KR20170023717A - Optical member with surface protection film - Google Patents

Abstract

Provided is an optical member with a surface protective film, which is an optical member with a surface protective film having an optical member and a surface protective film, capable of highly maintaining shear adhesion of an adhesive layer of a surface protective film and lowering peeling strength when a surface protective film is taken off from an optical member. The optical member with a surface protective film comprises, in order: a laminate of an optical member and a surface protective film; an adhesive layer (2) provided on the side opposite to the surface protective film of the optical member; and a release liner provided on the side opposite to the optical member of the adhesive layer (2). The surface protective film includes a base layer and an adhesive layer (1). The adhesive layer (1) of the surface protective film is an optical member-side. The shear adhesive strength of the adhesive layer (1) is greater than or equal to 10 N/ 10 mm. The peel strength of the surface protective film is less than or equal to 2.0 N/ 25 mm at the speed of 300 mm/min.

Description

OPTICAL MEMBER WITH SURFACE PROTECTION FILM

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

BACKGROUND ART [0002] In an optical product such as a liquid crystal display device, a surface protective film is generally adhered to an exposed surface side of an optical member such as a polarizing plate in order to prevent surface scratches during processing, assembling, inspection, and transportation . Such a surface protective film is peeled off from the optical member when the need for surface protection is eliminated (see, for example, Patent Document 1).

Such a surface protective film generally has a base layer and a pressure-sensitive adhesive layer. The pressure-sensitive adhesive layer of such a surface protective film is required to have a high shear adhesive strength. This is because when the shear adhesive strength of the pressure sensitive adhesive layer of the surface protective film adhered to the optical member such as the polarizing plate is low, the adhesive force in the transverse direction (adhesive surface direction) is lowered, It becomes easy to do so. Such a problem is remarkable particularly when the optical member is thin.

Conventionally, if the shear adhesive strength of the pressure-sensitive adhesive layer of the surface protective film adhered to an optical member such as a polarizing plate is increased, the instrument peel force at the time of peeling the surface protective film from the optical member becomes high, A problem of discarding occurs.

Japanese Patent No. 3972676

An object of the present invention is to provide an optical member having a surface protective film provided with an optical member and a surface protective film and capable of preventing the surface protective film from peeling off from the optical member while maintaining a high shear adhesive strength of the pressure sensitive adhesive layer of the surface protective film And an optical member having a surface protective film which can lower the peeling force.

In the optical member having the surface protective film of the present invention,

An optical member having a surface protective film having an optical member and a surface protective film,

The surface protective film comprises a substrate layer and a pressure-sensitive adhesive layer (1)

Sensitive adhesive layer (1) of the surface protective film is on the optical member side,

, The pressure-sensitive adhesive layer (1) has a shear adhesive strength of 10 N / 10 mm or more,

The instrument peel strength of the surface protective film is 2.0 N / 25 mm or less at a peeling speed of 300 mm / min.

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

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

In one embodiment, the thickness of the release liner is 1 占 퐉 to 500 占 퐉.

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

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

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

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

In one embodiment, the urethane pressure-sensitive adhesive comprises 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 the NCO group and the OH group in the urethane prepolymer (C) and the polyfunctional isocyanate compound (B) is 2.0 or less as the NCO group / OH group.

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

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

According to the present invention, there is provided an optical member having a surface protective film provided with an optical member and a surface protective film, and is capable of preventing the surface protective film from peeling off from the optical member while maintaining a high shear adhesive strength of the pressure- It is possible to provide an optical member having a surface protective film capable of reducing the force.

1 is a schematic sectional view of an optical member having a surface protection film according to one embodiment of the present invention.

<< Optical member having surface protective film »

The optical member having the 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 opposite side of the surface protective film of the optical member, And a peeling liner provided on the side opposite to the optical member in this order, wherein the surface protective film comprises a base layer and a pressure-sensitive adhesive layer (1), and the pressure-sensitive adhesive layer (1) is on the optical member side.

The optical member having the 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 opposite side of the surface protective film of the optical member, Provided with a release liner provided on the opposite side to the optical member, may have any suitable other layer as long as the effect of the present invention is not impaired.

1 is a schematic sectional view of an optical member having a surface protective film according to one embodiment of the present invention. 1, an optical member 1000 having a surface protecting film of the present invention is formed by laminating a release liner 10, a pressure-sensitive adhesive layer (2) 20, an optical member 30, a pressure- 40 and a base layer 50 in this order and the pressure sensitive adhesive layers 1 and 40 and the base layer 50 constitute a surface protective film 100. [

The thickness of the optical member is preferably 1 탆 to 500 탆, more preferably 3 탆 to 450 탆, still more preferably 5 탆 to 400 탆, and particularly preferably 10 탆 to 300 탆. The optical member having the surface protective film of the present invention can prevent the surface protective film from being peeled off from the optical member while maintaining the high shear adhesive strength of the pressure sensitive adhesive layer 1 of the surface protective film even when the thickness of the optical member is so small It is possible to lower the peeling force of the gauge at the time of

The thickness of the surface protective film is preferably 5 占 퐉 to 500 占 퐉, more preferably 10 占 퐉 to 450 占 퐉, still more preferably 15 占 퐉 to 400 占 퐉, and particularly preferably 20 占 퐉 to 300 占 퐉. By adjusting the thickness of the surface protective film within the above range, the optical member having the surface protective film of the present invention can prevent the surface protective film from peeling off from the optical member while maintaining the shear adhesive strength of the pressure sensitive adhesive layer (1) It is possible to lower the detachment force of the gauge at the time of the operation.

The thickness of the release liner is preferably 1 占 퐉 to 500 占 퐉, more preferably 3 占 퐉 to 450 占 퐉, still more preferably 5 占 퐉 to 400 占 퐉, and particularly preferably 10 占 퐉 to 300 占 퐉. By adjusting the thickness of the release liner within the above range, the optical member having the surface protective film of the present invention can prevent the surface protective film from being peeled off from the optical member while maintaining the shear adhesive strength of the pressure sensitive adhesive layer (1) It is possible to lower the detachment force of the gauge at the time of the present invention.

In the optical member having the surface protective film of the present invention, the pressure-sensitive adhesive layer (1) has a shear adhesive strength of 10 N / 10 mm or more, preferably 12 N / 10 mm or more, more preferably 14 N / , And particularly preferably 15 N / 10 mm or more. The upper limit value of the shear adhesive strength of the pressure-sensitive adhesive layer 1 is preferably 100 N / 10 mm, more preferably 50 N / 10 mm, still more preferably 40 N / 10 mm, and particularly preferably 30 N / 10 mm. When the shear adhesive strength of the pressure-sensitive adhesive layer 1 is within the above-mentioned range, the adhesive force in the transverse direction (adhesive surface direction) can be sufficiently secured, and curling is hardly caused in the optical member to which such surface protective film is adhered. In particular, when the optical member is thin, this effect is remarkably expressed.

In the optical member having the surface protective film of the present invention, the instrument peel strength of the surface protective film is 2.0 N / 25 mm or less at the peeling speed of 300 mm / min, more preferably 1.8 N / More preferably not more than 1.5 N / 25 mm, more preferably not more than 1.3 N / 25 mm, more preferably not more than 1.0 N / 25 mm, particularly preferably not more than 0.5 N / 25 mm, Is not more than 0.3 N / 25 mm. The lower limit value of the instrument peeling force of the surface protective film is preferably 0.01 N / 25 mm, more preferably 0.03 N / 25 mm, more preferably 0.05 N / / 25 mm, particularly preferably 0.07 N / 25 mm, and most preferably 0.1 N / 25 mm. When the surface peeling force of the surface protective film is within the above range at the peeling speed of 300 mm / min, the peeling of the surface protective film from the optical member can be sufficiently lightly performed.

In the optical member having the surface protective film of the present invention, the instrument peel strength of the surface protective film is 3.5 N / 25 mm or less at the peeling speed of 6 m / min, more preferably 3.0 N / More preferably not more than 2.5 N / 25 mm, more preferably not more than 2.0 N / 25 mm, more preferably not more than 1.8 N / 25 mm, particularly preferably not more than 1.5 N / 25 mm, Is not more than 1.3 N / 25 mm. In practice, the lower limit value of the instrument peel force of the surface protective film is preferably 0.01 N / 25 mm, more preferably 0.05 N / 25 mm, more preferably 0.1 N / / 25 mm, particularly preferably 0.3 N / 25 mm, and most preferably 0.5 N / 25 mm. When the surface peeling force of the surface protective film is within the above range at the peeling speed of 6 m / min, the peeling of the surface protective film from the optical member can be performed more sufficiently.

&Quot; Optical member &

As the optical member, any suitable optical member can be employed as long as the effect of the present invention is not impaired. The optical member may be a single layer or a multilayer. Preferable examples of such an optical member include a polarizing plate, a multilayer optical element including a polarizing plate, a touch panel using a retardation plate, an LCD, and an LCD, and a color filter used in an LCD.

«Surface protective film»

The surface protective film comprises a substrate layer and a pressure-sensitive adhesive layer (1). The surface protective film may include any suitable other layer insofar as the effect of the present invention is not impaired by including the base layer and the pressure-sensitive adhesive layer (1).

The wetting speed of the surface protective film on the surface of the optical member is preferably 5 cm 2 / second or more, more preferably 7 cm 2 / second or more, further preferably 8 cm 2 / second or more, particularly preferably 8.5 Lt; 2 &gt; / second or more. When the wetting rate of the surface protective film with respect to the surface of the optical member is within the above range, the wetting rate of the surface protective film against the surface of the optical member is excellent and bubbles are hardly present, for example, between the surface of the optical member and the surface protective film.

The surface protective film can be produced by any suitable method. As such a manufacturing method, for example,

(1) a method of applying a solution or a hot melt of the forming material of the pressure-sensitive adhesive layer (1)

(2) a method in which the pressure-sensitive adhesive layer (1) coated and formed in the form of a separator is adhered onto the base layer,

(3) a method in which a forming material of the pressure-sensitive adhesive layer 1 is formed by extrusion over a base layer,

(4) a method of extruding the base layer and the pressure-sensitive adhesive layer (1) into two layers or multiple layers,

(5) a method in which the pressure-sensitive adhesive layer (1) is laminated on the base layer or a method in which the pressure-sensitive adhesive layer (1) is laminated in two layers together with the laminate layer,

(6) a method of laminating a pressure-sensitive adhesive layer (1) and a base layer forming material such as a film or a laminate layer in a two-layer or multilayer manner,

, And the like.

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

<Base layer>

The base layer may be a single layer or two or more layers. The base layer may be stretched.

The thickness of the base layer is preferably 4 to 450 탆, more preferably 8 to 400 탆, further preferably 12 to 350 탆, and particularly preferably 16 to 250 탆. By adjusting the thickness of the base layer within the above range, the optical member having the surface protective film of the present invention can prevent the surface protective film from being peeled off from the optical member while maintaining the shear adhesive strength of the pressure sensitive adhesive layer (1) It is possible to lower the detachment force of the gauge at the time of the present invention.

The surface of the substrate layer on which the pressure-sensitive adhesive layer (1) is not laid is not particularly limited. For example, a fatty acid amide, a polyethyleneimine, a long chain alkyl-based additive and the like are added to the substrate layer Or a coat layer containing any appropriate releasing agent such as a silicone type, a long chain alkyl type or a fluorine type can be formed.

As the material of the base layer, any suitable material may be employed depending on the application. Examples thereof include plastics, paper, metal films, and nonwoven fabrics. Preferably, it is a plastic. That is, the base layer is preferably a plastic film. The substrate 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 kinds of plastics.

Examples of the plastic include a polyester resin, a polyamide resin, and a polyolefin resin. Examples of the polyester-based resin include polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate. Examples of the polyolefin-based resin include homopolymers of olefin monomers and copolymers of olefin monomers. Specific examples of the polyolefin-based resin include homopolypropylene; Propylene-based copolymers such as a block system, a random system and a graft system having an ethylene component as a copolymerization component; Reactor TPO; Ethylene polymers such as low density, high density, linear low density and ultra low density; Ethylene / propylene copolymer, ethylene / vinyl acetate copolymer, ethylene / methyl acrylate copolymer, ethylene · ethyl acrylate copolymer, ethylene · butyl acrylate copolymer, ethylene · methacrylic acid copolymer, ethylene · methyl methacrylate copolymer And the like; And the like.

The substrate layer may contain any suitable additive, if desired. Examples of additives that can be contained in the base layer include antioxidants, ultraviolet absorbers, light stabilizers, antistatic agents, fillers, pigments and the like. The kind, quantity, and amount of the additive that may be contained in the base layer may be appropriately set according to the purpose. Particularly, 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 or the like. From the viewpoint of improvement in weatherability and the like, additives such as antioxidants, ultraviolet absorbers, light stabilizers and fillers are particularly preferable.

As the antioxidant, any suitable antioxidant may be employed. Examples of such an antioxidant include a phenol-based antioxidant, a phosphorus-based heat stabilizer, a lactone-based heat stabilizer, a sulfur-based heat stabilizer, and a phenol-phosphorus antioxidant. The content of the antioxidant is preferably 1% by weight or less, more preferably 0.5% by weight or less based on the base resin of the base layer (when the base layer is a blend, the blend is a base resin) More preferably 0.01% by weight to 0.2% by weight.

As the ultraviolet absorber, any appropriate ultraviolet absorber can be employed. Examples of such ultraviolet absorbers include benzotriazole ultraviolet absorbers, triazine ultraviolet absorbers, benzophenone ultraviolet absorbers, and the like. The content of the ultraviolet absorber is preferably not more than 2% by weight, more preferably not more than 1% by weight, based on the base resin forming the base layer (when the base layer is a blend, the blend is the base resin) By weight, and more preferably 0.01% by weight to 0.5% by weight.

As the light stabilizer, any suitable light stabilizer can be employed. Examples of such light stabilizers include hindered amine light stabilizers and benzoate light stabilizers. The content of the light stabilizer is preferably not more than 2% by weight, more preferably not more than 1% by weight, based on the base resin forming the base layer (when the base layer is a blend, the blend is base resin) By weight, and more preferably 0.01% by weight to 0.5% by weight.

As the filler, any suitable filler can be employed. Examples of such fillers include inorganic fillers. Specific examples of the inorganic filler include carbon black, titanium oxide, zinc oxide and the like. The content of the filler is preferably 20% by weight or less, more preferably 10% 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) By weight, more preferably 0.01% by weight to 10% by weight.

Further, for the purpose of imparting antistatic property, additives such as surfactants, inorganic salts, polyhydric alcohols, metal compounds, carbon and the like, inorganic low molecular weight systems and high molecular weight antistatic agents are also preferable. Particularly, from the viewpoints of keeping contamination and tackiness, high molecular weight antistatic agents and carbon are preferable.

&Lt; Pressure-sensitive 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 forming a pressure-sensitive adhesive layer (1) on a base layer by applying a composition as a forming material of the pressure-sensitive adhesive layer (1) on the base layer. Examples of such a coating method include roll coats, gravure coats, reverse coats, roll brushes, spray coats, air knife coating methods, extrusion coats with die coaters, and the like.

The thickness of the pressure-sensitive adhesive layer 1 is preferably 1 to 150 占 퐉, more preferably 2 to 140 占 퐉, still more preferably 3 to 130 占 퐉, and particularly preferably 4 to 120 占 퐉 to be. By adjusting the thickness of the pressure-sensitive adhesive layer 1 within the above-mentioned range, the optical member having the surface protective film of the present invention can prevent the pressure-sensitive adhesive layer (1) It is possible to lower the instrument peeling force at the time of peeling.

The content of the pressure-sensitive adhesive in the pressure-sensitive 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% by weight to 100% by weight, and most preferably 90% by weight to 100% by weight. By adjusting the content of the pressure-sensitive adhesive in the pressure-sensitive adhesive layer 1 within the above-mentioned range, the optical member having the surface-protective film of the present invention can prevent the surface- It is possible to lower the instrument peeling force when peeling off the optical element from the optical member.

The pressure-sensitive adhesive contained in the pressure-sensitive adhesive layer (1) may employ any suitable pressure-sensitive adhesive within a range not to impair the effect of the present invention. From the viewpoint that the effect of the present invention can be further exerted, it is more preferable that the urethane pressure-sensitive adhesive is at least one selected from urethane pressure-sensitive adhesives and silicone pressure-sensitive adhesives, .

[Urethane-Based Adhesive]

The urethane pressure sensitive adhesive includes a polyurethane resin.

The content of the polyurethane resin in the urethane pressure-sensitive adhesive is preferably 50% by weight to 100% by weight, more preferably 70% by weight to 100% by weight, still more preferably 90% by weight to 100% by weight, , Preferably 95% by weight to 100% by weight, and most preferably 98% by weight to 100% by weight. By adjusting the content of the polyurethane resin in the urethane pressure-sensitive adhesive within the above-mentioned range, the optical member having the surface protective film of the present invention can prevent the surface protective film from adhering to the surface protective film while maintaining the shear adhesive strength of the pressure- The instrument peeling force at the time of peeling from the optical member can be lowered.

The urethane pressure-sensitive adhesive may contain, in addition to the polyurethane resin, any other appropriate components as long as the effect of the present invention is not impaired. Examples of such other components include a resin component other than a polyurethane resin, a tackifier, an inorganic filler, an organic filler, a metal powder, a pigment, a thin film, a softener, an antioxidant, a conductive agent, an ultraviolet absorber, Surface lubricants, leveling agents, corrosion inhibitors, heat stabilizers, polymerization inhibitors, lubricants, solvents, catalysts and the like.

As the polyurethane resin, any suitable polyurethane resin can be employed as long as the effect of the present invention is not impaired. The polyurethane resin is preferably a polyurethane resin formed from a composition containing a polyol (A) and a polyfunctional isocyanate compound (B), or a composition containing a urethane prepolymer (C) and a polyfunctional isocyanate compound (B) Is a polyurethane-based resin. By employing the same as the polyurethane resin, the optical member having the surface protective film of the present invention can be obtained by peeling the surface protective film from the optical member while maintaining the shear adhesive strength of the pressure sensitive adhesive layer (1) It is possible to lower the detachment force of the gauge at the time of the present invention.

The polyurethane resin may contain any suitable other components as long as the effect of the present invention is not impaired. Examples of such other components include a resin component other than a polyurethane resin, a tackifier, an inorganic filler, an organic filler, a metal powder, a pigment, a thin film, a softener, an antioxidant, a conductive agent, an ultraviolet absorber, Surface lubricants, leveling agents, corrosion inhibitors, heat stabilizers, polymerization inhibitors, lubricants, solvents, catalysts and the like.

The polyurethane resin preferably includes an antioxidant such as an antioxidant, an ultraviolet absorber, or a light stabilizer. Since the polyurethane resin contains a deterioration inhibitor, it is possible to obtain excellent adhesive residue retention property, for example, it is difficult for the adhesive to remain on the adherend even after it is adhered to the adherend and then stored in a heated state. The deterioration inhibitor may be one kind or two or more kinds. As the deterioration inhibitor, particularly preferably, it is an antioxidant.

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

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

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

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

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

Examples of the bisphenol-based antioxidant include 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2,2'-methylenebis , 3'-thiobis (3-methyl-6-t-butylphenol), 4,4'-butylidenebis Propyloxy] ethyl] 2,4,8,10-tetraoxaspiro [5,5] undecane, and the like were added to a solution of .

Examples of the polymer type phenolic antioxidant include 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 1,3,5-trimethyl- Tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, tetrakis- [methylene- (3'-hydroxy-3'-t-butylphenyl) butyrate] glycol ester, 1,3,5-tris (3 ', 5'- Di-t-butyl-4'-hydroxybenzyl) -S-triazine-2,4,6- (1H, 3H, 5H) trione and tocophenol.

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

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

Examples of the ultraviolet absorber include benzophenone ultraviolet absorbers, benzotriazole ultraviolet absorbers, salicylic acid ultraviolet absorbers, oxalanilide ultraviolet absorbers, cyanoacrylate ultraviolet absorbers, triazine-based ultraviolet absorbers, and the like.

Examples of the benzophenone ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2- -Dodecyloxybenzophenone, 2,2'-dihydroxy-4-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4- 5-sulfobenzophenone, bis (2-methoxy-4-hydroxy-5-benzoylphenyl) methane and the like.

Examples of the benzotriazole ultraviolet absorber include 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-5'- Butylphenyl) benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) Benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) 3'- (3 ", 4 &quot;, 5" -tetramethylphenyl) benzotriazole, 2- (2'- , 6 ", -tetrahydrophthalimidemethyl) -5'-methylphenyl] benzotriazole, 2,2'methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- 2-yl) phenol], 2- (2'-hydroxy-5'-methacryloxyphenyl) -2H-benzotriazole and the like.

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

Examples of the cyanoacrylate ultraviolet absorber include 2-ethylhexyl-2-cyano-3,3'-diphenylacrylate, ethyl-2-cyano- .

Examples of the light stabilizer 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- Piperidyl) sebacate, methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacate, and the like.

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

The urethane pressure sensitive adhesive may contain a fatty acid ester. The fatty acid ester may be one kind or two or more kinds.

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, 350. By adjusting the number average molecular weight Mn of the fatty acid ester within the above range, the wetting rate can be further improved. If the number-average molecular weight Mn of the fatty acid ester is too small, there is a fear that the wetting rate may not be improved even if the number of the addition groups is large. If the number-average molecular weight Mn of the fatty acid ester is too large, the curing property of the pressure-sensitive adhesive at the time of drying deteriorates, which may not only affect the wetting property but also adversely affect other adhesive properties.

As the fatty acid ester, any suitable fatty acid ester can be employed as long as the effect of the present invention is not impaired. Examples of such fatty acid esters include polyoxyethylene bisphenol A lauric acid ester, butyl stearate, 2-ethylhexyl palmitate, 2-ethylhexyl stearate, behenic acid monoglyceride, 2-ethylhexanoate, Methyl stearate, myristyl isostearate, isopropyl palmitate, cholesteryl isostearate, lauryl methacrylate, methyl coconut fatty acid methyl, methyl laurate, methyl oleate, methyl stearate, myristyl myristate, Dodecyl pentaerythritol monooleate, pentaerythritol monostearate, pentaerythritol tetrapalmitate, stearyl stearate, isostearyl stearate, 2-ethylhexanoic acid triglyceride, butyl laurate, octyl oleate And the like.

The blending ratio of the fatty acid ester in producing the urethane pressure-sensitive adhesive is preferably 5% by weight to 50% by weight, more preferably 7% by weight to 45% by weight, based on 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 fluoro organic anion. The urethane pressure sensitive adhesive contains an ionic liquid containing a fluoro organic anion, thereby providing an urethane pressure sensitive adhesive having an excellent antistatic property. The ionic liquid may be of only one type, or two or more types.

In the present invention, an ionic liquid means a molten salt (ionic compound) which exhibits a liquid phase at 25 占 폚.

As the ionic liquid, any suitable ionic liquid can be employed as far as it does not impair the effects of the present invention, provided that it is an ionic liquid containing a fluoro organic anion. Such an ionic liquid is preferably an ionic liquid composed of a fluoro organic anion and an onium cation. By employing an ionic liquid composed of a fluoro organic anion and an onium cation as the ionic liquid, it is possible to provide an urethane-based pressure sensitive adhesive having an extremely excellent antistatic property.

Any suitable onium cation can be employed as the onium cation that can constitute the ionic liquid, provided that the effect of the present invention is not impaired. The onium cation is preferably at least one selected from a nitrogen-containing onium cation, a sulfur-containing onium cation, and a phosphorus-containing onium cation. By selecting these onium cation, it is possible to provide an urethane-based pressure-sensitive adhesive which is extremely excellent in antistatic property.

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

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

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

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

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

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

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

Specific examples of the cation represented by the general formula (1) include, for example, 1-ethylpyridinium cation, 1-butylpyridinium cation, 1-hexylpyridinium cation, 1-ethyl- Butyl-3-methylpyridinium cation, 1-hexyl-3-methylpyridinium cation, 1-butyl-4-methylpyridinium cation, 1-octyl- Pyridinium cations such as dimethylpyridinium cation and 1,1-dimethylpyrrolidinium cation; Methyl-1-propylpyrrolidinium cation, 1-methyl-1-butylpyrrolidinium cation, 1-methyl-1-pentylpyrrolidinium cation, 1- Methyl-1-heptylpyrrolidinium cation, a 1-ethyl-1-butylpyrrolidinium cation, a 1-ethyl-1-butylpyrrolidinium cation, Ethyl-1-hexylpyrrolidinium cation, 1-ethyl-1-heptylpyrrolidinium cation, 1,1-dipropylpyrrolidinium cation, 1-propyl-1-butyl Pyrrolidinium cations such as pyrrolidinium cation and 1,1-dibutylpyrrolidinium cation; 1-propylpiperidinium cation, 1-methylpiperidinium cation, 1-methyl-1-ethylpiperidinium cation, 1-methyl-1-propylpiperidinium cation, Methyl-1-heptylpiperidinium cation, 1-methyl-1-pentylpiperidinium cation, 1-methyl-1-pentylpiperidinium cation, Ethyl-1-butylpiperidinium cation, 1-ethyl-1-pentylpiperidinium cation, 1-ethyl-1-pentylpiperidinium cation, 1- Piperidinium cations such as propyl-1-butylpiperidinium cation, 1,1-dimethylpiperidinium cation, 1,1-dipropylpiperidinium cation and 1,1-dibutylpiperidinium cation; 2-methyl-1-pyrroline cations; 1-ethyl-2-phenylindole cations; 1,2-dimethylindole cations; 1-ethylcarbazole cations; And the like.

Of these, preferred are 1-ethylpyridinium cation, 1-butylpyridinium cation, 1-hexylpyridinium cation, 1-ethyl-3-methylpyridine Butyl-4-methylpyridinium cation such as 1-butyl-3-methylpyridinium cation, 1-hexyl-3-methylpyridinium cation, Cation; Methyl-1-propylpyrrolidinium cation, 1-methyl-1-butylpyrrolidinium cation, 1-methyl-1-pentylpyrrolidinium cation, 1- Methyl-1-heptylpyrrolidinium cation, a 1-ethyl-1-butylpyrrolidinium cation, a 1-ethyl-1-butylpyrrolidinium cation, Pyrrolidinium cations such as 1-pentylpyrrolidinium cation, 1-ethyl-1-hexylpyrrolidinium cation and 1-ethyl-1-heptylpyrrolidinium cation; Methyl-1-propylpiperidinium cation, 1-methyl-1-butylpiperidinium cation, 1-methyl-1-pentylpiperidinium cation, 1- Ethyl-1-propylpiperidinium cation, 1-ethyl-1-butylpiperidinium cation, 1-ethyl-1-pentylpiperidinium cation, Piperidinium cations such as 1-pentylpiperidinium cation, 1-ethyl-1-hexylpiperidinium cation, 1-ethyl-1-heptylpiperidinium cation and 1-propyl-1-butylpiperidinium cation; And more preferably 1-hexylpyridinium cation, 1-ethyl-3-methylpyridinium cation, 1-butyl-3-methylpyridinium cation, 1-octyl- A 1-methyl-1-propylpyrrolidinium cation, and a 1-methyl-1-propylpiperidinium cation.

Examples of the cations represented by the 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-decyl-3-methylimidazolium cation, 1-decyl-3-methylimidazolium cation, 1- Methylimidazolium cation, 1-tetradecyl-3-methylimidazolium cation, 1,2-dimethyl-3-propylimidazolium cation, 1-ethyl-2,3-dimethylimidazolium cation Imidazolium cations such as 1-butyl-2,3-dimethylimidazolium cation and 1-hexyl-2,3-dimethylimidazolium cation; 1,3-dimethyl-1,4,5,6-tetrahydropyrimidinium cation, 1,2,3-trimethyl-1,4,5,6-tetrahydropyrimidinium cation, 1,2,3- Tetrahydropyrimidinium cations such as 4-tetramethyl-1,4,5,6-tetrahydropyrimidinium cation and 1,2,3,5-tetramethyl-1,4,5,6-tetrahydropyrimidinium cation, Midium cation; 1,3-dimethyl-1,4-dihydropyrimidinium cation, 1,3-dimethyl-1,6-dihydropyrimidinium cation, 1,2,3-trimethyl-1,4-dihydropyrimidine 1,2,3-trimethyl-1,6-dihydropyrimidinium cation, 1,2,3,4-tetramethyl-1,4-dihydropyrimidinium cation, 1,2,3- Dihydropyrimidinium cations such as 4-tetramethyl-1,6-dihydropyrimidinium cation and the like; And the like.

Among these, from the viewpoint that the effects of the present invention can be further enhanced, preferred are 1,3-dimethylimidazolium cation, 1,3-diethylimidazolium cation, 1-ethyl- 3-methylimidazolium cation, 1-hexyl-3-methylimidazolium cation, 1-octyl-3-methylimidazolium cation, 1-decyl- Methylimidazolium cation, 1-dodecyl-3-methylimidazolium cation, and 1-tetradecyl-3-methylimidazolium cation, and more preferably an imidazolium cation such as 1-ethyl- , 1-hexyl-3-methylimidazolium cation.

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

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

Examples of the cation represented by the general formula (4) include tetraalkylammonium cations, trialkylsulfonium cations and tetraalkylphosphonium cations, and those in which a part of the alkyl group is substituted with an alkenyl group, an alkoxyl group, .

Specific examples of the cations represented by the general formula (4) include, for example, tetramethylammonium cations, tetraethylammonium cations, tetrabutylammonium cations, tetrapentylammonium cations, tetrahexylammonium cations, tetraheptylammonium cations, (2-methoxyethyl) ammonium cation, a glycidyltrimethylammonium cation, a trimethylsulfammonium cation, a trimethylammonium cation, an N, N-diethyl- And examples of the cation selected from the group consisting of a sulfonium cation, a sulfonium cation, a sulfonium cation, a sulfonium cation, a sulfonium cation, a sulfonium cation, a sulfonium cation, a sulfonium cation, Tetrabutylphosphonium cation, tetrahexylphosphonium cation, tetraoctylphosphonium cation, triethylphosphonium cation, tetrabutylphosphonium cation, tetrabutylphosphonium cation, Tributylethylphosphonium cation, trimethyldecylphosphonium cation, diallyldimethylammonium cation, and the like can be given.

Among these, from the viewpoint that the effect of the present invention can be further manifested, it is preferable to use a cation such as triethylmethylammonium cation, tributylethylammonium cation, trimethyldecylammonium cation, diethylmethylsulfonium cation, dibutylethylsulfonium cation Tetramethylammonium cation, tetramethylammonium cation, tetramethylammonium cation, tetramethylammonium cation, tetramethylammonium cation, tetramethylammonium cation, tetramethylammonium cation, tetramethylammonium cation, tetramethylammonium cation, tetramethylammonium cation, tetramethylammonium cation, N-dimethyl-N-ethyl-N-propylammonium cation, N, N-dimethyl-N-ethyl-N-propylammonium cation, glycidyltrimethylammonium cation, diallyldimethylammonium cation, N-dimethyl-N-ethyl-N-butylammonium cation, N, N-dimethyl-N-ethyl-N-pentylammonium cation, N, Dimethyl-N-ethyl-N-heptylammonium cation, N, N-dimethyl- N-dimethyl-N-propyl-N-butylammonium cation, N, N-dimethyl-N-dipropylammonium cation, N-dimethyl-N-propyl-N-heptylammonium cation, N, N-dimethyl-N-butyl- N, N-dimethyl-N-butyl-N-heptylammonium cation, N, N-dimethyl-N-pentyl-N-hexylammonium cation, N-diethyl-N-methyl-N-propylammonium cation, N, N-diethyl-N-methyl-N-pentylammonium cation, N, Methyl-N-heptylammonium cation, N, N-diethyl-N-propyl-N-pentylammonium cation, triethylpropylammonium cation, triethylpentylammonium cation, triethylheptylammonium cation, Methyl-N-ethylammonium cation, N, N-dipropyl-N-methyl-N-pentylammonium cation, N, N-dibutyl-N-methyl-N-methyl-N-pentylammonium cation, N, N-dibutyl-N, N-dibutylammonium cation, N-methyl-N-ethyl-N-propyl-N-pentylammonium cation, and more preferably a trimethylpropylammonium cation.

As the fluoroorganic anion capable of constituting the ionic liquid, any appropriate fluoro organic anion can be employed as long as the effect of the present invention is not impaired. Such a fluoro organic anion may be completely fluorinated (perfluorinated) or partially fluorinated.

Examples of such fluoro organic anions include fluorinated arylsulfonate, perfluoroalkanesulfonate, bis (fluorosulfonyl) imide, bis (perfluoroalkanesulfonyl) imide, cyano perfluoro (Perfluoroalkanesulfonyl) methide, tris (perfluoroalkanesulfonyl) methide, trifluoroacetone (methanesulfonyl) methide, bis , Perfluoroalkalate, tris (perfluoroalkanesulfonyl) methide, (perfluoroalkanesulfonyl) trifluoroacetamide, and the like.

Of these fluoro organic anions, perfluoroalkylsulfonate, bis (fluorosulfonyl) imide and bis (perfluoroalkanesulfonyl) imide are more preferable. More specifically, for example, Heptafluoropropanesulfonate, nonafluorobutanesulfonate, bis (fluorosulfonyl) imide, bis (trifluoromethanesulfonyl) imide, and the like. .

As specific examples of the ionic liquid, a combination of the cation component and the anionic component may be appropriately selected and used. Specific examples of such ionic liquids include 1-hexylpyridinium bis (fluorosulfonyl) imide, 1-ethyl-3-methylpyridinium trifluoromethanesulfonate, 1-ethyl- Methylpyridinium heptafluoropropanesulfonate, 1-ethyl-3-methylpyridinium nonafluorobutanesulfonate, 1-butyl-3-methylpyridinium 1-butyl-3-methylpyridinium bis (trifluoromethanesulfonyl) imide, 1-butyl-3-methylpyridinium bis (pentafluoroethanesulfonyl) 1-methyl-1-ethylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1,1-dimethylpyrrolidinium bis (trifluoromethanesulfonyl) imide, (Trifluoromethanesulfonyl) imide, 1-methyl-1-propylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-propylpyrrolidinium bis Methyl-1-butylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-pentylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-hexylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-heptylpyrrolidinium bis (trifluoromethanesulfonyl) 1-propylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-ethyl-1-butylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-ethyl-1-pentylpyrrole Ethyl-1-hexylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-ethyl-1-heptylpyrrolidinium bis (trifluoromethanesulfonyl) imide, Propyl-1-butylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1,1-dipropylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1,1-dibutylpyrrolidinium bis ( (Trifluoromethanesulfonyl) imide, 1-propylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-pentylpiperidinium bis (trifluoromethanesulfonyl) imide, Dimethylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-ethylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-propylpiperidinium bis Methyl-1-propylpiperidinium bis (fluorosulfonyl) imide, 1-methyl-1-butylpiperidinium bis (trifluoromethanesulfonyl) imide, Methyl-1-pentylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-methyl-1-hexylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-methyl- 1-heptylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-ethyl-1-propylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-ethyl-1-butylpiperidinium Bis (trifluo Ethyl-1-pentylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-ethyl-1-hexylpiperidium bis (trifluoromethanesulfonyl) imide , 1-ethyl-1-heptylpiperidinium bis (trifluoromethanesulfonyl) imide, 1,1-dipropylpiperidinium bis (trifluoromethanesulfonyl) Butylpiperidinium bis (trifluoromethanesulfonyl) imide, 1,1-dibutylpiperidinium bis (trifluoromethanesulfonyl) imide, 1,1-dimethylpyrrolidinium bis (pentafluoro Methyl-1-ethylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-propylpyrrolidinium bis (pentafluoroethanesulfonyl) imide Methyl-1-butylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-pentylpyrrolidinium bis (pentafluoroethanesulfonyl) - hexylpyrrolidinium bis (pentaprene Methyl-1-heptylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-propylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, Ethyl-1-pentylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-butylpyrrolidinium bis (pentafluoroethanesulfonyl) imide, 1-hexylpyrrolidinium 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 Pentafluoroethane Methyl-1-ethylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-propylpiperidinium bis (pentafluoroethanesulfonyl) imide, Methyl-1-butylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-methyl-1-pentylpiperidinium bis (pentafluoroethanesulfonyl) imide, Methyl-1-heptylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-propylpiperidinium bis (pentafluoroethanesulfonyl) imide, Ethyl-1-butylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-pentylpiperidinium bis (pentafluoroethanesulfonyl) imide 1-ethyl-1-hexylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-1-heptylpiperidinium bis (pentafluoroethanesulfonyl) Dipropylpiperidinium bis (penta Propyl-1-butylpiperidinium bis (pentafluoroethanesulfonyl) imide, 1,1-dibutylpiperidinium bis (pentafluoroethanesulfonyl) imide, Ethyl-3-methylimidazolium trifluoromethanesulfonate, 1-ethyl-3-methylimidazolium trifluoromethanesulfonate, 1-ethyl-3-methylimidazolium trifluoromethanesulfonate, Ethyl-3-methylimidazolium heptafluoropropanesulfonate, 1-ethyl-3-methylimidazolium nonafluorobutanesulfonate, 1-ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) Ethyl-3-methylimidazolium bis (pentafluoroethanesulfonyl) imide, 1-ethyl-3-methylimidazoliumbis (fluorosulfonyl) imide, -3-methylimidazolium tris (trifluoromethanesulfonyl) methide, 1-butyl-3-methylimidazolium trifluoroacetate, 1-butyl-3-methylimidazolium heptaflu 3-methylimidazolium trifluoromethanesulfonate, 1-butyl-3-methylimidazolium perfluorobutanesulfonate, 1-butyl-3-methylimidazolium bis (tri 3-methylimidazolium bis (fluorosulfonyl) imide, 1-hexyl-3-methylimidazolium trifluoromethanesulfonate, 1-hexyl- Dimethyl-3-propylimidazolium bis (trifluoromethanesulfonyl) imide, 1-ethyl-2,3,5-trimethylpyrazoliumbis (trifluoromethanesulfonyl) , 3,5-trimethylpyrazoliumbis (trifluoromethanesulfonyl) imide, 1-butyl-2,3,5-trimethylpyrazoliumbis (trifluoromethanesulfonyl) imide, , 3,5-trimethylpyrazoliumbis (pentafluoroethanesulfonyl) imide, 1-propyl-2,3,5-trimethylpyrazoliumbis (pentafluoroethanesulfonyl) imide, , 3,5-trimethylpyrazoliumbis (penta Ethyl-2,3,5-trimethylpyrazolium (trifluoromethanesulfonyl) trifluoroacetamide, 1-propyl-2,3,5-trimethylpyrazolium ( (Trifluoromethanesulfonyl) trifluoroacetamide, 1-butyl-2,3,5-trimethylpyrazolium (trifluoromethanesulfonyl) trifluoroacetamide, trimethylpropylammonium bis (trifluoromethanesulfonyl) N-dimethyl-N-ethyl-N-butylammonium bis (trifluoromethanesulfonyl) imide, N-dimethyl-N-ethyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl- N-dimethyl-N-ethyl-N-heptylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl- (Trifluoromethanesulfo (Trifluoromethanesulfonyl) imide, N, N-dimethyl-N-propyl-N-butylammonium bis (trifluoromethanesulfonyl) imide, (Trifluoromethanesulfonyl) imide, N, N-dimethyl-N-propyl-N-hexylammonium bis (trifluoromethylsulfonyl) imide, N-dimethyl-N-butyl-N-hexylammonium bis (trifluoromethanesulfonyl) imide, N, N-dimethyl- 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 (trifluoromethane N, N-diethyl-N-methyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, N, N-diethyl-N-propyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, triethylpropylammonium bis (trifluoromethanesulfonyl) imide, (Trifluoromethanesulfonyl) imide, triethylheptylammonium bis (trifluoromethanesulfonyl) imide, N, N-dipropyl-N-methyl- N, N-dipropyl-N-methyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, N, N-dipropyl- N, N-dipropyl-N, N-dibutylammonium bis (trifluoromethanesulfonyl) imide, N, N-dibutyl -N-methyl-N-pentylammonium bis (trifluoromethanesulfo Imide, N, N-dibutyl-N-methyl-N-hexylammonium bis (trifluoromethanesulfonyl) imide, trioctylmethylammonium bis (trifluoromethanesulfonyl) Propyl-N-pentylammonium bis (trifluoromethanesulfonyl) imide, 1-butylpyridinium (trifluoromethanesulfonyl) trifluoroacetamide, 1-butyl- (Trifluoromethanesulfonyl) trifluoroacetamide, 1-ethyl-3-methylimidazolium (trifluoromethanesulfonyl) trifluoroacetamide, tetrahexylammonium bis (trifluoromethane) (Pentafluoroethanesulfonyl) imide, diallyldimethylammonium trifluoromethanesulfonate, diallyldimethylammonium bis (trifluoromethanesulfonyl) imide, diallyldimethylammonium bis (pentafluoroethanesulfonyl) imide, N , N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium trifluoromethanesulfonate, N, (Trifluoromethanesulfonyl) imide, N, N-diethyl-N-methyl-N- (2-methoxyethyl) ammonium bis (pentafluoroethane Glycidyltrimethylammonium bis (trifluoromethanesulfonyl) imide, glycidyltrimethylammonium bis (pentafluoroethanesulfonyl) imide, glycidyltrimethylammonium trifluoromethanesulfonate, glycidyltrimethylammonium bis (Pentafluoroethanesulfonyl) imide, lithium bis (trifluoromethanesulfonyl) imide, lithium bis (trifluoromethanesulfonyl) imide, diallyldimethylbis &Lt; RTI ID = 0.0 &gt; rosulfonyl) &lt; / RTI &gt; imide.

Among these ionic liquids, more preferred are 1-hexylpyridinium bis (fluorosulfonyl) imide, 1-ethyl-3-methylpyridinium trifluoromethanesulfonate, 1-ethyl- Methylpyridinium heptafluoropropanesulfonate, 1-ethyl-3-methylpyridinium nonafluorobutanesulfonate, 1-butyl-3-methylpyridinium Methyl-3-methylpyridinium bis (trifluoromethanesulfonyl) imide, 1-octyl-4-methylpyridinium bis (fluorosulfonyl) imide, 1-methyl Propylpyrrolidinium bis (fluorosulfonyl) imide, 1-methyl-1-propylpiperidinium bis (trifluoromethanesulfonyl) imide, (Trifluoromethanesulfonyl) imide, 1-methyl-1-propylpiperidinium bis (fluorosulfonyl) imide, 1-ethyl-3-methylimidazolium trifluoro Ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide, 1-ethyl-3-methyl (methylsulfonyl) imide, Imidazolium bis (fluorosulfonyl) imide, 1-hexyl-3-methylimidazolium bis (fluorosulfonyl) imide, trimethylpropylammonium bis (trifluoromethanesulfonyl) imide, lithium bis (Trifluoromethanesulfonyl) imide, and lithium bis (fluorosulfonyl) imide.

As the ionic liquid, a commercially available liquid may be used, but it may be synthesized as follows. The method for synthesizing an ionic liquid is not particularly limited as long as an intended ionic liquid is obtained, but generally it is described in "Frontier and Future of Ionic Liquid - Development" published by CMC Publishing Co., Ltd. A halide method, a hydroxide method, an acid ester method, an emulsion formation method, and a neutralization method.

The method of synthesizing the nitrogen containing onium salt is described below with reference to the halide method, the hydroxide method, the acid ester method, the polymerization method and the neutralization method, but other methods such as a sulfur-containing onium salt, a phosphorus containing onium salt, The ionic liquid can also be obtained by the same method.

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

Ionic liquid anion structure (A ^-) of the objective and the resulting halide acid (HA) or a salt thereof with a (MA, M is a cation to form a negative ion and a salt for the purpose, such as ammonium, lithium, sodium, potassium) and The reaction is carried out to obtain a target ionic liquid (R ₄ NA).

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

The intended ionic liquid (R ₄ NA) is obtained by using the reaction of the reaction formulas (7) to (8) with the obtained hydroxide in the same manner as the halogenation method.

The acid ester method is a method carried out by a reaction as shown in the reaction formulas (9) to (11). First, an acid ester is obtained by reacting a tertiary amine (R ₃ N) with an acid ester (reaction formula (9)). Examples of the acid ester include esters of inorganic acids such as sulfuric acid, sulfuric acid, phosphoric acid, phosphorous acid, and carbonic acid, Esters of organic acids such as formic acid, formic acid, etc.) are used.

The desired ionic liquid (R ₄ NA) is obtained by using the reaction of the reaction formulas (10) to (11) in the same manner as in the halogenation method for the obtained acid ester. Further, by using methyl trifluoromethane sulfonate, methyl trifluoroacetate or the like as the acid ester, a direct ionic liquid can be obtained.

The neutralization method is a method carried out by a reaction as shown in the reaction formula (12). Tertiary amine and _{CF 3 COOH, CF 3 SO 3} H, (CF 3 SO 2) 2 NH, (CF 3 SO 2) 3 CH, (C 2 F 5 SO 2) 2 is obtainable by reacting an organic acid, such as NH have.

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

The amount of the ionic liquid to be blended is not uniformly defined because it varies depending on the compatibility of the polymer to be used and the ionic liquid. In general, it is preferably 0.001 to 50 parts by weight per 100 parts by weight of the polyurethane resin 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, most preferably 0.01 to 10 parts by weight, Parts by weight. By adjusting the blending amount of the ionic liquid within the above range, it is possible to provide an urethane pressure-sensitive adhesive excellent in antistatic property. If the amount of the ionic liquid is less than 0.01 part by weight, sufficient antistatic properties may not be obtained. If the above amount of the ionic liquid is more than 50 parts by weight, contamination of the adherend tends to increase.

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

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

As the modified silicone oil, any appropriate modified silicone oil may be employed as long as the effect of the present invention is not impaired. As such modified silicone oil, for example, a modified silicone oil available from Shin-Etsu Chemical Co., Ltd. may be mentioned.

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

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

(A polyurethane resin formed from a composition containing a polyol (A) and a polyfunctional isocyanate compound (B)),

The polyurethane resin formed from the composition containing the polyol (A) and the polyfunctional isocyanate compound (B) is preferably obtained by curing a composition containing the polyol (A) and the polyfunctional isocyanate compound (B) Is a polyurethane resin to be obtained.

The polyol (A) may be either one kind alone or two or more kinds.

The multifunctional isocyanate compound (B) may be used alone or in combination of two or more.

The polyol (A) is preferably a polyester polyol, a polyether polyol, a polycaprolactone polyol, a polycarbonate polyol or a castor oil-based polyol, for example. The polyol (A) is more preferably a polyether polyol.

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

Examples of the polyol component include ethylene glycol, diethylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, , 3-propanediol, 2,4-diethyl-1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 1,8-octanediol, Methyl-1,8-octanediol, 1,8-decanediol, octadecanediol, glycerin, trimethylolpropane, pentaerythritol, hexanetriol, polypropylene glycol and the like. Examples of the acid component include succinic acid, methylsuccinic acid, adipic acid, pimelic acid, azelaic acid, sebacic acid, 1,12-dodecanedioic acid, 1,14-tetradecanedioic acid, dimeric acid, , 4-cyclohexane dicarboxylic acid, 2-ethyl-1,4-cyclohexane dicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, isophthalic acid, terephthalic acid, 1,4-naphthalene dicarboxylic acid, '-Biphenyl dicarboxylic acid, and these acid anhydrides.

Examples of the polyether polyols include water, low molecular polyols (propylene glycol, ethylene glycol, glycerin, trimethylol propane, pentaerythritol, etc.), bisphenols (such as bisphenol A), dihydroxybenzenes (catechol, resorcin, Hydroquinone, etc.) as an initiator and addition polymerization of an alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide and the like. Specific examples thereof include polyethylene glycol, polypropylene glycol, and polytetramethylene glycol.

Examples of the polycaprolactone polyols include caprolactone polyester diols obtained by ring-opening polymerization of cyclic ester monomers such as? -Caprolactone and? -Valerolactone.

Examples of polycarbonate polyols include polycarbonate polyols obtained by polycondensation reaction of the polyol component and phosgene; The above-mentioned polyol component is mixed with the carbonic acid di (methane) carbonate such as dimethyl carbonate, diethyl carbonate, dipropyl carbonate, diisopropyl carbonate, dibutyl carbonate, ethylbutyl carbonate, ethylene carbonate, propylene carbonate, diphenyl carbonate, Polycarbonate polyols obtained by ester exchange condensation of esters; A copolymerized polycarbonate polyol obtained by using two or more of the above polyol components in combination; A polycarbonate polyol obtained by esterifying the above various polycarbonate polyols and a carboxyl group-containing compound; A polycarbonate polyol obtained by etherifying the various polycarbonate polyols and a hydroxyl group-containing compound; A polycarbonate polyol obtained by transesterifying various polycarbonate polyols and an ester compound; A polycarbonate polyol obtained by transesterifying the various polycarbonate polyols and a hydroxyl group-containing compound; A polyester polycarbonate polyol obtained by polycondensation reaction of the various polycarbonate polyols and a dicarboxylic acid compound; A copolymerized polyether polycarbonate polyol obtained by copolymerizing the various polycarbonate polyols and an alkylene oxide; And the like.

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

The number average molecular weight Mn of the polyol (A) is preferably 400 to 20,000, more preferably 500 to 17,000, still more preferably 600 to 15,000, and particularly preferably 800 to 12,000. By adjusting the number average molecular weight Mn of the polyol (A) to the above-mentioned range, the optical member having the surface protective film of the present invention can prevent the surface protective film from peeling off the surface protective film while maintaining the shear adhesive strength of the pressure- The instrument peeling force at the time of peeling from the optical member can be lowered.

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

The content of the polyol (A1) in the polyol (A) is preferably 70% by weight or more, more preferably 70% by weight to 100% by weight, and still more preferably 70% by weight to 90% by weight. By adjusting the content ratio of the polyol (A1) in the polyol (A) within the above range, the optical member having the surface protective film of the present invention can prevent the surface It is possible to further reduce the instrument peeling force when the protective film is peeled from the optical member.

The number average molecular weight Mn of the polyol (A1) is preferably 8,000 to 20,000, more preferably 8,000 to 18,000, still more preferably 8500 to 17,000, still more preferably 9,000 to 16,000, 9500 to 15,500, and most preferably from 10,000 to 15,000. By adjusting the number average molecular weight Mn of the polyol (A1) within the above-mentioned range, the optical member having the surface protective film of the present invention can prevent the surface protective film from adhering to the surface protective film while maintaining the shear adhesive strength of the pressure sensitive adhesive layer (1) The instrument peeling force at the time of peeling from the optical member can be lowered.

The polyol (A) may contain a polyol (A2) having 3 or more OH groups and a number average molecular weight Mn of 5000 or less. The polyol (A2) may be either one kind alone, or two or more kinds. The number average molecular weight Mn of the polyol (A2) is preferably 500 to 5000, more preferably 800 to 4500, still more preferably 1000 to 4000, particularly preferably 1000 to 3500, and most preferably, Lt; / RTI &gt; If the number-average molecular weight Mn of the polyol (A2) is out of the above-mentioned range, there is a possibility that the rise of the adhesive strength with time may be increased, and the excellent reworkability may not be exhibited. As the polyol (A2), a polyol (triol) having three OH groups, a polyol (tetraol) having four OH groups, a polyol (pentanol) having five OH groups, a polyol having six OH groups Come).

The total amount of the polyol (A) as the polyol (A2) in the polyol (tetraol) having 4 OH groups, the polyol (pentanol) having 5 OH groups and the polyol having 6 OH groups (hexanol) 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 one of polyol (tetraol) having 4 OH groups, polyol (pentanol) having 5 OH groups, and polyol (hexanol) having 6 OH groups in the polyol (A) , It is possible to provide an urethane-based pressure-sensitive adhesive which is further superior in transparency.

The content of the polyol (A2) in the polyol (A) is preferably 30% by weight or less, and more preferably 0% by weight to 30% by weight. By adjusting the content ratio of the polyol (A2) in the polyol (A) within the above range, the optical member having the surface protective film of the present invention can prevent the surface It is possible to further reduce the instrument peeling force when the protective film is peeled from the optical member.

The content of the polyol having a number average molecular weight Mn of not more than 5,000 in the polyol (A2) having 4 or more OH groups therein is preferably less than 10% by weight based on the total amount of the polyol (A) Is not more than 8 wt%, more preferably not more than 7 wt%, particularly preferably not more than 6 wt%, and most preferably not more than 5 wt%. When the content of the polyol having 4 or more OH groups in the polyol (A2) and having a number average molecular weight Mn of 5,000 or less is 10% by weight or more based on the total amount of the polyol (A), the urethane- There is a concern.

The multifunctional isocyanate compound (B) may be used alone or in combination of two or more.

As the polyfunctional isocyanate compound (B), any suitable polyfunctional isocyanate compound which can be used for the urethanization reaction can be employed. Examples of the polyfunctional isocyanate compound (B) include a polyfunctional aliphatic isocyanate compound, a polyfunctional alicyclic isocyanate, and a polyfunctional aromatic isocyanate compound.

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

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

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

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

The equivalent ratio of the NCO group and the OH group 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 group / OH group, Is from 0.2 to 1.8, particularly preferably from 0.3 to 1.7, and most preferably from 0.5 to 1.6. By adjusting the equivalent ratio of the NCO group and the OH group to the above range, the optical member having the surface protective film of the present invention can maintain the shear adhesive strength of the pressure-sensitive adhesive layer (1) It is possible to lower the instrument peeling force at the time of peeling.

The content of the polyfunctional isocyanate compound (B) is preferably 1.0 to 20% by weight, more preferably 1.5 to 19% by weight, based on the polyol (A), of the polyfunctional isocyanate compound (B) %, More preferably 2.0 wt% to 18 wt%, particularly preferably 2.3 wt% to 17 wt%, and most preferably 2.5 wt% to 16 wt%. By adjusting the content ratio of the polyfunctional isocyanate compound (B) within the above range, the optical member having the surface protective film of the present invention can prevent the surface protective film It is possible to lower the instrument peeling force when peeling off the optical element from the optical member.

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

As a method for forming a polyurethane resin by curing a composition containing a polyol (A) and a polyfunctional isocyanate compound (B), there are methods such as a urethane polymerization reaction method using bulk polymerization or solution polymerization, Any suitable method in the range may be employed.

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

Examples of the organometallic compounds include iron compounds, tin compounds, titanium compounds, zirconium compounds, lead compounds, cobalt compounds, zinc compounds and the like. Of these, iron-based compounds and tin-based compounds are preferable from the viewpoints of the reaction rate and the available time of the pressure-sensitive adhesive layer (1).

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

Examples of the tin compound include dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin maleate, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin sulfide, Tributyltin dichloride, tributyltin dichloride, tributyltin dichloride, tributyltin dichloride, tributyltin dichloride, tributyltin dichloride, tributyltin dichloride, tributyltin dichloride, tributyltin dichloride, tributyltin dichloride, - ethylhexanoate tin, and the like.

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

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

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

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

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

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

The catalyst may be of only one type, or two or more types. In addition, a catalyst and a crosslinking retarder may be used in combination. The amount of the catalyst is preferably 0.02% by weight to 0.10% by weight, more preferably 0.02% by weight to 0.08% by weight, more preferably 0.02% by weight to 0.06% by weight, relative to the polyol (A) Preferably 0.02% by weight to 0.05% by weight. By adjusting the amount of the catalyst within the above range, the optical member having the surface protective film of the present invention can prevent the surface protective film from peeling off from the optical member while maintaining the shear adhesive strength of the pressure sensitive adhesive layer (1) It is possible to lower the detachment force of the gauge.

The composition containing the polyol (A) and the polyfunctional isocyanate compound (B) may contain any suitable other components as long as the effect of the present invention is not impaired. Such other components include, for example, a resin component other than a polyurethane resin, a tackifier, an inorganic filler, an organic filler, a metal powder, a pigment, a thin film, a softener, an antioxidant, a conductive agent, an ultraviolet absorber, Surface lubricants, leveling agents, corrosion inhibitors, heat stabilizers, polymerization inhibitors, lubricants, solvents, catalysts and the like.

(A polyurethane resin formed from a composition containing a urethane prepolymer (C) and a polyfunctional isocyanate compound (B)),

The polyurethane resin formed from the composition containing the urethane prepolymer (C) and the polyfunctional isocyanate compound (B) may be any polyurethane resin obtained by using the so-called &quot; urethane prepolymer &quot; Can be adopted.

The polyurethane resin formed from the composition containing the urethane prepolymer (C) and the polyfunctional isocyanate compound (B) is obtained, for example, by mixing the polyurethane polyol as the urethane prepolymer (C) and the polyfunctional isocyanate compound (B) And a polyurethane resin formed from a composition. The urethane prepolymer (C) may be used alone or in combination of two or more. The multifunctional isocyanate compound (B) may be used alone or in combination of two or more.

The polyurethane polyol as the urethane prepolymer (C) is preferably produced by reacting the polyester polyol (a1) and the polyether polyol (a2) with the organic polyisocyanate compound (a3) in the presence or in the absence of a catalyst will be.

As the polyester polyol (a1), any suitable polyester polyol can be used. As such a polyester polyol (a1), there can be mentioned, for example, a polyester polyol obtained by reacting an acid component with a glycol component. Examples of the acid component include terephthalic acid, adipic acid, azelaic acid, sebacic acid, phthalic anhydride, isophthalic acid and trimellitic acid. Examples of the glycol component include ethylene glycol, propylene glycol, diethylene glycol, butylene glycol, 1,6-hexane glycol, 3-methyl-1,5-pentanediol, 3,3'-dimethylolheptane, Ethylene glycol, polyoxypropylene glycol, 1,4-butanediol, neopentyl glycol, butyl ethyl pentane diol, and polyol components such as glycerin, trimethylol propane and pentaerythritol. As the polyester polyol (a1), polyester polyol obtained by ring-opening polymerization of lactones such as polycaprolactone, poly (beta -methyl- gamma -valerolactone), polyvalerolactone and the like can be given.

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

As the polyether polyol (a2), any suitable polyether polyol can be used. Examples of the polyether polyol (a2) include low molecular weight polyols such as water, propylene glycol, ethylene glycol, glycerin and trimethylol propane as initiators, and ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran And a polyether polyol obtained by polymerizing an oxyl compound such as furan. Specific examples of the polyether polyol (a2) include a polyether polyol having two or more functional groups such as polypropylene glycol, polyethylene glycol, and polytetramethylene glycol.

The molecular weight of the polyether polyol (a2) can be from low molecular weight to high molecular weight. The molecular weight of the polyether polyol (a2) is preferably 1,000 to 5,000. If the number average molecular weight is less than 1000, the reactivity becomes high, and gelation tends to occur. If the number average molecular weight exceeds 5000, the reactivity is lowered, and further, the cohesive force of the polyurethane polyol itself may be reduced. The amount of the polyether polyol (a2) to be used is preferably 20% by mole to 80% by mole in the polyol constituting the polyurethane polyol.

If necessary, the polyether polyol (a2) may be partially substituted with a glycol such as ethylene glycol, 1,4-butanediol, neopentyl glycol, butyl ethyl pentanediol, glycerin, trimethylol propane, pentaerythritol, N-aminoethylethanolamine, isophorone diamine, xylylenediamine, and other polyamines.

As the polyether polyol (a2), only a bifunctional polyether polyol may be used, or a polyether polyol having a number average molecular weight of 1000 to 5000 and at least three hydroxyl groups in one molecule may be partially or wholly used. As the polyether polyol (a2), when a polyether polyol having an average molecular weight of 1000 to 5000 and having at least three or more hydroxyl groups in one molecule is partially or wholly used, the balance between adhesive strength and re-peelability can be improved. In such a polyether polyol, if the number average molecular weight is less than 1,000, it becomes high, and gelation tends to occur. Further, in such a polyether polyol, if the number average molecular weight exceeds 5000, the reactivity is lowered, and further, the cohesive force of the polyurethane polyol itself may be reduced. The number average molecular weight of such a polyether polyol is more preferably from 2500 to 3500.

As the organic polyisocyanate compound (a3), any suitable organic polyisocyanate compound can be used. Examples of the organic polyisocyanate compound (a3) include aromatic polyisocyanates, aliphatic polyisocyanates, aromatic aliphatic polyisocyanates, alicyclic polyisocyanates, and the like.

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

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

Examples of the aromatic aliphatic polyisocyanate include ω, ω'-diisocyanate-1,3-dimethylbenzene, ω'-diisocyanate-1,4-dimethylbenzene, ω, ω'-diisocyanate-1,4 -Diethylbenzene, 1,4-tetramethyl xylylene diisocyanate, and 1,3-tetramethyl xylylene diisocyanate.

Examples of the alicyclic polyisocyanate include 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate, 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4- Cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), 1,4-bis (isocyanatomethyl) cyclohexane, , 4-bis (isocyanatomethyl) cyclohexane, and the like.

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

Any suitable catalyst may be used as the catalyst that can be used to obtain the polyurethane polyol. Examples of such catalysts include tertiary amine compounds and organometallic compounds.

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

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

As the tin compound, for example, dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin dimaleate, dibutyltin dilaurate (DBTDL), dibutyltin diacetate, dibutyl Tributyl tin oxide, tributyl tin acetate, triethyl tin ethoxide, tributyl tin ethoxide, dioctyl tin oxide, tributyl tin chloride, tributyl tin trichloroacetate , 2-ethylhexanoate tin, and the like.

Examples of non-saponified compounds include titanium-based compounds such as dibutyltitanium dichloride, tetrabutyl titanate, and butoxy titanium trichloride; Lead compounds such as lead oleate, lead 2-ethylhexanoate, lead benzoate and lead naphthene; Iron-based compounds such as 2-ethylhexanoate and iron acetylacetonate; Cobalt compounds such as cobalt benzoate and cobalt 2-ethylhexanoate; Zinc-based compounds such as zinc naphthenate, and zinc 2-ethylhexanoate; Zirconium compounds such as zirconium naphthenate; And the like.

In the case where a catalyst is used to obtain a polyurethane polyol and a system in which two kinds of polyols such as a polyester polyol and a polyether polyol are present, due to the difference in reactivity thereof, in a system of a single catalyst, gelation, Is likely to occur. Therefore, by using two kinds of catalysts to obtain the polyurethane polyol, it becomes easy to control the reaction rate, the catalyst selectivity, and the like, and these problems can be solved. Examples of combinations of these two types of catalysts include tertiary amines / organometallic compounds, tin compounds / non-tin compounds and tin compounds / tin compounds, preferably tin compounds / tin compounds, Butyl tin dilaurate and 2-ethylhexanoic acid tin. The compounding ratio thereof is preferably 2-ethylhexanoate / dibutyltin dilaurate in a weight ratio of preferably less than 1, more preferably 0.2 to 0.6. If the compounding ratio is 1 or more, gelation tends to occur due to the balance of the catalytic activity.

When a catalyst is used to obtain the polyurethane polyol, the amount of the catalyst to be used is preferably 0.01 to 1.0 wt.% (Based on the total amount of the polyester polyol (a1), the polyether polyol (a2) and the organic polyisocyanate compound %to be.

When a catalyst is used to obtain the polyurethane polyol, the reaction temperature is preferably less than 100 占 폚, more preferably 85 占 폚 to 95 占 폚. When the temperature is higher than 100 ° C, there is a fear that the reaction rate and control of the crosslinking structure become difficult, and it is difficult to obtain a polyurethane polyol having a predetermined molecular weight.

When a polyurethane polyol is obtained, a catalyst may not be used. In that case, the reaction temperature is preferably 100 占 폚 or higher, and more preferably 110 占 폚 or higher. When the polyurethane polyol is obtained in the absence of a catalyst, the reaction is preferably carried out for 3 hours or more.

Examples of the method for obtaining the polyurethane polyol include 1) a method of putting all of the polyester polyol, polyether polyol, catalyst, and organic polyisocyanate into a flask, 2) a method in which a polyester polyol, a polyether polyol, Isocyanate is added dropwise. As a method of obtaining a polyurethane polyol, the method 2) is preferred in controlling the reaction.

When a polyurethane polyol is obtained, any appropriate solvent can be used. Examples of such a solvent include methyl ethyl ketone, ethyl acetate, toluene, xylene, acetone and the like. Among these solvents, toluene is preferable.

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

The composition containing the urethane prepolymer (C) and the polyfunctional isocyanate compound (B) may contain any other appropriate components as long as the effect of the present invention is not impaired. Such other components include, for example, a resin component other than a polyurethane resin, a tackifier, an inorganic filler, an organic filler, a metal powder, a pigment, a thin film, a softener, an antioxidant, a conductive agent, an ultraviolet absorber, 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), as a method for producing a polyurethane resin by using a so-called urethane prepolymer as a raw material, Any suitable manufacturing method may be employed.

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

The equivalent ratio of the NCO group and the OH group in the urethane prepolymer (C) and the polyfunctional isocyanate compound (B) is preferably 2.0 or less, more preferably 0.1 to 1.9 as NCO group / OH group, Preferably 0.2 to 1.8, particularly preferably 0.3 to 1.7, and most preferably 0.5 to 1.6. By adjusting the equivalent ratio of the NCO group and the OH group to the above range, the optical member having the surface protective film of the present invention can maintain the shear adhesive strength of the pressure-sensitive adhesive layer (1) It is possible to lower the instrument peeling force at the time of peeling.

The content of the polyfunctional isocyanate compound (B) is preferably 1.0% by weight to 10% by weight, more preferably 1.5% by weight to 10% by weight, based on the urethane prepolymer (C) 9.5% by weight, more preferably 2.0% by weight to 9% by weight, particularly preferably 2.3% by weight to 8.5% by weight, and most preferably 2.5% by weight to 8% by weight. By adjusting the content ratio of the polyfunctional isocyanate compound (B) within the above range, the optical member having the surface protective film of the present invention can prevent the surface protective film It is possible to lower the instrument peeling force when peeling off the optical element from the optical member.

[Silicone-based adhesive]

As the silicone adhesive, arbitrary suitable silicone adhesive can be employed as long as the effect of the present invention is not impaired, such as a known silicone adhesive described in, for example, Japanese Patent Laid-Open Publication No. 2014-47280. These may be one kind alone, or two or more kinds.

«Peeling liner»

As the release liner, for example, a release liner in which the surface of a substrate (liner base) such as paper or plastic film is subjected to silicone treatment, a release liner in which the surface of a substrate (liner base) such as paper or plastic film is laminated with a polyolefin- And the like. Examples of the plastic film as the liner substrate include a polyethylene film, a polypropylene film, a polybutene film, a polybutadiene film, a polymethylpentene film, a polyvinyl chloride film, a vinyl chloride copolymer film, a polyethylene terephthalate film, A phthalate film, a polyurethane film, and an ethylene-vinyl acetate copolymer film. The plastic film as the liner substrate is preferably a polyethylene film.

&Quot; Pressure sensitive adhesive layer (2) &quot;

The pressure-sensitive adhesive layer (2) can be produced by any suitable production method. As such a production method, for example, a method of applying a composition as a forming material of the pressure-sensitive adhesive layer 2 on a release liner and forming the pressure-sensitive adhesive layer 2 on the release liner can be mentioned. Examples of such a coating method include roll coats, gravure coats, reverse coats, roll brushes, spray coats, air knife coating methods, extrusion coats with die coaters, and the like.

The thickness of the pressure-sensitive adhesive layer 2 is preferably 1 to 500 占 퐉, more preferably 2 to 400 占 퐉, further preferably 5 to 350 占 퐉, particularly preferably 10 to 300 占 퐉 to be. By adjusting the thickness of the pressure-sensitive adhesive layer 2 within the above-mentioned range, the optical member having the surface protective film of the present invention can prevent the optical member from peeling off from the surface protective film together with the release liner when peeling the release liner, It is possible to further improve the effect that peeling is unlikely to occur at the interface between the optical member and the surface protective film.

The content of the pressure-sensitive adhesive in the pressure-sensitive adhesive layer 2 is preferably 50% by weight to 100% by weight, more preferably 60% by weight to 100% by weight, still more preferably 70% by weight to 100% Particularly preferably 80% by weight to 100% by weight, and most preferably 90% by weight to 100% by weight. By adjusting the content ratio of the pressure-sensitive adhesive in the pressure-sensitive adhesive layer (2) within the above range, the optical member having the surface protective film of the present invention can prevent the optical member from being peeled from the surface protective film together with the release liner It is possible to further improve the effect that peeling is unlikely to occur at the interface between the optical member and the surface protective film.

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

The acrylic pressure-sensitive adhesive contains an acrylic resin.

The content of the acrylic resin in the acrylic pressure-sensitive adhesive is preferably 50% by weight to 100% by weight, more preferably 70% by weight to 100% by weight, still more preferably 90% by weight to 100% By weight, preferably 95% by weight to 100% by weight, and most preferably 98% by weight to 100% by weight. By adjusting the content ratio of the acrylic resin in the acrylic pressure-sensitive adhesive within the above range, the optical member having the surface protective film of the present invention can prevent the optical member from peeling off from the surface protective film together with the release liner, That is, the effect that peeling is unlikely to occur at the interface between the optical member and the surface protective film can be further enhanced.

The acrylic pressure-sensitive adhesive may contain, in addition to the acrylic resin, any other appropriate components as long as the effect of the present invention is not impaired. Examples of such other components include a resin component other than the acrylic resin, a tackifier, an inorganic filler, an organic filler, a metal powder, a pigment, a thin film, a softener, an antioxidant, a conductive agent, an ultraviolet absorber, Lubricants, leveling agents, corrosion inhibitors, heat stabilizers, polymerization inhibitors, lubricants, solvents, catalysts and the like.

As the acrylic resin, any suitable acrylic resin may be employed as long as the effect of the present invention is not impaired. The acrylic pressure-sensitive adhesive is preferably at least one selected from the group consisting of (a) a (meth) acrylic acid alkyl ester having an alkyl group of 4 to 12 carbon atoms in the alkyl ester moiety, (b) a (meth) acrylate having an OH group, , (c) a polyfunctional isocyanate crosslinking agent, and an epoxy crosslinking agent.

The content of the component (a) in the composition for forming an acrylic resin is preferably 85% by weight to 99.9% by weight, more preferably 90% by weight to 99.8% by weight, still more preferably 92.5% by weight to 99.7% By weight, particularly preferably 95% by weight to 99.6% by weight. By adjusting the content ratio of the component (a) in the composition for forming an acrylic resin within the above-mentioned range, the optical member having the surface protective film of the present invention, when the release liner is peeled off, It is possible to further enhance the effect that peeling from the film is difficult, that is, peeling is unlikely to occur at the interface between the optical member and the surface protective film.

The content of the component (b) in the composition for forming an acrylic resin is preferably 0.1% by weight to 15% by weight, more preferably 0.2% by weight to 10% by weight, still more preferably 0.3% by weight to 7.5% By weight, and particularly preferably 0.4% by weight to 5% by weight. By adjusting the content ratio of the component (b) in the composition for forming an acrylic resin within the above-mentioned range, the optical member having the surface protective film of the present invention, when the release liner is peeled off, It is possible to further enhance the effect that peeling from the film is difficult, that is, peeling is unlikely to occur at the interface between the optical member and the surface protective film.

The content of the component (c) in the composition for forming the acrylic resin is preferably from 0.01 to 1.5% by weight, more preferably from 0.02 to 1.0% by weight, still more preferably from 0.03 to 0.8% By weight, particularly preferably 0.05% by weight to 0.7% by weight. By adjusting the content ratio of the component (c) in the composition for forming an acrylic resin within the above-mentioned range, the optical member having the surface protective film of the present invention, when the release liner is peeled off, It is possible to further enhance the effect that peeling from the film is difficult, that is, peeling is unlikely to occur at the interface between the optical member and the surface protective film.

(Meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, n Hexyl (meth) acrylate, isohexyl (meth) acrylate, n-heptyl (meth) acrylate, iso-pentyl (meth) acrylate, (Meth) acrylate, iso-octyl (meth) acrylate, n-octyl (meth) acrylate, (Meth) acrylate, stearyl (meth) acrylate, and cyclohexyl (meth) acrylate. These may be one kind alone, or two or more kinds.

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

Examples of the (meth) acrylate ester having an OH group include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (Meth) acrylate, 3-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 5-hydroxypentyl (Meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxydecyl (meth) acrylate, -Hydroxy lauryl (meth) acrylate, and (4-hydroxymethylcyclohexyl) -methylacrylate. These may be one kind alone, or two or more kinds.

Examples of the polyfunctional isocyanate crosslinking agent include aliphatic polyisocyanates such as butylene diisocyanate and hexamethylene diisocyanate, alicyclic isocyanates such as cyclopentylene diisocyanate, cyclohexylene diisocyanate and isophorone diisocyanate, Aromatic isocyanates such as 4-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate and xylylene diisocyanate, trimethylolpropane / tolylene diisocyanate trimeric adduct (trade name: Coronate L, manufactured by Nippon Polyurethane Industry Co., (Trade name &quot; Coronate HL &quot;, manufactured by Nippon Polyurethane Industry Co., Ltd.), isocyanurate of hexamethylene diisocyanate (trade name: Coronate HX, manufactured by Nippon Polyurethane Industry Co., Ltd.), trimethylolpropane / hexamethylene diisocyanate trimer adduct ) Additional isocyanate may be mentioned water or the like. These may be one kind alone, or two or more kinds.

Examples of the epoxy cross-linking agent include bisphenol A, epichlorohydrin type epoxy resin, ethylene glycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, 1,6 - hexanediol glycidyl ether, trimethylol propane triglycidyl ether, diglycidyl aniline, diamine glycidyl amine, N, N, N ', N'-tetraglycidyl-m-xylenediamine (trade name " (Trade name &quot; TETRAD-C &quot; manufactured by Mitsubishi Gas Chemical Company), and the like can be given. . These may be one kind alone, or two or more kinds.

The composition for forming an acrylic resin may also contain a crosslinking catalyst. Examples of the crosslinking catalyst include metal-based crosslinking catalysts (particularly, tin-based crosslinking catalysts) such as tetra-n-butyl titanate, tetraisopropyl titanate, ferric sulfate, butyl tin oxide, dioctyltin dilaurate, . These crosslinking catalysts may be either one kind or two or more kinds.

The composition for forming an acrylic resin may contain any suitable other monomer as long as the effect of the present invention is not impaired. Examples of such other monomers include benzyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxymethyl (meth) acrylate, phenoxyethyl (meth) acrylate, (meth) , (Meth) acrylonitrile, and the like. These may be one kind alone, or two or more kinds.

The composition for forming an acrylic resin may contain any other appropriate components as long as the effect of the present invention is not impaired. Examples of such other components include a resin component other than the acrylic resin, a tackifier, an inorganic filler, an organic filler, a metal powder, a pigment, a thin film, a softener, an antioxidant, a conductive agent, an ultraviolet absorber, 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 not less than 1,000,000, more preferably not less than 1,100,000 to 2,500,000, as measured by a gel permeation chromatography (GPC) method using a tetrahydrofuran solvent More preferably from 1.2 to 2.3 million, and particularly preferably from 1.3 to 2.1 million. By adjusting the weight average molecular weight (Mw) of the acrylic resin within the above range, the optical member having the surface protective film of the present invention can prevent the optical member from being peeled off from the surface protective film together with the release liner That is, the effect that the peeling is unlikely to occur slowly at the interface of the surface protective film.

The acrylic resin can be produced by any suitable method as long as the effect of the present invention is not impaired. Such a method includes, for example, a polymerization reaction of a composition for forming 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). Particularly, from the viewpoints of cost and productivity, a solution polymerization method is preferable. As a solution polymerization method, for example, there can be mentioned 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.

As the solvent, for example, aromatic hydrocarbons such as toluene, benzene, and xylene; Esters such as ethyl acetate and n-butyl acetate; aliphatic hydrocarbons such as n-hexane and n-heptane; Alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; Ketones such as methyl ethyl ketone and methyl isobutyl ketone; And the like. The solvent may be one kind or two or more kinds.

Examples of the polymerization initiator which can be used in the solution polymerization method include a peroxide-based polymerization initiator and an azo-based polymerization initiator. Examples of the peroxide-based polymerization initiator include peroxycarbonate, ketone peroxide, peroxyketal, hydroperoxide, dialkyl peroxide, diacyl peroxide and peroxy ester. More specifically, Butyl peroxide, di-t-butyl peroxide, t-butyl peroxybenzoate, dicumyl peroxide, 1,1-bis (t-butylperoxy) Trimethylcyclohexane, and 1,1-bis (t-butylperoxy) cyclododecane. Examples of the azo-based polymerization initiator include 2,2'-azobisisobutyronitrile, 2,2'-azobis-2-methylbutyronitrile, 2,2'-azobis (2,4- (2-methylpropionic acid), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 1,1'-azobis Azobis (2,4,4-trimethylpentane), 4,4'-azobis-4-cyanovaleric acid, 2,2'-azobis 2-aminodopropane) dihydrochloride, 2,2'-azobis [2- (5-methyl-2-imidazolin- Azobis (N, N'-dimethyleneisobutylamidine) hydrochloride, 2,2'-azobis [N- (2-carboxyethyl) -2 -Methylpropionamidine] hydrate. &Lt; / RTI &gt; The polymerization initiator may be a single kind or two or more kinds.

The content of the polymerization initiator is preferably 0.01 parts by weight to 5 parts by weight, more preferably 0.05 parts by weight to 3 parts by weight, based on 100 parts by weight of the whole monomer component constituting the base polymer.

As the heating temperature at the time of polymerization by heating in the solution polymerization method, any suitable heating temperature can be set within a range not to impair the effect of the present invention. The heating temperature is preferably 50 to 80 占 폚. In the solution polymerization method, any appropriate heating time can be set as the heating time in heating and polymerizing within the range not to impair the effect of the present invention. The heating time is preferably 1 hour to 24 hours.

<< Manufacturing Method of Optical Member Having Surface Protective Film >>

A manufacturing method of an optical member having a surface protective film of the present invention is an optical member having a surface protective film provided with an optical member and a surface protective film, wherein the surface protective film includes a base layer and a pressure sensitive adhesive layer (1) Any suitable method can be adopted as long as the pressure-sensitive adhesive layer 1 of the surface protective film can be a constitution on the optical member side.

In the method for producing an optical member having a surface protective film of the present invention, it is preferable that, for example, when joining the surface protective film, bonding is performed to the optical member while applying tension to the surface protective film. The tension may be appropriately set according to the constitution (for example, thickness, forming material, elastic modulus, tensile elongation, etc.) of the surface protective film. And can be produced by the above-described operation.

[Example]

Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited to these examples. Tests and evaluation methods in Examples and the like are as follows. In addition, in the case of "part (s)", "weight part" means unless otherwise specified, and "%" means "% by weight" unless otherwise specified.

[Production Example 1] Production of pressure-sensitive adhesive for polarizing plate

In a four-necked flask equipped with a stirrer blade, a thermometer, a nitrogen gas introducing tube and a condenser, 99 parts by weight of butyl acrylate (manufactured by Nippon Sourcing Co., Ltd.), 4 parts by weight of 4-hydroxybutyl acrylate , 0.1 part by weight of 2,2'-azobisisobutyronitrile (manufactured by Wako Pure Chemical Industries, Ltd.) as a polymerization initiator, and 100 parts by weight of ethyl acetate were charged and slowly added with nitrogen And the polymerization reaction was carried out for 8 hours while maintaining the liquid temperature in the flask at around 55 캜 to prepare an acrylic polymer solution (50% by weight) having a weight average molecular weight of 1,600,000. The resulting acrylic polymer solution (50% by weight) was diluted to 20% by weight with ethyl acetate, and 0.1 part by weight of Coronate L (manufactured by Nippon Polyurethane Kogyo K.K.) as a crosslinking agent was added to 100% To prepare an acrylic pressure-sensitive adhesive solution.

[Production Example 2]: Production of polarizing plate

(Production of Polarizer)

The polyvinyl alcohol film having a degree of polymerization of 2400, a degree of saponification of 99.9%, and a thickness of 30 占 퐉 was immersed in hot water at 30 占 폚 to swell, while being uniaxially stretched so that the length of the polyvinyl alcohol film was 2.0 times the original length. Subsequently, the film was immersed in an aqueous solution (dyeing bath) having a concentration of 0.3% by weight of a mixture of iodine and potassium iodide (weight ratio = 0.5: 8), and the film was uniaxially stretched so that the length of the polyvinyl alcohol film was 3.0 times the original length. Dyed. Thereafter, the polyvinyl alcohol film was stretched so that the length of the polyvinyl alcohol film was 3.7 times the original length while immersed in an aqueous solution (crosslinking bath 1) of 5% by weight of boric acid and 3% by weight of potassium iodide. Then, 4% by weight of boric acid at 60 DEG C, The film was stretched so that the length of the polyvinyl alcohol film was six times the original length in an aqueous solution (crosslinking bath 2) of potassium 5% by weight. Thereafter, an iodine ion impregnation treatment was carried out with an aqueous solution of 3% by weight of potassium iodide (iodine impregnation bath), followed by drying in an oven at 60 ° C for 4 minutes to obtain a polarizer. The thickness of the obtained polarizer was 12 占 퐉.

(Preparation of aqueous adhesive)

(Average degree of polymerization: 1200, degree of saponification: 98.5 mol%, degree of acetacetylation: 5 mol%) containing acetoacetyl groups was dissolved in pure water under a temperature condition of 30 캜 and adjusted to a solid content concentration of 4% Aqueous adhesive was obtained.

(Production of polarizing plate)

The water-based adhesive was applied to triacetyl cellulose (TAC) having a thickness of 25 탆 so that the thickness of the dried adhesive layer became 80 nm to obtain a polarizer protective film having an adhesive layer. Subsequently, a polarizer protective film having the adhesive layer was bonded to both surfaces of the polarizer by a roll machine under a temperature condition of 23 캜, and then dried at 55 캜 for 6 minutes to prepare a polarizing plate. The polarizer and the polarizer protective film having the adhesive layer were bonded so that the polarizer and the adhesive layer of the polarizer protective film having the adhesive layer were in contact with each other. Thus, a polarizing plate was produced.

[Production Example 3]: Preparation of release liner

The pressure-sensitive adhesive for a polarizing plate prepared in Production Example 1 was applied to a silicon-treated surface of a base material containing a polyester resin having a thickness of 38 mu m which was subjected to a silicone treatment on one side and a silicone-treated surface of a substrate containing a polyester resin , Respectively, and dried and cured under the conditions of a drying temperature of 150 占 폚 and a drying time of 2 minutes so that the thickness after drying was 20 占 퐉, thereby forming a pressure-sensitive adhesive layer. Thus, a laminate of a release liner having a thickness of 38 mu m and a pressure-sensitive adhesive layer and a laminate of a release liner and a pressure-sensitive adhesive layer having a thickness of 50 mu m were produced.

[Production Example 4]: Production of a polarizing plate with a laminate of release liner and pressure-sensitive adhesive layer

On one side of the polarizing plate obtained in Production Example 2, the pressure-sensitive adhesive layer side of the laminated product of the release liner and the pressure-sensitive adhesive layer obtained in Production Example 3 was bonded to produce a polarizing plate with a laminate of release liner and pressure- The thickness of the polarizing plate having the pressure-sensitive adhesive layer excluding the release liner was 82 占 퐉.

[Production Example 5]: Production of urethane pressure-sensitive adhesive composition (U1), which is a material for forming a pressure-sensitive adhesive layer contained in a surface protective film

(Manufactured by Asahi Kasei Corporation), which is a polyol having three hydroxyl groups (Mn = 10000), polyanhydride GP-3000 having three OH groups (manufactured by Sanyo Chemical Industries, Ltd.) (Manufactured by Sanyo Chemical Industries, Ltd., Mn = 1000), polyfunctional alicyclic isocyanate compound (Coronate HX) as a polyfunctional isocyanate compound (B) (Manufactured by Nippon Polyurethane Industry Co., Ltd.), a catalyst (manufactured by Nihon Kagaku Kogyo K.K., trade name: Nasem® 2 iron), an anti-deterioration agent (Irganox 1010 manufactured by BASF), myristic acid isopropyl Ethylhexanoate (trade name: Saracosu 816T, Mn = 368, manufactured by Nissin Oil Group Co., Ltd.), 1-ethyl-3-methyl If the midazolium bis (fluoromethanesulfonyl) Terminal type polyether-modified silicone oil (trade name: KF-6004, manufactured by Shin-Etsu Chemical Co., Ltd.), ethyl acetate as a diluting solvent, And the mixture was stirred to prepare a urethane pressure-sensitive adhesive composition. The mixing ratios are shown in Table 1.

[Production Example 6]: Production of urethane pressure-sensitive adhesive composition (U2) as a pressure-sensitive adhesive layer forming material contained in the surface protective film

(Manufactured by Nippon Polyurethane Industry Co., Ltd.), which is a polyfunctional alicyclic isocyanate compound as polyfunctional isocyanate compound (B), is used as the urethane prepolymer (C) ), Toluene was added as a diluting solvent, and the mixture was stirred to adjust the urethane pressure-sensitive adhesive composition (U2). The mixing ratios are shown in Table 1. In addition, the number of the blendings of each material except toluene is all in terms of solid content, and the number of toluene is the total amount of the solvent contained in the pressure-sensitive adhesive.

[Production Example 7]: Production of acrylic pressure-sensitive adhesive composition (Ac1), which is a material for forming a pressure-sensitive adhesive layer contained in a surface protective film

A four-necked flask equipped with a stirrer blade, a thermometer, a nitrogen gas introducing tube and a condenser was charged with 100 parts by weight of 2-ethylhexyl acrylate (manufactured by Nippon Sourcing Co., Ltd.), 2-hydroxyethyl acrylate 4 parts by weight as a polymerization initiator, 0.2 part by weight of 2,2'-azobisisobutyronitrile (manufactured by Wako Pure Chemical Industries, Ltd.) and 156 parts by weight of ethyl acetate were added as a polymerization initiator, (40% by weight) of an acrylic polymer (Ac1P) having a weight average molecular weight of 550,000 was prepared by introducing a gas into the flask and maintaining the liquid temperature in the flask at about 65 DEG C for 6 hours. Coronate HX (manufactured by NIPPON POLYURETHANE CHEMICAL INDUSTRIES, LTD.) And a catalyst (manufactured by NIPPON POLYURETHANE CHEMICAL INDUSTRY CO., LTD.) As a cross-linking agent and a catalyst Ethyl acetate as a diluting solvent, and mixing and stirring were carried out to prepare an acrylic pressure-sensitive adhesive composition (Ac1). The mixing ratios are shown in Table 1. In addition, the number of the blendings of the respective materials except ethyl acetate is all converted to the solid content, and the number of the ethyl acetate is the total amount of the solvent contained in the pressure-sensitive adhesive.

[Production Example 8]: Production of acrylic pressure-sensitive adhesive composition (Ac2), which is a material for forming a pressure-sensitive adhesive layer contained in a surface protective film

95 parts by weight of butyl acrylate (manufactured by Nippon Denshoku Co., Ltd.), 5 parts by weight of acrylic acid (manufactured by Toagosei Co., Ltd.), 5 parts by weight of acrylic acid , 0.2 part by weight of 2,2'-azobisisobutyronitrile (produced by Wako Pure Chemical Industries, Ltd.) as a polymerization initiator, and 186 parts by weight of ethyl acetate were introduced, and nitrogen gas which was slowly stabilized was introduced into the flask A polymerization reaction was carried out for 10 hours while maintaining the liquid temperature at around 63 占 폚 to prepare a solution (35% by weight) of an acrylic polymer (Ac2P) having a weight average molecular weight of 500,000. To the obtained solution (35 wt.%) Of the acrylic polymer (Ac2P) having a weight average molecular weight of 500,000, Tetrad C (manufactured by Mitsubishi Gas Chemical Company) and a catalyst (manufactured by Nihon Gagaku Sanayaku Co., Ltd., trade name: Ethyl acetate as a diluting solvent and mixing and stirring were conducted to prepare an acrylic pressure-sensitive adhesive composition (Ac2). The mixing ratios are shown in Table 1. In addition, the number of the blendings of the respective materials except ethyl acetate is all converted to the solid content, and the number of the ethyl acetate is the total amount of the solvent contained in the pressure-sensitive adhesive.

[Production Example 9]: Production of a silicone-based pressure-sensitive adhesive composition (S) as a pressure-sensitive adhesive layer forming material contained in a surface protective film

(Trade name: CAT-PL-50T, manufactured by Shin-Etsu Chemical Co., Ltd.) was used in place of the addition reaction type silicone adhesive (trade name: X-40-3306, manufactured by Shinetsu Chemical Industry Co., Ltd.) Were mixed to prepare a silicone-based pressure-sensitive adhesive composition (S). The mixing ratios are shown in Table 1.

[Production Example 10]: Production of a surface protective film having a separator

The resulting pressure-sensitive adhesive composition was coated on a substrate "LM Mirror S10" (thickness 38 μm, manufactured by Dorey Corporation) containing a polyester resin so as to have a thickness of 10 μm after drying with a fountain roll, Sec. &Lt; / RTI &gt; Thus, a pressure-sensitive adhesive layer was formed on the substrate. Subsequently, the surface of the pressure-sensitive adhesive layer was bonded to the silicone-treated surface of a base material (separator) containing a polyester resin having a thickness of 25 占 퐉, which had been subjected to a silicone treatment on one surface thereof to obtain a surface protective film having a separator.

&Lt; Measurement of instrument peeling force of surface protective film >

Preparation of Evaluation Sample: The polarizing plate with the laminate of the release liner and the pressure-sensitive adhesive layer obtained in Production Example 4 was cut to a width of 70 mm and a length of 100 mm. The separator was peeled off from the surface protective film having the separator obtained in Production Example 10, and the pressure-sensitive adhesive layer side of the surface protective film was laminated to the cut polarizing plate at a pressure of 0.25 MPa. Thereafter, .

Measurement of instrument peeling force: The produced evaluation sample was allowed to stand under an environment of 23 캜 x 50% RH for 24 hours, and then a single-sided adhesive tape (manufactured by Nichiban Co., Ltd., : Cellophane Tape (registered trademark)) was pressed on the back surface side of the surface protective film so as to have an end face of 1 mm, and left for 10 seconds. Thereafter, the single-sided adhesive tape was peeled off using a universal tensile tester (product name: TCM-1kNB, manufactured by Minebea Kabushiki Kaisha) at a peeling speed of 300 mm / min and 6 m / min, , The maximum stress applied at the beginning of peeling was called the peeling force (N / 25 mm). The measurement was carried out in an environment of 23 캜 x 50% RH.

&Lt; Measurement of Shear Adhesion of Surface Protective Film >

The surface protective film having the separator obtained in Production Example 10 was cut into a size of 10 mm in width and 100 mm in length, and the separator was peeled off. Thereafter, the polarizing plate with a laminate of the release liner and the pressure-sensitive adhesive layer obtained in Production Example 4 was cut into a width of 70 mm and a length of 100 mm, and a pressure-sensitive adhesive layer adhesive surface area of the surface protective film of 1 cm & So as to obtain an evaluation sample. After lamination, the laminate was stretched in a shearing direction at a tensile rate of 0.06 mm / min at 23 DEG C, and the maximum load (N / 10 mm) at that time was referred to as shear adhesion.

&Lt; Measurement of initial adhesion of surface protective film >

The surface protective film having the separator obtained in Production Example 10 was cut to a size of 25 mm in width and 80 mm in length, and the separator was peeled off. Thereafter, the polarizing plate with a laminate of the release liner and the pressure-sensitive adhesive layer obtained in Production Example 4 was cut into a width of 70 mm and a length of 100 mm, and the pressure-sensitive adhesive layer side of the surface protective film was pressed at a pressure of 0.25 MPa And laminated to prepare an evaluation sample. After the lamination, the laminate was allowed to stand for 30 minutes under an environment of 23 占 폚 and 50% RH. Using a universal tensile tester (product name: TCM-1kNB, manufactured by Minebea Kabushiki Kaisha), a peeling speed of 300 mm / min, When the surface protective film was peeled off, the adhesive force in the area where the value became stable was measured. The measurement was carried out in an environment of 23 캜 x 50% RH.

&Lt; Measurement of wetting speed of surface protective film &

The surface protective film having the separator obtained in Production Example 10 was cut into 2.5 cm wide and 10 cm long to obtain evaluation samples. A polarizing plate having a laminate of the release liner and the pressure-sensitive adhesive layer obtained in Production Example 4 as an adherend was used. One end of the width side of the pressure-sensitive adhesive layer side of the evaluation sample from which the separator was peeled off was fixed on the side opposite to the release liner of the adherend, and the end of the width side that was not fixed was lifted to measure the time (Unit: sec / 2.5 cm 占 10 cm). The wetting rate (unit: cm 2 / sec) was calculated from the time taken.

&Lt; Measurement of weight average molecular weight >

The weight average molecular weight (Mw) of the acrylic polymer obtained in Production Examples 7 and 8 was measured using a GPC apparatus (HLC-8220GPC, manufactured by Tosoh Corporation). The measurement conditions are as follows. In addition, the weight average molecular weight was determined in terms of polystyrene conversion.

Sample concentration: 0.2 wt% (THF solution)

Sample injection volume: 10 μl Eluent

THF flow rate: 0.6 ml / min

Measuring temperature: 40 ° C

Sample column: TSKguardcolumn SuperHZ-H (1) + TSKgel SuperHZM-H (2)

Reference column: TSKgel SuperH-RC (1)

Detector: Differential refractometer (RI)

[Examples 1 to 13, Comparative Examples 1 to 3]

The surface protective film having the separator obtained in Production Example 10 was cut to a size of 25 mm in width and 80 mm in length according to the number of components shown in Table 1, and the separator was peeled off. Thereafter, the polarizing plate with a laminate of the release liner and the pressure-sensitive adhesive layer obtained in Production Example 4 was cut into a width of 70 mm and a length of 100 mm, and the pressure-sensitive adhesive layer side of the surface protective film was pressed at a pressure of 0.25 MPa (1) to (13), (C1) to (C3) having a surface protective film constituted of a release liner / pressure-sensitive adhesive layer / optical member / surface protective film (pressure-

The results are shown in Table 1.

The optical member having the surface protective film of the present invention can be used in any suitable application. Preferably, the optical member having the surface protective film of the present invention is preferably used in the field of optical members and electronic members.

10: peeling liner
20: pressure-sensitive adhesive layer (2)
30: optical member
40: pressure-sensitive adhesive layer (1)
50: substrate layer
100: Surface protective film
1000: Optical member having a surface protective film

Claims (12)

A laminate of an optical member and a surface protective film; a pressure-sensitive adhesive layer (2) provided on a side opposite to the surface protective film of the optical member; and a release liner provided on a side opposite to the optical member of the pressure- An optical member having a surface protective film in this order,
The surface protective film comprises a substrate layer and a pressure-sensitive adhesive layer (1)
Sensitive adhesive layer (1) of the surface protective film is on the optical member side,
, The pressure-sensitive adhesive layer (1) has a shear adhesive strength of 10 N / 10 mm or more,
Wherein the surface peeling strength of the surface protective film is 2.0 N / 25 mm or less at a peeling speed of 300 mm /
An optical member having a surface protective film. The method according to claim 1,
Wherein the optical member has a thickness of 1 占 퐉 to 500 占 퐉. 3. The method according to claim 1 or 2,
Wherein the surface protective film has a thickness of 5 to 500 占 퐉. 4. The method according to any one of claims 1 to 3,
Wherein the release liner has a thickness of 1 占 퐉 to 500 占 퐉. 5. The method according to any one of claims 1 to 4,
Wherein the base layer is a plastic film. 6. The method according to any one of claims 1 to 5,
Wherein the pressure-sensitive adhesive contained in the pressure-sensitive adhesive layer (1) is at least one selected from a urethane pressure-sensitive adhesive and a silicone pressure-sensitive adhesive. The method according to claim 6,
The optical member having a surface protective film comprising a polyurethane resin wherein the urethane pressure-sensitive adhesive is formed from a composition containing a polyol (A) and a polyfunctional isocyanate compound (B). 8. The method of claim 7,
Wherein the equivalent ratio of the NCO group and the OH group in the polyol (A) and the polyfunctional isocyanate compound (B) is 2.0 or less as the NCO group / OH group. The method according to claim 6,
Wherein the urethane pressure-sensitive adhesive contains a urethane prepolymer (C) and a polyfunctional isocyanate compound (B). 10. The method of claim 9,
Wherein the equivalent ratio of the NCO group and the OH group in the urethane prepolymer (C) and the polyfunctional isocyanate compound (B) is 2.0 or less as the NCO group / OH group. 11. The method according to any one of claims 7 to 10,
Wherein the urethane pressure-sensitive adhesive comprises a surface-protective film comprising a fatty acid ester. 12. The method according to any one of claims 1 to 11,
Wherein the surface protective film has a wetting rate of 5 cm &lt; 2 &gt; / sec or more with respect to the surface of the optical member.

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