produce an organic polyisocyanate. can be added dropwise. As a method for obtaining a polyurethane polyol, the method 2) is preferable from the viewpoint of controlling the reaction.

Any suitable solvent may be used in obtaining the polyurethane polyol. Examples of such solvents include methyl ethyl ketone, ethyl acetate, toluene, xylene and acetone. Among these solvents, toluene is preferred.

As the polyfunctional isocyanate compound (B), those mentioned above can be used.

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. Such other components include, for example, resin components other than polyurethane resins, tackifiers, inorganic fillers, organic fillers, metal powders, pigments, foils, softeners, anti-aging agents, conductive agents, UV absorbers, antioxidants, light stabilizers, surface lubricants, leveling agents, corrosion inhibitors, heat stabilizers, polymerization inhibitors, lubricants, solvents, catalysts and the like.

As a method for producing a polyurethane resin formed from a composition containing a urethane prepolymer (C) and a polyfunctional isocyanate compound (B), a so-called "urethane prepolymer" is used as a raw material to produce a polyurethane resin. Any appropriate manufacturing method can be adopted as far as the method is concerned.

The urethane prepolymer (C) preferably has a number average molecular weight Mn of 1,000 to 100,000.

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

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

[Acrylic adhesive]
Acrylic pressure-sensitive adhesives contain acrylic resins.

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 of the acrylic resin in the acrylic pressure-sensitive adhesive within the above range, the surface protective film-attached optical member of the present invention is such that when the release liner is to be peeled off, the optical member and the release liner are separated from each other. Together, it is difficult to peel off from the surface protective film, that is, the effect that peeling hardly occurs at the interface between the optical member and the surface protective film can be further exhibited.

The acrylic pressure-sensitive adhesive may contain any appropriate other component in addition to the acrylic resin within a range that does not impair the effects of the present invention. Such other components include, for example, resin components other than acrylic resins, tackifiers, inorganic fillers, organic fillers, metal powders, pigments, foil materials, softeners, anti-aging agents, conductive agents, UV absorbers, antioxidants, light stabilizers, surface lubricants, leveling agents, corrosion inhibitors, heat stabilizers, polymerization inhibitors, lubricants, solvents, catalysts and the like.

As the acrylic resin, any appropriate acrylic resin can be adopted as long as the effects of the present invention are not impaired. The acrylic pressure-sensitive adhesive preferably comprises (a) a (meth)acrylic acid alkyl ester in which the alkyl group of the alkyl ester moiety has 4 to 12 carbon atoms, (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 polyfunctional isocyanate cross-linking agents and epoxy cross-linking agents.

The content of 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 even more preferably is 92.5% to 98% by weight, particularly preferably 95% to 97.5% by weight. By adjusting the content 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 can be easily peeled off when the release liner is to be peeled off. is less likely to be released from the surface protective film together with the release liner, that is, the effect of being less likely to be released at the interface between the optical member and the surface protective film can be exhibited.

The content of component (b) in the composition forming the acrylic resin is preferably 0.5% to 15% by weight, more preferably 1.5% to 10% by weight, and even more preferably 1.5% to 10% by weight. 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 can be easily peeled off when the release liner is to be peeled off. is less likely to be released from the surface protective film together with the release liner, that is, the effect of being less likely to be released at the interface between the optical member and the surface protective film can be exhibited.

The content of the component (c) in the composition forming the acrylic resin is preferably 1 wt% to 10 wt%, more preferably 1.5 wt% to 9 wt%, still more preferably 2 % to 8% by weight, particularly preferably 2.5% to 7% by weight. By adjusting the content ratio of the component (c) in the composition forming the acrylic resin within the above range, the optical member with a surface protective film of the present invention can be easily peeled off when the release liner is to be peeled off. is less likely to be released from the surface protective film together with the release liner, that is, the effect of being less likely to be released at the interface between the optical member and the surface protective film can be exhibited.

Examples of (meth)acrylic acid alkyl esters in which the alkyl group in the alkyl ester portion has 4 to 12 carbon atoms 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 , cyclohexyl (meth) acrylate. These may be of only one type, or may be of two or more types.

The number of carbon atoms in the alkyl group in the (meth)acrylic acid alkyl ester having 4 to 12 carbon atoms in the alkyl ester portion is preferably 4 to 10, more preferably 4 to 8. Alkyl groups can be straight or branched.

Examples of (meth)acrylic acid esters 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-hydroxymethylcyclohexyl)-methyl acrylate. These may be of only one type, or may be of two or more types.

Polyfunctional isocyanate-based cross-linking agents include, for example, lower aliphatic polyisocyanates such as butylene diisocyanate and hexamethylene diisocyanate; alicyclic isocyanates such as cyclopentylene diisocyanate, cyclohexylene diisocyanate and isophorone diisocyanate; Aromatic isocyanates such as tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, and xylylene diisocyanate, trimethylolpropane/tolylene diisocyanate trimer adduct (trade name “Coronate L” manufactured by Nippon Polyurethane Industry Co., Ltd.), trimethylol Isocyanate adducts such as propane/hexamethylene diisocyanate trimer adduct (trade name "Coronate HL" manufactured by Nippon Polyurethane Industry Co., Ltd.), isocyanurate form of hexamethylene diisocyanate (trade name "Coronate HX" manufactured by Nippon Polyurethane Industry Co., Ltd.) etc. These may be of only one type, or may be of two or more types.

Epoxy cross-linking agents include, for example, 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, diglycidylaniline, diamine glycidylamine, N,N,N',N'-tetraglycidyl-m-xylylenediamine (trade name "TETRAD-X" manufactured by Mitsubishi Gas Chemical Co., Ltd.), 1,3-bis (N,N-diglycidylaminomethyl)cyclohexane (trade name “TETRAD-C” manufactured by Mitsubishi Gas Chemical Co., Ltd.) and the like. These may be of only one type, or may be of two or more types.

The composition forming the acrylic resin may further contain a cross-linking catalyst. Examples of cross-linking catalysts include metal-based cross-linking catalysts (especially tin-based cross-linking catalysts) such as tetra-n-butyl titanate, tetraisopropyl titanate, Nasem ferric iron, butyltin oxide, and dioctyltin dilaurate. Only one kind of such a crosslinking catalyst may be used, or two or more kinds thereof may be used.

The composition forming the acrylic resin may contain any appropriate other monomers within a range that does not impair the effects of the present invention. Such other monomers include, for example, benzyl (meth)acrylate, methoxyethyl (meth)acrylate, ethoxymethyl (meth)acrylate, phenoxyethyl (meth)acrylate, (meth)acrylamide, vinyl acetate, (meth)acrylonitrile etc. These may be of only one type, or may be of two or more types.

The composition forming the acrylic resin may contain any appropriate other component within a range that does not impair the effects of the present invention. Such other components include, for example, resin components other than acrylic resins, tackifiers, inorganic fillers, organic fillers, metal powders, pigments, foils, softeners, anti-aging agents, conductive agents, UV absorbers, antioxidants, light stabilizers, surface lubricants, leveling agents, corrosion inhibitors, heat stabilizers, polymerization inhibitors, lubricants, solvents, catalysts and the like.

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 chromatography (GPC) method using a tetrahydrofuran solvent. , more preferably 200,000 to 2,000,000, and 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 easily peeled off together with the release liner when the release liner is to be peeled off. The effect that it is difficult to peel off from the surface protective film, that is, the effect that peeling hardly occurs at the interface between the optical member and the surface protective film can be exhibited.

The acrylic resin can be produced by any suitable method as long as the effects of the present invention are not impaired. Such a method includes, for example, 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, the solution polymerization method is preferable from the viewpoint of cost and productivity. The solution polymerization method includes, for example, a method of dissolving a monomer component, a polymerization initiator, etc. in a solvent and heating and polymerizing to obtain a base polymer solution containing the base polymer.

Examples of solvents include aromatic hydrocarbons such as toluene, benzene and xylene; esters such as ethyl acetate and n-butyl acetate; aliphatic hydrocarbons such as n-hexane and n-heptane; cyclohexane and methylcyclohexane. and alicyclic hydrocarbons; ketones such as methyl ethyl ketone and methyl isobutyl ketone; and organic solvents. Only one kind of solvent may be used, or two or more kinds thereof may be used.

Polymerization initiators that can be used in the solution polymerization method include, for example, peroxide polymerization initiators and azo polymerization initiators. Peroxide-based polymerization initiators include, for example, peroxycarbonates, ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxyesters, etc. More specifically, benzoyl peroxide, t-butyl hydroperoxide, di-t-butyl peroxide, t-butyl peroxybenzoate, dicumyl peroxide, 1,1-bis(t-butylperoxy)-3,3,5- trimethylcyclohexane, 1,1-bis(t-butylperoxy)cyclododecane. Examples of azo polymerization initiators include 2,2'-azobisisobutyronitrile, 2,2'-azobis-2-methylbutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile ), 2,2′-azobis(2-methylpropionate)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'-dimethyleneisobutylamidine) hydrochloride, 2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine]hydrate. 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 to 5 parts by weight, more preferably 0.05 to 3 parts by weight, relative to the total amount (100 parts by weight) of the monomer components constituting the base polymer. Department.

Any appropriate heating temperature can be set as the heating temperature for polymerization by heating in the solution polymerization method as long as the effects of the present invention are not impaired. Such heating temperature is preferably 50 to 80°C. Any appropriate heating time can be set as the heating time for polymerization by heating in the solution polymerization method, as long as the effects of the present invention are not impaired. Such heating time is preferably 1 hour to 24 hours.

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

[Silicone adhesive]
As the silicone-based pressure-sensitive adhesive, any suitable silicone-based pressure-sensitive adhesive such as known silicone-based pressure-sensitive adhesives described in JP-A-2014-047280 can be employed as long as the effects of the present invention are not impaired. . These may be of only one type, or may be of two or more types.

≪Release liner≫
The release liner includes, for example, a release liner in which the surface of a base material (liner base material) such as paper or plastic film is treated with silicone, or a base material (liner base material) such as paper or plastic film whose surface is coated with a polyolefin resin. Examples include laminated release liners. Examples of plastic films as liner substrates include polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate film, polybutylene terephthalate film, Polyurethane films, ethylene-vinyl acetate copolymer films and the like are included. A polyethylene film is preferable as the plastic film as the liner base material.

<<Adhesive layer (2)>>
The pressure-sensitive adhesive layer (2) can be produced by any suitable production method. Examples of such a production method include a method of applying a composition, which is a material for forming the adhesive layer (2), onto a release liner to form the adhesive layer (2) on the release liner. Examples of such coating methods include roll coating, gravure coating, reverse coating, roll brushing, spray coating, air knife coating, and extrusion coating using a die coater.

The thickness of the adhesive layer (2) is preferably 1 μm to 500 μm, more preferably 2 μm to 400 μm, even more preferably 5 μm to 350 μm, and particularly preferably 10 μm to 300 μm. By adjusting the thickness of the pressure-sensitive adhesive layer (2) within the above range, the surface protective film-attached optical member of the present invention allows the optical member to adhere to the surface together with the release liner when the release liner is to be peeled off. The effect that it is difficult to peel off from the protective film, that is, the effect that peeling hardly occurs at the interface between the optical member and the surface protective film can be exhibited.

The content of the adhesive in the adhesive layer (2) is preferably 50 wt% to 100 wt%, more preferably 60 wt% to 100 wt%, still more preferably 70 wt% to 100 wt%. , particularly preferably 80% to 100% by weight, most preferably 90% to 100% by weight. By adjusting the content of the pressure-sensitive adhesive in the pressure-sensitive adhesive layer (2) within the above range, the surface protective film-attached optical member of the present invention is such that, when the release liner is to be peeled off, the optical member will adhere to the release liner. Together with this, it is difficult to peel off from the surface protective film, that is, the effect that peeling hardly occurs at the interface between the optical member and the surface protective film can be further exhibited.

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

Acrylic pressure-sensitive adhesives contain acrylic resins.

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 of the acrylic resin in the acrylic pressure-sensitive adhesive within the above range, the surface protective film-attached optical member of the present invention is such that when the release liner is to be peeled off, the optical member and the release liner are separated from each other. Together, it is difficult to peel off from the surface protective film, that is, the effect that peeling hardly occurs at the interface between the optical member and the surface protective film can be further exhibited.

The acrylic pressure-sensitive adhesive may contain any appropriate other component in addition to the acrylic resin within a range that does not impair the effects of the present invention. Such other components include, for example, resin components other than acrylic resins, tackifiers, inorganic fillers, organic fillers, metal powders, pigments, foil materials, softeners, anti-aging agents, conductive agents, UV absorbers, antioxidants, light stabilizers, surface lubricants, leveling agents, corrosion inhibitors, heat stabilizers, polymerization inhibitors, lubricants, solvents, catalysts and the like.

As the acrylic resin, any appropriate acrylic resin can be adopted as long as the effects of the present invention are not impaired. The acrylic pressure-sensitive adhesive preferably comprises (a) a (meth)acrylic acid alkyl ester in which the alkyl group of the alkyl ester moiety has 4 to 12 carbon atoms, (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 polyfunctional isocyanate cross-linking agents and epoxy cross-linking agents.

The content of component (a) in the composition forming the acrylic resin is preferably 85% by weight to 99.9% by weight, more preferably 90% by weight to 99.8% by weight, and even more preferably is 92.5% to 99.7% by weight, particularly preferably 95% to 99.6% by weight. By adjusting the content 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 can be easily peeled off when the release liner is to be peeled off. is less likely to be released from the surface protective film together with the release liner, that is, the effect of being less likely to be released at the interface between the optical member and the surface protective film can be exhibited.

The content 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 even more preferably is 0.3% to 7.5% by weight, particularly preferably 0.4% 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 can be easily peeled off when the release liner is to be peeled off. is less likely to be released from the surface protective film together with the release liner, that is, the effect of being less likely to be released at the interface between the optical member and the surface protective film can be exhibited.

The content of 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 wt % to 0.8 wt %, and particularly preferably 0.05 wt % to 0.7 wt %. By adjusting the content ratio of the component (c) in the composition forming the acrylic resin within the above range, the optical member with a surface protective film of the present invention can be easily peeled off when the release liner is to be peeled off. is less likely to be released from the surface protective film together with the release liner, that is, the effect of being less likely to be released at the interface between the optical member and the surface protective film can be exhibited.

Examples of (meth)acrylic acid alkyl esters in which the alkyl group in the alkyl ester portion has 4 to 12 carbon atoms 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 , cyclohexyl (meth) acrylate. These may be of only one type, or may be of two or more types.

The number of carbon atoms in the alkyl group in the (meth)acrylic acid alkyl ester having 4 to 12 carbon atoms in the alkyl ester portion is preferably 4 to 10, more preferably 4 to 8. Alkyl groups can be straight or branched.

Examples of (meth)acrylic acid esters 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-hydroxymethylcyclohexyl)-methyl acrylate. These may be of only one type, or may be of two or more types.

Polyfunctional isocyanate-based cross-linking agents include, for example, lower aliphatic polyisocyanates such as butylene diisocyanate and hexamethylene diisocyanate; alicyclic isocyanates such as cyclopentylene diisocyanate, cyclohexylene diisocyanate and isophorone diisocyanate; Aromatic isocyanates such as tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, and xylylene diisocyanate, trimethylolpropane/tolylene diisocyanate trimer adduct (trade name “Coronate L” manufactured by Nippon Polyurethane Industry Co., Ltd.), trimethylol Isocyanate adducts such as propane/hexamethylene diisocyanate trimer adduct (trade name "Coronate HL" manufactured by Nippon Polyurethane Industry Co., Ltd.), isocyanurate form of hexamethylene diisocyanate (trade name "Coronate HX" manufactured by Nippon Polyurethane Industry Co., Ltd.) etc. These may be of only one type, or may be of two or more types.

Epoxy cross-linking agents include, for example, 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, diglycidylaniline, diamine glycidylamine, N,N,N',N'-tetraglycidyl-m-xylylenediamine (trade name "TETRAD-X" manufactured by Mitsubishi Gas Chemical Co., Ltd.), 1,3-bis (N,N-diglycidylaminomethyl)cyclohexane (trade name “TETRAD-C” manufactured by Mitsubishi Gas Chemical Co., Ltd.) and the like. These may be of only one type, or may be of two or more types.

The composition forming the acrylic resin may further contain a cross-linking catalyst. Examples of cross-linking catalysts include metal-based cross-linking catalysts (especially tin-based cross-linking catalysts) such as tetra-n-butyl titanate, tetraisopropyl titanate, Nasem ferric iron, butyltin oxide, and dioctyltin dilaurate. Only one kind of such a crosslinking catalyst may be used, or two or more kinds thereof may be used.

The composition forming the acrylic resin may contain any appropriate other monomers within a range that does not impair the effects of the present invention. Such other monomers include, for example, benzyl (meth)acrylate, methoxyethyl (meth)acrylate, ethoxymethyl (meth)acrylate, phenoxyethyl (meth)acrylate, (meth)acrylamide, vinyl acetate, (meth)acrylonitrile etc. These may be of only one type, or may be of two or more types.

The composition forming the acrylic resin may contain any appropriate other component within a range that does not impair the effects of the present invention. Such other components include, for example, resin components other than acrylic resins, tackifiers, inorganic fillers, organic fillers, metal powders, pigments, foils, softeners, anti-aging agents, conductive agents, UV absorbers, antioxidants, light stabilizers, surface lubricants, leveling agents, corrosion inhibitors, heat stabilizers, polymerization inhibitors, lubricants, solvents, catalysts and the like.

The weight average molecular weight (Mw) of the acrylic resin is preferably 1,000,000 or more, more preferably 1,100,000 to 2,500,000 as measured by a gel permeation chromatography (GPC) method using a tetrahydrofuran solvent. , more preferably 1,200,000 to 2,300,000, and particularly preferably 1,300,000 to 2,100,000. 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 easily peeled off together with the release liner when the release liner is to be peeled off. The effect that it is difficult to peel off from the surface protective film, that is, the effect that peeling hardly occurs at the interface between the optical member and the surface protective film can be exhibited.

The acrylic resin can be produced by any suitable method as long as the effects of the present invention are not impaired. Such a method includes, for example, 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, the solution polymerization method is preferable from the viewpoint of cost and productivity. The solution polymerization method includes, for example, a method of dissolving a monomer component, a polymerization initiator, etc. in a solvent and heating and polymerizing to obtain a base polymer solution containing the base polymer.

Examples of solvents include aromatic hydrocarbons such as toluene, benzene and xylene; esters such as ethyl acetate and n-butyl acetate; aliphatic hydrocarbons such as n-hexane and n-heptane; cyclohexane and methylcyclohexane. and alicyclic hydrocarbons; ketones such as methyl ethyl ketone and methyl isobutyl ketone; and organic solvents. Only one kind of solvent may be used, or two or more kinds thereof may be used.

Polymerization initiators that can be used in the solution polymerization method include, for example, peroxide polymerization initiators and azo polymerization initiators. Peroxide-based polymerization initiators include, for example, peroxycarbonates, ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxyesters, etc. More specifically, benzoyl peroxide, t-butyl hydroperoxide, di-t-butyl peroxide, t-butyl peroxybenzoate, dicumyl peroxide, 1,1-bis(t-butylperoxy)-3,3,5- trimethylcyclohexane, 1,1-bis(t-butylperoxy)cyclododecane. Examples of azo polymerization initiators include 2,2'-azobisisobutyronitrile, 2,2'-azobis-2-methylbutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile ), 2,2′-azobis(2-methylpropionate)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'-dimethyleneisobutylamidine) hydrochloride, 2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine]hydrate. 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 to 5 parts by weight, more preferably 0.05 to 3 parts by weight, relative to the total amount (100 parts by weight) of the monomer components constituting the base polymer. Department.

Any appropriate heating temperature can be set as the heating temperature for polymerization by heating in the solution polymerization method as long as the effects of the present invention are not impaired. Such heating temperature is preferably 50 to 80°C. Any appropriate heating time can be set as the heating time for polymerization by heating in the solution polymerization method, as long as the effects of the present invention are not impaired. Such heating time is preferably 1 hour 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 side of the optical member opposite to the surface protective film, and the adhesive An optical member with a surface protective film having a release liner provided on the side opposite to the optical member of the agent layer (2) in this order, wherein the surface protective film comprises the substrate layer and the pressure-sensitive adhesive layer (1). Any appropriate method can be adopted as long as it is a method that includes a surface protective film and allows the pressure-sensitive adhesive layer (1) of the surface protection film to be on the optical member side.

In the method for producing the surface protective film-attached optical member of the present invention, for example, when the surface protective film is adhered, it is preferable to adhere the surface protective film to the optical member while applying tension to the surface protective film. The tension can be appropriately set according to the structure of the surface protection film (for example, thickness, forming material, elastic modulus, tensile elongation, etc.). It can be manufactured by the operation as described above.

EXAMPLES The present invention will be specifically described below with reference to Examples, but the present invention is not limited to these Examples. The tests and evaluation methods used in Examples and the like are as follows. "Parts" means "parts by weight" unless otherwise specified, and "%" means "% by weight" unless otherwise specified.

[Production Example 1]: Production of adhesive for polarizing plate In a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen gas inlet tube, and a cooler, butyl acrylate (manufactured by Nippon Shokubai Co., Ltd.): 99 parts by weight, 4 -Hydroxybutyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.): 1 part by weight, 2,2'-azobisisobutyronitrile as a polymerization initiator (manufactured by Wako Pure Chemical Industries, Ltd.): 0.1 parts by weight, acetic acid Ethyl: 100 parts by weight was charged, nitrogen gas was introduced while gently stirring, the liquid temperature in the flask was maintained at around 55 ° C., and the polymerization reaction was performed for 8 hours. %) were prepared. The obtained acrylic polymer solution (50% by weight) was diluted with ethyl acetate to 20% by weight, and 0.1 part by weight of Coronate L (manufactured by Nippon Polyurethane Industry Co., Ltd.) as a cross-linking agent was added to 100 parts by weight of this solution. In addition, mixing and stirring was 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 degree of polymerization of 2400, a degree of saponification of 99.9%, and a thickness of 30 μm was immersed in warm water of 30° C. and swollen so that the length of the polyvinyl alcohol film was 2.0 times its original length. was uniaxially stretched. Next, the mixture of iodine and potassium iodide (weight ratio = 0.5:8) was immersed in an aqueous solution (dyeing bath) with a concentration of 0.3% by weight, and the polyvinyl alcohol film length was 3.0 times the original length. The film was dyed while being uniaxially stretched so that After that, while immersed in an aqueous solution of 5% by weight of boric acid and 3% by weight of potassium iodide (crosslinking bath 1), the polyvinyl alcohol film was stretched so that its length was 3.7 times its original length, and then stretched by 60%. The polyvinyl alcohol film was stretched in an aqueous solution (crosslinking bath 2) containing 4% by weight of boric acid and 5% by weight of potassium iodide at 0° C. so that the length of the polyvinyl alcohol film was 6 times the original length. Then, after performing an iodine ion impregnation treatment with an aqueous solution of 3% by weight of potassium iodide (iodine impregnation bath), it was 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 water-based adhesive)
A polyvinyl alcohol resin containing an acetoacetyl group (average degree of polymerization: 1200, degree of saponification: 98.5 mol%, degree of acetoacetylation: 5 mol%) was dissolved in pure water at a temperature of 30°C, A water-based adhesive was obtained by adjusting the solid content concentration to 4%.
(Manufacture of polarizing plate)
A 25 μm-thick triacetyl cellulose (TAC) was coated with the water-based adhesive so that the thickness of the adhesive layer after drying was 80 nm to obtain a polarizer protective film with an adhesive layer. Then, the adhesive layer-attached polarizer protective film was attached to both sides of the polarizer with a roll machine under a temperature condition of 23° C., and then dried at 55° C. for 6 minutes to prepare a polarizing plate. The polarizer and the adhesive layer-attached polarizer protective film were bonded together so that the adhesive layer of the adhesive layer-attached polarizer protective film was in contact with the polarizer. Thus, a polarizing plate was produced.

[Production Example 3]: Production of release liner The pressure-sensitive adhesive for polarizing plate produced in Production Example 1 was applied to one surface of a silicone-treated surface of a 38 µm-thick polyester resin base material and a 50 µm-thick silicone-treated surface of the substrate. Each is applied to the silicone-treated surface of the base material made of a polyester resin, and cured and dried under the conditions of a drying temperature of 150 ° C. and a drying time of 2 minutes so that the thickness after drying is 20 μm. formed. Thus, a 38 μm-thick laminate of the release liner and the pressure-sensitive adhesive layer and a 50 μm-thick laminate of the release liner and the pressure-sensitive adhesive layer were produced.

[Production Example 4]: Production of polarizing plate with laminate of release liner and adhesive layer A polarizing plate having a laminate of a release liner and an adhesive layer was prepared by laminating the adhesive layer side of the laminate of No. The thickness of the pressure-sensitive adhesive layer-attached polarizing plate 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 the pressure-sensitive adhesive layer contained in the surface protective film As the polyol (A), Preminol S3011 ( Asahi Glass Co., Ltd., Mn = 10000), Sannics GP-3000 (manufactured by Sanyo Chemical Co., Ltd., Mn = 3000), which is a polyol having three OH groups, Sannics GP-1000, which is a polyol having three OH groups (manufactured by Sanyo Kasei Co., Ltd., Mn = 1000), Coronate HX (manufactured by Nippon Polyurethane Industry Co., Ltd.), which is a polyfunctional alicyclic isocyanate compound as a polyfunctional isocyanate compound (B), catalyst (manufactured by Nippon Kagaku Sangyo Co., Ltd., Product name: Nasem ferric), Irganox 1010 (manufactured by BASF) as a deterioration inhibitor, isopropyl myristate (manufactured by Kao Corporation, product name: Excepar IPM, Mn = 270) or cetyl 2-ethylhexanoate (Japan) as a fatty acid ester Sei Oilio Group Co., Ltd., trade name: Sarakos 816T, Mn = 368), 1-ethyl-3-methylimidazolium bis (fluoromethanesulfonyl) imide (Daiichi Kogyo Seiyaku Co., Ltd., trade name: AS110), both A terminal-type polyether-modified silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KF-6004) and ethyl acetate as a diluting solvent were added and mixed with stirring to produce a urethane pressure-sensitive adhesive composition. The number of parts to be blended is shown in Table 1.

[Production Example 6]: Production of urethane-based pressure-sensitive adhesive composition (U2), which is a material for forming the pressure-sensitive adhesive layer contained in the surface protective film Siabain SH-109 (manufactured by Toyochem Co., Ltd.) was used as the urethane prepolymer (C). , Coronate HX (manufactured by Nippon Polyurethane Industry Co., Ltd.), which is a polyfunctional alicyclic isocyanate compound as a polyfunctional isocyanate compound (B), and toluene as a dilution solvent are added and mixed and stirred to obtain a urethane pressure-sensitive adhesive composition (U2 ) was adjusted. The number of parts to be blended is shown in Table 1. The number of parts of each material except toluene is converted to solid content, and the number of parts of toluene indicates the total amount of solvent contained in the 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 protection film In a 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'-azobisisobutyl as a polymerization initiator Lonitrile (manufactured by Wako Pure Chemical Industries, Ltd.): 0.2 parts by weight, ethyl acetate: 156 parts by weight were charged, nitrogen gas was introduced while gently stirring, and the liquid temperature in the flask was maintained 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.) as a cross-linking agent and a catalyst (manufactured by Nippon Kagaku Sangyo Co., Ltd., trade name: Nasem ferric iron) and ethyl acetate as a diluting solvent were added and mixed and stirred to produce an acrylic pressure-sensitive adhesive composition (Ac1). The number of parts to be blended is shown in Table 1. The number of parts of each material except for ethyl acetate is converted to solid content, and the number of parts of ethyl acetate refers to the amount of all solvents contained in the 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 In a neck flask, butyl acrylate (manufactured by Nippon Shokubai Co., Ltd.): 95 parts by weight, acrylic acid (manufactured by Toagosei Co., Ltd.): 5 parts by weight, 2,2'-azobisisobutyronitrile (Wako Jun) as a polymerization initiator Yakukogyo Co., Ltd.): 0.2 parts by weight and ethyl acetate: 186 parts by weight were charged, nitrogen gas was introduced while gently stirring, and the liquid temperature in the flask was maintained at around 63°C to allow the polymerization reaction to proceed for 10 hours. to prepare a solution (35% by weight) of an acrylic polymer (Ac2P) having a weight average molecular weight of 500,000. Tetrad C (manufactured by Mitsubishi Gas Chemical Co., Ltd.) as a cross-linking agent and a catalyst (manufactured by Nippon Kagaku Sangyo Co., Ltd., product Nasem ferric iron) and ethyl acetate as a diluting solvent were added and mixed and stirred to produce an acrylic pressure-sensitive adhesive composition (Ac2). The number of parts to be blended is shown in Table 1. The number of parts of each material except for ethyl acetate is converted to solid content, and the number of parts of ethyl acetate refers to the amount of all solvents contained in the adhesive.

[Production Example 9]: Production of a rubber-based adhesive composition (G), which is a material for forming an adhesive layer contained in a surface protective film Hybler 5127 (manufactured by Kuraray Co., Ltd.): 100 parts by weight, toluene as a diluting solvent was added and mixed and stirred to produce a rubber-based pressure-sensitive adhesive composition (G). The number of parts to be blended 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 Kagaku Kogyo Co., Ltd.) and a platinum catalyst (trade name: CAT-PL-50T, Shin-Etsu Chemical Co., Ltd.) were mixed to produce a silicone adhesive composition (S). The number of parts to be blended is shown in Table 1.

[Production Example 11]: Production of separator-attached surface protective film The various pressure-sensitive adhesive compositions obtained are applied to a polyester resin substrate "Lumirror S10" (thickness 38 µm, manufactured by Toray Industries, Inc.), and the thickness after drying with a fountain roll. was applied so as to have a thickness of 10 μm, and dried by curing under the conditions of a drying temperature of 130° C. and a drying time of 30 seconds. Thus, a pressure-sensitive adhesive layer was produced on the substrate. Next, the silicone-treated surface of a substrate (separator) made of a polyester resin having a thickness of 25 μm and having one surface silicone-treated was laminated to the surface of the pressure-sensitive adhesive layer to obtain a separator-attached surface protective film.

<Measurement of trigger peel force P of optical member>
A surface protective film was laminated with a pressure of 0.25 MPa to the surface opposite to the release liner of the polarizing plate having the laminate of the release liner and the pressure-sensitive adhesive layer produced in Production Example 4 to protect the surface. A film-attached polarizing plate was produced. The prepared polarizing plate with a surface protective film was cut into a size of 25 mm in width and 80 mm in length. As a method for cutting the polarizing plate with a surface protective film, a cutter was used, but a supercutter may be used for cutting. After being left in an environment of 23°C and 50% RH for 24 hours, the release liner of the polarizing plate with a surface protective film was peeled off, and a single-sided adhesive tape (manufactured by Nichiban Co., Ltd., trade name " Cellotape (registered trademark)") was pressed against the pressure-sensitive adhesive layer side of the polarizing plate with a surface protective film so that the end face protruded by 1 mm, and left for 10 seconds. After that, the single-sided adhesive tape was peeled at a peeling speed of 300 mm / min and 6.0 m / min and a peeling angle of 180 ° using a universal tensile tester (Minebea Co., Ltd., product name: TCM-1kNB). The maximum stress applied at the beginning of peeling was defined as the trigger peeling force (N/25 mm). The measurement was performed under the environment of 23° C.×50% RH.

<Measurement of trigger release force Q of release liner>
A surface protective film was laminated with a pressure of 0.25 MPa to the surface opposite to the release liner of the polarizing plate having the laminate of the release liner and the pressure-sensitive adhesive layer produced in Production Example 4 to protect the surface. A film-attached polarizing plate was produced. The prepared polarizing plate with a surface protective film was cut into a size of 25 mm in width and 80 mm in length. As a method for cutting the polarizing plate with a surface protective film, a cutter was used, but a supercutter may be used for cutting. After being left for 24 hours in an environment of 23 ° C. × 50% RH, a single-sided adhesive tape (manufactured by Nichiban Co., Ltd., trade name "Cellotape (registered trademark)") cut to a size of 25 mm in width and 50 mm in length was applied, and the end surface was 1 mm. It was pressure-bonded to the release liner side of the polarizing plate with a surface protective film so as to protrude, and left for 10 seconds. After that, the single-sided adhesive tape was peeled at a peeling speed of 300 mm / min and 6.0 m / min and a peeling angle of 180 ° using a universal tensile tester (Minebea Co., Ltd., product name: TCM-1kNB). The maximum stress applied at the beginning of peeling was defined as the trigger peeling force (N/25 mm). The measurement was performed under the environment of 23° C.×50% RH.
When the thickness of the release liner was 38 μm and the release speed 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 speed 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 speed 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 protection film>
The separator-attached surface protective film obtained in Production Example 11 was cut into a size of 25 mm in width and 80 mm in length, and the separator was peeled off. After that, the polarizing plate with the laminate of the release liner and the adhesive layer obtained in Production Example 4 was cut into a width of 70 mm and a length of 100 mm. The agent layer surface was laminated at a pressure of 0.25 MPa to prepare an evaluation sample. After lamination, it is left in an environment of 23° C.×50% RH for 30 minutes, and a universal tensile tester (manufactured by Minebea Co., Ltd., product name: TCM-1kNB) is used at a peel speed of 300 mm/min and a peel angle of 180 degrees. , the adhesive force was measured in the region where the value stabilized when the surface protective film was peeled off. The measurement was performed under the environment of 23° C.×50% RH.

<Measurement of Wetting Speed of Surface Protection Film>
The separator-attached surface protection film obtained in Production Example 11 was cut into a piece having a width of 2.5 cm and a length of 10 cm to obtain an evaluation sample. As an adherend, the polarizing plate having the laminate of the release liner and the pressure-sensitive adhesive layer obtained in Production Example 4 was used. On the surface opposite to the release liner of the adherend, fix one end of the width side of the adhesive layer side of the evaluation sample from which the separator was removed, lift the unfixed end of the width side, and hold it with your hand. The time from release to wetting and spreading by 100 mm was measured. (Unit: seconds/2.5 cm x 10 cm). Wetting speed (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 apparatus (manufactured by Tosoh Corporation, HLC-8220GPC). The measurement conditions are as follows. In addition, the weight average molecular weight was calculated|required by the polystyrene conversion value.
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 column)
Detector: differential refractometer (RI)

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

The surface protective film-attached optical member of the present invention can be used for any appropriate application. Preferably, the surface protective film-attached optical member 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 layer 100 surface protective film 1000 optical member with surface protective film

Claims (7)

A laminate of an optical member and a surface protection film, a pressure-sensitive adhesive layer (2) provided on the side of the optical member opposite to the surface protection film, and a pressure-sensitive adhesive layer (2) provided on the side opposite to the optical member and a release liner coated with a surface protective film in this order,
The surface protection film includes a substrate layer and an adhesive layer (1),
The pressure-sensitive adhesive layer (1) of the surface protection film is on the optical member side,
The adhesive contained in the adhesive layer (1) is a urethane-based adhesive,
The urethane adhesive is
(1) A polyurethane resin formed from a composition containing a polyol (A) and a polyfunctional isocyanate compound (B), wherein NCO groups and OH in the polyol (A) and the polyfunctional isocyanate compound (B) A urethane pressure-sensitive adhesive having a group equivalent ratio of 0.1 to 1.7 as NCO group/OH group ,
and
the trigger release force P of the optical member from the laminate is greater than the trigger release force Q of the release liner;
Optical member with surface protective film. 2. 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. 3. The optical member with a surface protective film according to claim 1, wherein the surface protective film has a thickness of 5 μm to 500 μm. 4. The optical member with a surface protection film according to claim 1, wherein the release liner has a thickness of 1 μm to 500 μm. 5. 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 optical member with a surface protective film according to any one of claims 1 to 5, wherein the urethane pressure-sensitive adhesive contains a fatty acid ester. The optical member with a surface protective film according to any one of claims 1 to 6, wherein the surface protective film has a wetting rate of 5 cm ² /sec or more on the surface of the optical member.

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