KR20180121319A - Adhesive composition and adhesive film - Google Patents

Abstract

The present invention provides an adhesive composition and an adhesive film capable of achieving both excellent antistatic performance and durability including adhesive performance. In the adhesive composition, an acrylic polymer has a glass transition temperature of 0°C or lower; and a crosslinking agent is at least one crosslinking agent selected from the group consisting of an isocyanate compound having three or more functional groups and an epoxy compound having two or more functional groups. The adhesive composition comprises a monomer type or oligomer type silane coupling agent containing at least one functional group selected from the group consisting of an epoxy group, a mercapto group and an acid anhydride group. An antistatic agent is an ionic compound having a melting point of 25°C or higher, and is composed of positive and negative ions, and the negative ions are selected from the group consisting of trifluoromethane sulfonate negative ions, pentafluoroethane sulfonate negative ions, heptafluoropropane sulfonate negative ions, and nonafluorobutane sulfonate negative ions.

Description

[0001] ADHESIVE COMPOSITION AND ADHESIVE FILM [0002]

The present invention relates to a pressure-sensitive adhesive composition containing an antistatic agent and a pressure-sensitive adhesive film. More particularly, the present invention relates to a pressure-sensitive adhesive composition comprising an ionic compound having a specific sulfonate anion such as nonafluorobutane sulfonate as an antistatic agent, thereby to provide a pressure-sensitive adhesive composition having durability and antistatic performance, The present invention relates to an adhesive film used.

A variety of pressure-sensitive adhesive films for bonding an optical member such as a polarizing plate and a retarder to an adherend such as a liquid crystal cell through a pressure-sensitive adhesive layer have been proposed (see, for example, Patent Documents 1 and 2).

Patent Document 1 discloses a pressure-sensitive adhesive composition for optical purposes containing an acryl-based polymer obtained by copolymerizing an acrylamide compound or the like with butyl acrylate or the like as a main component monomer.

Patent Document 2 discloses a pressure-sensitive adhesive composition for optical use which contains an acrylic polymer obtained by copolymerizing a carboxyl-containing monomer and a nitrogen-containing vinyl monomer with a (meth) acrylate having an alkyl group having 4 to 8 carbon atoms as a main component monomer.

Japanese Laid-Open Patent Publication No. 2012-177022 Japanese Laid-Open Patent Publication No. 2012-201734

However, when the surface of the optical film is subjected to the antifouling treatment or the low-reflection surface treatment with a composition containing a silicone compound or the like, the peeling electrification voltage at the time of peeling off the adhesive film used for such an optical film from the adherend becomes high .

The relationship between the antistatic property of the pressure-sensitive adhesive composition having an antistatic property and the pressure-sensitive adhesive property of the pressure-sensitive adhesive film using the pressure-sensitive adhesive composition and the durability including the pressure-sensitive adhesive property to an adherend has a trade-off relationship. It has been difficult to improve durability.

Therefore, even when the surface of the optical film is surface-treated with a composition containing a silicon compound or the like, the peeling electrification voltage at the time of peeling the adhesive film from the optical film can be suppressed to a low level and the durability Has been demanded.

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and provides a pressure-sensitive adhesive composition and a pressure-sensitive adhesive film using the pressure-sensitive adhesive composition capable of achieving both excellent antistatic performance and durability including adhesive performance.

The present inventors have found that a copolymer obtained by copolymerizing two or more kinds of alkyl (meth) acrylates in a specific combination while limiting the number of carbon atoms in the alkyl group of the alkyl (meth) acrylate constituting the acrylic polymer of the pressure-sensitive adhesive composition to a specific range, Butane sulfonate and the like, and an antistatic agent comprising an ionic compound having a specific sulfonate anion having a melting point of 25 占 폚 or more. Thus, the present inventors have found that a pressure-sensitive adhesive composition having durability including excellent adhesive performance and no deterioration with time and having excellent peeling electrification preventing performance can be obtained as compared with the conventional pressure-sensitive adhesive composition for a pressure-sensitive adhesive film.

In particular, the pressure-sensitive adhesive film according to the present invention has durability including excellent adhesive performance as compared with the prior art, and does not deteriorate with time and has excellent peeling electrification preventing performance. Therefore, in view of both of antistatic performance and durability including adhesive performance It proved to be effective.

In order to solve the above problems, the present invention provides a pressure-sensitive adhesive composition containing an acrylic polymer, an antistatic agent, and a crosslinking agent,

Wherein the acrylic polymer has a glass transition temperature of 0 DEG C or lower,

Wherein the crosslinking agent (D) is at least one crosslinking agent selected from the group consisting of an isocyanate compound having three or more functional groups and an epoxy compound having two or more functional groups,

Wherein the pressure-sensitive adhesive composition further comprises (H) a monomer type or oligomer type silane coupling agent containing at least one functional group selected from the group consisting of an epoxy group, a mercapto group and an acid anhydride group,

Wherein the antistatic agent is an ionic compound having a melting point of not lower than 25 占 폚, which is composed of a cation and an anion, and the anion is a trifluoromethanesulfonate anion, a pentafluoroethanesulfonate anion, a heptafluoropropanesulfonate anion, A cationic anion, and a cationic anion,

Wherein the antistatic agent is contained in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the acryl-based polymer as essential components.

The acrylic polymer

(A) at least one alkyl (meth) acrylate monomer having an alkyl group having from 1 to 14 carbon atoms,

(B) at least one copolymerizable vinyl monomer containing a hydroxyl group and / or a carboxyl group,

(C) at least one copolymerizable vinyl monomer containing an aromatic group, wherein the copolymer is an acrylic polymer,

The total amount of at least one copolymerizable vinyl monomer containing a hydroxyl group and / or a carboxyl group (B) in an amount of 0.1 to 5 parts by weight relative to 100 parts by weight of the total of the components (A) and (C) ,

A pressure-sensitive adhesive layer having a thickness of 20 占 퐉 in which the pressure-sensitive adhesive composition was crosslinked was laminated to a polarizing plate having a total thickness of 80 占 퐉. The pressure-sensitive adhesive layer having a thickness of 20 占 퐉 had an adhesive force of 6N / It is preferable that there is no foaming and peeling even after the durability test at 105 ° C x 500 hr.

Wherein the cation is selected from the group consisting of pyridinium, imidazolium, phosphonium, sulfonium, pyrrolidinium, guanidinium, ammonium, isooronium, thiouronium, piperidinium, paraazolium, methylium, lithium, morpholinium And the like.

It is preferable that the pressure-sensitive adhesive layer crosslinked with the pressure-sensitive adhesive composition has a surface resistivity of 1.0 x 10 ^{+ 12} ? /? Or less.

Wherein the (B) copolymerizable vinyl monomer containing a hydroxyl group and / or a carboxyl group is at least one or more selected from the group consisting of a copolymerizable monomer containing a hydroxyl group and a copolymerizable monomer containing a carboxyl group,

(Meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (Meth) acrylate, N-hydroxy (meth) acrylamide, N-hydroxymethyl (meth) acrylamide and N-hydroxyethyl

Wherein the copolymerizable monomer containing a carboxyl group is selected from the group consisting of (meth) acrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, 2- (meth) acryloyloxyethylhexahydrophthalic acid, 2- (Meth) acryloyloxyethylmaleic acid, 2- (meth) acryloyloxyethylphthalic acid, 2- (meth) acryloyloxyethylsuccinic acid, carboxypolycaprolactone mono (Meth) acrylate, and 2- (meth) acryloyloxyethyl tetrahydrophthalic acid.

The present invention also provides an adhesive film comprising a resin film laminated on one side thereof with a pressure-sensitive adhesive layer formed by crosslinking the pressure-sensitive adhesive composition.

The present invention also provides an optical film with a pressure-sensitive adhesive layer in which a pressure-sensitive adhesive layer formed by crosslinking the pressure-sensitive adhesive composition on at least one surface of an optical film is laminated.

Further, the present invention provides an adhesive film in which antistatic treatment and antifouling treatment are carried out on one side of the resin film opposite to the side on which the pressure-sensitive adhesive layer is laminated.

The present invention also provides an adhesive film for a polarizing plate using the adhesive film.

The present invention also relates to a pressure-sensitive adhesive sheet comprising a pressure-sensitive adhesive layer formed by crosslinking the pressure-sensitive adhesive composition on one side of a release film, the pressure-sensitive adhesive layer being laminated with a thickness of 1 to 25 m and being constituted of a release film / pressure- Film.

Further, the present invention provides a liquid crystal panel characterized in that the optical film with the pressure-sensitive adhesive layer is used.

According to the present invention, it is possible to provide a pressure-sensitive adhesive composition and a pressure-sensitive adhesive film capable of achieving both excellent antistatic performance and durability including tackiness.

INDUSTRIAL APPLICABILITY The pressure-sensitive adhesive composition and the pressure-sensitive adhesive film using the pressure-sensitive adhesive composition according to the present invention have durability including excellent adhesive performance as compared with the prior art even when the surface of the optical film as the adherend is subjected to surface treatment with a composition containing a silicone compound, Further, it does not deteriorate with time and has excellent peeling electrification preventing performance.

That is, the pressure-sensitive adhesive composition of the present invention and the pressure-sensitive adhesive film using the pressure-sensitive adhesive composition of the present invention have excellent durability including excellent antistatic performance and excellent adhesive performance.

Hereinafter, the present invention will be described based on preferred embodiments.

The pressure-sensitive adhesive composition of the present embodiment is a pressure-sensitive adhesive composition containing an acrylic polymer, an antistatic agent and a crosslinking agent, wherein the acrylic polymer has a glass transition temperature of 0 캜 or lower, and the crosslinking agent (D) And a bifunctional or higher functional epoxy compound, wherein the pressure-sensitive adhesive composition further comprises (H) a monomer type containing at least one functional group selected from the group consisting of an epoxy group, a mercapto group and an acid anhydride group Or an oligomer type silane coupling agent, wherein the antistatic agent is an ionic compound having a melting point of 25 占 폚 or more comprising a cation and an anion and the anion is a trifluoromethanesulfonate anion, a pentafluoroethanesulfonate anion, Heptafluoropropanesulfonate Ions, and one member selected from the group consisting of butane sulfonate anion nonafluorobutyl, characterized in that formed by containing, as an essential component in a proportion of 0.01 to 10 parts by weight of the antistatic agent based on 100 parts by weight of the acrylic polymer.

The antistatic agent is preferably an ionic compound having a melting point of 25 占 폚 or higher which is a solid at a temperature of 25 占 폚, and more preferably the melting point of the antistatic agent is 450 占 폚 or lower.

The acrylic polymer used in the pressure-sensitive adhesive composition of this embodiment has a glass transition temperature of 0 占 폚 or lower. The acrylic polymer is preferably a copolymer having as a main component at least one alkyl (meth) acrylate monomer having an alkyl group of C1-C14 as the alkyl group.

Examples of alkyl (meth) acrylate monomers having (C1) to (C14) carbon atoms in the alkyl group (A) include methyl (meth) acrylate, ethyl (meth) acrylate, (Meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (Meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, undecyl Tetradecyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, and the like. The alkyl group of the alkyl (meth) acrylate monomer may be linear, branched or cyclic.

The acrylic polymer used in the pressure-sensitive adhesive composition of the present embodiment may be copolymerized with (B) at least one copolymerizable vinyl monomer containing a hydroxyl group and / or a carboxyl group as an optional component. (B) a copolymerizable vinyl monomer containing a hydroxyl group and / or a carboxyl group is preferably selected from the group consisting of a copolymerizable monomer containing a hydroxyl group (a hydroxyl group-containing monomer) and a copolymerizable monomer containing a carboxyl group (a carboxyl group-containing monomer) At least one of them may be mentioned. That is, either the hydroxyl group-containing monomer or the carboxyl group-containing monomer may be selected and copolymerized, or both the hydroxyl group-containing monomer and the carboxyl group-containing monomer may be copolymerized.

(B) 0.1 to 5 parts by weight of a total of at least one copolymerizable vinyl monomer containing a hydroxyl group and / or a carboxyl group, based on 100 parts by weight of the total of (A) and (C) , More preferably 0.1 to 4.2 parts by weight, particularly preferably 0.1 to 2.8 parts by weight.

Examples of the hydroxyl group-containing monomer include 8-hydroxyhexyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxyethyl (Meth) acrylate, N-hydroxy (meth) acrylamide, N-hydroxymethyl (meth) acrylamide and N-hydroxyethyl . The proportion of the hydroxyl group-containing monomer contained in the pressure-sensitive adhesive composition of the present embodiment is preferably 0.1 to 5 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the total of the components (A) and (C) More preferably 4.2 parts by weight, and particularly preferably 0.1 to 2.8 parts by weight.

Examples of the carboxyl group-containing monomer include (meth) acrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, 2- (meth) acryloyloxyethylhexahydrophthalic acid, 2- (Meth) acryloyloxyethylmaleic acid, 2- (meth) acryloyloxyethylphthalic acid, 2- (meth) acryloyloxyethylsuccinic acid, 2- (meth) acryloyloxyethylmaleic acid, carboxypolycaprolactone mono (Meth) acrylate, 2- (meth) acryloyloxyethyltetrahydrophthalic acid, and the like. The proportion of the carboxyl group-containing monomer in the pressure-sensitive adhesive composition according to the present embodiment is preferably 0 to 5.0 parts by weight based on 100 parts by weight of the total of the components (A) and (C) in the acrylic polymer (when the carboxyl group- More preferably in a range of 0.1 to 2.4 parts by weight, particularly preferably in a proportion of 0.1 to 1.2 parts by weight, in the case of copolymerizing a carboxyl group-containing monomer, desirable.

The acrylic polymer used in the pressure-sensitive adhesive composition of this embodiment may be copolymerized with a copolymerizable vinyl monomer (C) containing an aromatic group as an optional component. Examples of the copolymerizable vinyl monomer containing (C) an aromatic group include benzyl (meth) acrylate, naphthyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxybutyl (Meth) acrylate, 6 (1-naphthyloxy) ethyl (meth) acrylate, 2- At least one (meth) acrylate such as - (2-naphthyloxy) hexyl (meth) acrylate, 8- (1-naphthyloxy) More than species. When a copolymerizable vinyl monomer containing an aromatic group contains a (meth) acrylate monomer containing an aromatic group, it is preferable because it is excellent in copolymerization with an alkyl (meth) acrylate monomer.

The method for producing the acrylic polymer to be contained in the pressure-sensitive adhesive composition according to the present embodiment is not particularly limited, and a well-known polymerization method such as a solution polymerization method or an emulsion polymerization method can be used. It is preferable that the pressure-sensitive adhesive composition according to the present embodiment has a weight average molecular weight of 100 to 3,000,000 of the copolymer of the acrylic polymer to be used.

The pressure-sensitive adhesive composition according to the present embodiment contains (G) an antistatic agent to obtain an antistatic property. (G) The antistatic agent is an ionic compound composed of a cation and an anion having a melting point of 25 ° C or higher, and the anion is a trifluoromethanesulfonate anion (CF ₃ SO ₃ ^- ), a pentafluoroethanesulfonate anion (CF ₃ CF ₂ SO ₃ ^- ), heptafluoropropane sulfonate anion (CF ₃ CF ₂ CF ₂ SO ₃ ^- ), and nonafluorobutane sulfonate anion (CF ₃ CF ₂ CF ₂ CF ₂ SO ₃ ^- ). It is a species. The pressure-sensitive adhesive composition according to this embodiment preferably contains (G) an antistatic agent as an essential component in a proportion of 0.01 to 10 parts by weight based on 100 parts by weight of the acrylic polymer, further enhancing the antistatic property of the pressure- It is more preferable to contain the antistatic agent (G) in a proportion of from 0.01 to 15 parts by weight, in order to reduce the lower limit value of the antistatic agent to 1.0 x 10 ^{+ 10} ? /? Or less.

Examples of the cation included in the ionic compound include pyridinium, imidazolium, phosphonium, sulfonium, pyrrolidinium, guanidinium, ammonium, isooronium, thiouronium, piperidinium, paraazolium, methyl Potassium, lithium, and morpholinium.

Specific examples of the antistatic agent (G) include lithium trifluoromethanesulfonate, lithium nonafluorobutanesulfonate, 1-methyl-3-octylpyridinium trifluoromethanesulfonate salt, 3-methyl-1-octyl Pyridinium trifluoromethanesulfonate salts, 1-methyl-4-octylpyridinium nonafluorobutanesulfonate salts, 4-methyl-1-octylpyridinium nonafluorobutanesulfonate salts, dimethyldioctylammonium pentafluoro 1-methyl-3-octylpyridinium heptafluoropropanesulfonate salt, 3-methyl-1-octylpyridinium heptafluoropropanesulfonate salt, 1-methyl-3-octylpyridinium nonane 3-methyl-1-octylpyridinium nonafluorobutanesulfonate salts, 1-octyl-3-methylimidazolium nonafluorobutanesulfonate salts, and the like.

The pressure-sensitive adhesive composition according to the present embodiment further contains (D) at least one crosslinking agent selected from the group consisting of an isocyanate compound having three or more functional groups and an epoxy compound having two or more functional groups as the crosslinking agent. As the (D) crosslinking agent, an isocyanate compound having three or more functional groups and an epoxy compound having two or more functionalities may be used in combination. (D) a crosslinking agent is preferably 0.01 to 5 parts by weight, more preferably 0.01 to 2 parts by weight, further preferably 0.03 to 0.8 parts by weight, based on 100 parts by weight of the acrylic polymer Particularly preferred.

Examples of the trifunctional or higher isocyanate compound include biuret-modified products of diisocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, tolylene diisocyanate and xylylene diisocyanate, Modified substances, trimethylol propane, and adducts with tri- or higher-valent polyols such as glycerin.

Examples of the bifunctional or higher functional epoxy compound include diglycidyl ether of glycols, diglycidyl ether of bisphenol, triglycidyl ether of triol, diglycidyl ester of dicarboxylic acid, diglycidyl Amines of diallyl substitution, diamines of tetraglycidyl substitution, and the like.

The pressure-sensitive adhesive composition according to the present embodiment further contains (H) a silane coupling agent. (H) The silane coupling agent includes a compound having at least one organic functional group and at least one hydrolyzable group in one molecule, and the hydrolyzable group is an alkoxy group bonded to a silicon atom. (H) The silane coupling agent contains at least one or more functional groups selected from the group consisting of an epoxy group, a mercapto group and an acid anhydride group. (H) The silane coupling agent may use one or both of a monomer type and an oligomer type. The content of the silane coupling agent is, for example, preferably 0.01 to 2.0 parts by weight, more preferably 0.01 to 1.0 part by weight, and particularly preferably 0.01 to 0.5 part by weight, based on 100 parts by weight of the acrylic polymer.

Examples of the silane coupling agent having an epoxy group include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethylmethyldimethoxysilane, 2- (3,4- Epoxycyclohexyl) ethylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 5,6-epoxyhexyltrimethoxysilane, 5,6-epoxyhexylmethyldimethoxysilane, 5 , 6-epoxyhexylmethyldiethoxysilane, and 5,6-epoxyhexyltriethoxysilane.

Examples of the silane coupling agent having a mercapto group include 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldiethoxysilane, 3-mercur Mercaptopropyltriethoxysilane, 2-mercaptopropyltriethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, and the like.

Examples of the silane coupling agent having an acid anhydride group include 3-trimethoxysilylpropylsuccinic anhydride, 3-triethoxysilylpropylsuccinic anhydride, 3-dimethylmethoxysilylpropylsuccinic anhydride, 3-dimethyl 3-trimethoxysilylpropylcyclohexyldicarboxylic acid anhydride, 3-triethoxysilylpropylcyclohexyldicarboxylic acid anhydride, 3-dimethylmethoxysilylpropylcyclohexyldicarboxylic anhydride, 3-trimethoxysilylpropylcyclohexyldicarboxylic acid anhydride, , 3-dimethylethoxysilylpropylcyclohexyldicarboxylic acid anhydride, 3-trimethoxysilylpropylphthalic anhydride, and 3-triethoxysilylpropylphthalic anhydride.

An oligomerized alkoxy oligomer (alkoxy oligomer containing an alkoxy group) and the like can also be used as a silane coupling agent.

The silicone alkoxy oligomer may be, for example, a silicone alkoxy having a molecular weight of 600 or more and less than 3,000 and having a molecular weight of less than 3000 such as tetraalkoxysiloxane, trialkoxysiloxane, dialkoxysiloxane blocked with an alkoxysilyl group represented by Si- It is preferable to use an oligomer.

The pressure-sensitive adhesive composition of the present embodiment is not limited to the above-described additives, but may be appropriately blended with known additives such as an antioxidant, a surfactant, a curing accelerator, a plasticizer, a filler, a curing retarder, a processing aid and an antioxidant. These may be used alone or in combination of two or more.

The pressure-sensitive adhesive layer to which the pressure-sensitive adhesive composition of the present embodiment is crosslinked preferably has a pressure-sensitive adhesive layer having a surface resistivity of 1.0 x 10 ^{+ 12} ? /? Or less and more preferably a surface resistivity of 5.0 x 10 ^{+ 11} ? /? Particularly preferably 2.0 x 10 < ^{+ 11} > If the surface resistivity is large, the performance of releasing static electricity caused by charging when the pressure-sensitive adhesive layer is peeled off from the adherend is deteriorated. Therefore, by sufficiently reducing the surface resistivity of the pressure-sensitive adhesive layer, the peeling electrification voltage caused by the static electricity generated when the pressure-sensitive adhesive layer is peeled from the adherend can be reduced, and the influence on the adherend can be suppressed.

The pressure-sensitive adhesive composition of the present embodiment was obtained by bonding a pressure-sensitive adhesive layer having a thickness of 20 占 퐉 in which a pressure-sensitive adhesive composition was crosslinked to a polarizing plate having a total thickness of 80 占 퐉. The adhesive force of the pressure- Mm or less, and after the durability test at 105 ° C x 500 hr, neither foaming nor peeling occurs. The adhesive force of the pressure-sensitive adhesive layer having a thickness of 20 탆 to the alkali-free glass is preferably 1 N / 25 mm or more and 6 N / 25 mm or less, more preferably 1.5 N / 25 mm or more and 6 N / 25 mm or less.

The pressure-sensitive adhesive layer according to the present embodiment can be obtained by applying the pressure-sensitive adhesive composition of the present embodiment to a substrate such as a resin film or a release film, and then crosslinking the pressure-sensitive adhesive composition.

When the pressure-sensitive adhesive layer according to the present embodiment is used for bonding an optical member, it is necessary to reduce the reflection of light rays at the interface between the pressure-sensitive adhesive layer and the optical member. That is, the refractive index difference between the optical member and the pressure-sensitive adhesive layer is preferably as small as possible. Therefore, the refractive index of the pressure-sensitive adhesive layer is preferably 1.47 to 1.50.

The adhesive film according to the present embodiment can be produced by forming the pressure-sensitive adhesive layer according to the present embodiment on one side of a substrate such as a resin film or a release film. As the substrate of the resin film or the release film (separator), a polyester film or the like can be used. The releasing film may be subjected to releasing treatment by a silicone-based or fluorine-releasing agent or the like on the side of the pressure-sensitive adhesive layer to be combined with the pressure-sensitive adhesive surface. In the resin film to be the base material of the pressure-sensitive adhesive film according to the present embodiment, an anti-fouling treatment with a silicon type or fluorine type releasing agent, a coating agent, a fine silica particle, or the like is applied to the side opposite to the side where the pressure- It is possible to perform the antistatic treatment. The thickness of the pressure-sensitive adhesive layer of the pressure-sensitive adhesive film according to the present embodiment is preferably, for example, from 1 m to 25 m, more preferably from 3 m to 20 m, The thickness is particularly preferred.

The pressure-sensitive adhesive film according to the present embodiment may be configured as a "release film / pressure-sensitive adhesive layer / release film" by aligning the surfaces of the pressure-sensitive adhesive layers on both sides of the release film. In this case, by releasing the releasing films on both sides sequentially or simultaneously to expose the adhesive surface, it becomes possible to bond the optical member with an optical member such as an optical film. Examples of the optical film include a polarizing film, a retardation film, an antireflection film, an antiglare film, an ultraviolet absorbing film, an infrared absorbing film, an optical compensating film, and a brightness improving film. Examples of the device to which the optical member is applied include a liquid crystal panel, an organic EL panel, and a touch panel.

The pressure-sensitive adhesive film according to the present embodiment is preferable as a pressure-sensitive adhesive film for a polarizing plate. An optical film with a pressure-sensitive adhesive layer in which the pressure-sensitive adhesive layer is laminated on at least one surface of the optical film. Further, by using the above-mentioned pressure-sensitive adhesive film on one surface of the polarizing plate, a polarizing plate with a pressure-sensitive adhesive layer can be provided. The liquid crystal panel can be provided by using the optical film with the pressure-sensitive adhesive layer.

Specific examples of the lamination structure of the optical film with a pressure-sensitive adhesive layer include "releasing film / pressure-sensitive adhesive layer / optical film", "releasing film / pressure-sensitive adhesive layer / optical film / pressure-sensitive adhesive layer / release film" Film "," optical film / pressure-sensitive adhesive layer "and" pressure-sensitive adhesive layer / optical film / pressure-sensitive adhesive layer ". Sensitive adhesive layer / polarizer / polarizer / pressure-sensitive adhesive layer / release film "," polarizer / pressure-sensitive adhesive layer "," pressure-sensitive adhesive layer / polarizer plate " / Pressure-sensitive adhesive layer " As a partial structure of a liquid crystal panel or the like, an optical film with a pressure-sensitive adhesive layer or a polarizer with a pressure-sensitive adhesive layer may be introduced.

On the other hand, when the release film is included in the lamination structure such as "releasing film / pressure-sensitive adhesive layer / optical film", "releasing film / pressure-sensitive adhesive layer / polarizing plate", the release film is peeled off, The polarizing plate is adhered to the adherend.

Example

Hereinafter, the present invention will be described in detail by way of examples.

≪ Preparation of acrylic polymer &

[Example 1]

Nitrogen gas was introduced into a reactor equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen inlet tube to replace the air in the reactor with nitrogen gas. Thereafter, 50 parts by weight of butyl acrylate, 10 parts by weight of methyl acrylate, 20 parts by weight of 2-ethylhexyl acrylate, 1.0 part by weight of 6-hydrohexyl acrylate, and 0.5 part by weight of 4-hydroxybutyl acrylate And 100 parts by weight of a solvent (ethyl acetate) were added together with 20 parts by weight of benzyl acrylate. Thereafter, 0.1 part by weight of azobisisobutyronitrile as a polymerization initiator was added dropwise over 2 hours and reacted at 65 DEG C for 8 hours to obtain an acrylic polymer solution of Example 1. [

[Examples 2 to 6 and Comparative Examples 1 to 3]

The acrylic polymer solution used in Examples 2 to 6 and Comparative Examples 1 to 3 was obtained in the same manner as in the acrylic polymer solution used in Example 1 except that the compositions of the monomers were changed as shown in Table 1, respectively.

≪ Preparation of pressure-sensitive adhesive composition and pressure-sensitive adhesive film &

[Example 1]

To the acrylic polymer solution of Example 1 prepared as described above, 0.1 part by weight of D-110N and 0.01 part by weight of TX were used as a crosslinking agent, and 1-methyl-3-octylpyridinium nonafluorobutanesulfonate 1.5 parts by weight of a salt, 0.1 parts by weight of KBM-403 as a silane coupling agent and 0.1 parts by weight of X-41-1805 were added and stirred to obtain a pressure-sensitive adhesive composition of Example 1. This pressure-sensitive adhesive composition was coated on a releasing film made of a polyethylene terephthalate (PET) film coated with a silicone resin and dried at 90 DEG C to remove the solvent to obtain a pressure-sensitive adhesive layer having a thickness of 20 mu m. Thereafter, the pressure-sensitive adhesive layer obtained by crosslinking the pressure-sensitive adhesive composition on one side of the release film was aged under an atmosphere of 23 ° C and 50% RH for 7 days to obtain a pressure-sensitive adhesive film of Example 1 which is a constitution of a release film / pressure- ≪ / RTI >

[Examples 2 to 6 and Comparative Examples 1 to 3]

The pressure-sensitive adhesive films of Examples 2 to 6 and Comparative Examples 1 to 3 were obtained in the same manner as in the pressure-sensitive adhesive film of Example 1 except that the composition of the additives was changed as shown in Table 1, respectively.

In Table 1, the parts by weight of each component are the sum of (A) at least one alkyl (meth) acrylate monomer having C1-C14 carbon atoms in the alkyl group and (C) a total of at least one copolymerizable vinyl monomer containing an aromatic group Was determined as 100 parts by weight.

In Table 1, in the columns (D), (H), and (G) in Table 1, the acrylic polymer was used in an amount of 100 parts by weight and the content ratio (parts by weight) of each component was expressed by numerical values in brackets.

Table 2 shows the compound names of the weak symbols of the respective components used in Table 1. G-1 to G-7 are all ionic compounds having a melting point of 25 占 폚 or more and being solid at 25 占 폚.

D-110N, D-127N and Takenate (registered trademark) D-140N are trade names of Mitsui Chemicals, Inc., and TETRAD (trade name) is a trade name of Coronate HX, Coronate HL and Coronate L, (Registered trademark) -X is a trade name of Mitsubishi Gas Chemical Co., Also, HDI means hexamethylene diisocyanate, IPDI means isophorone diisocyanate, XDI means xylylene diisocyanate, TDI means tolylene diisocyanate, and TMP means trimethylol propane. KBM-403, X-12-967C and X-41-1805 are all trade names of Shin-Etsu Chemical Co.,

<Test Method and Evaluation>

The pressure-sensitive adhesive films of Examples 1 to 6 and Comparative Examples 1 to 3 were each aged for 7 days under an atmosphere of 23 ° C and 50% RH, and then evaluated by the following test methods.

<Test Method of Adhesive Force>

One release film was peeled from the pressure-sensitive adhesive films of Examples 1 to 6 and Comparative Examples 1 to 3 to expose one side of the pressure-sensitive adhesive layer of the pressure-sensitive adhesive film. Thereafter, the pressure-sensitive adhesive film was laminated on one side of a polarizing plate (resin film; polarizing plate having a polarizing protective layer of TAC was used) having a thickness of 80 占 퐉 and the pressure-sensitive adhesive film was laminated thereon to form a releasing film / pressure-sensitive adhesive layer / Sensitive adhesive layer-containing polarizer. Further, the release film of the polarizing plate with a pressure-sensitive adhesive layer was peeled off, and a polarizing plate with a pressure-sensitive adhesive layer was bonded to the surface washed with acetone of an alkali-free glass (Eagle XG manufactured by Corning Incorporated) with the pressure-sensitive adhesive layer therebetween. Thereafter, the test piece was autoclaved under the conditions of 50 占 폚 and 0.5 MPa 占 20 minutes. Thereafter, the film was returned to an atmosphere of 23 ° C × 50% RH and the peel strength of the polarizing plate with a pressure-sensitive adhesive layer after 1 hour was measured by a tensile tester in accordance with JIS Z0237 "Test method for pressure-sensitive adhesive tape and pressure- At a speed of 0.3 m / min as the adhesive strength of the pressure-sensitive adhesive layer to the alkali-free glass.

<Test Method of Surface Resistivity>

After the adhesive film was aged, the release film was peeled off before being adhered to the adherend to expose the pressure-sensitive adhesive layer, and the surface resistivity of the pressure-sensitive adhesive layer was measured using a resistivity meter Hirestr UP-HT450 (manufactured by Mitsubishi Chemical Engineering Co., Ltd.) .

<Test method of durability>

The releasing film of the 10 cm-square pressure-sensitive adhesive layer polarizing plate was peeled off in the same manner as in the measurement of the adhesive force, and was attached to a surface cleaned with acetone of an alkali-free glass to prepare a test piece. Thereafter, the test piece was subjected to a durability test under a test environment of 105 DEG C x 500 hr, taken out under an atmosphere of 23 DEG C x 50% RH, and after one hour, the state of the pressure sensitive adhesive layer was visually observed to evaluate the durability of the pressure- Respectively. The evaluation criteria of durability were "?" When the pressure-sensitive adhesive layer was not completely peeled or peeled, "?" When the pressure-sensitive adhesive layer was foamed or peeled in a part of the pressure-sensitive adhesive layer, Was evaluated as &quot; x &quot;.

Table 3 shows the evaluation results of the pressure-sensitive adhesive films in Examples 1 to 6 and Comparative Examples 1 to 3. The &quot; surface resistivity &quot; is represented by a method (m is an arbitrary real number value and n is a positive integer) in which "m x 10 ^{+ n} " is set to "mE + n".

The pressure-sensitive adhesive films of Examples 1 to 6 were obtained in the same manner as in Examples 1 to 6 except that the pressure-sensitive adhesive layer had a surface resistivity of 1.0 x 10 ^{+ 12} ? /? Or less and an adhesive force of 20 占 퐉 for the non- It was excellent in durability as well as excellent in adhesion and antistatic performance without foaming and peeling even after the durability test of 500 hours.

That is, the evaluation results shown in Table 3 for the adhesive films of Examples 1 to 6 demonstrate that the problems of the present invention can be solved.

The adhesive film of Comparative Example 1 as (G) an antistatic agent contained in the pressure-sensitive adhesive composition, PF ₆ ^-, since the ionic compound is used with an anion having a high surface resistivity of the pressure-sensitive adhesive layer was bad durability.

In the pressure-sensitive adhesive film of Comparative Example 2, the glass transition temperature of the acrylic polymer contained in the pressure-sensitive adhesive composition was 0 deg. C (+ 4.8 deg. C in calculation). For this reason, the adhesive property is poor and the adhesive force is excessive, the surface resistivity of the pressure-sensitive adhesive layer is high, and the durability is bad. On the other hand, in the acrylic polymer used in Comparative Example 2, the proportion of methyl acrylate and acrylic acid having a high glass transition temperature (higher than 0 ° C) of the homopolymer was high.

In the pressure-sensitive adhesive film of Comparative Example 3, since the pressure-sensitive adhesive composition was not blended with the (H) silane coupling system (G) antistatic agent, the pressure-sensitive adhesive film was excessive, and the surface resistivity of the pressure-sensitive adhesive layer was high and durability was poor.

As described above, the problems of the present invention were not solved in the adhesive films of Comparative Examples 1 to 3.

Claims (11)

A pressure-sensitive adhesive composition containing an acrylic polymer, an antistatic agent, and (D) a crosslinking agent,
Wherein the acrylic polymer has a glass transition temperature of 0 DEG C or lower,
Wherein the crosslinking agent (D) is at least one crosslinking agent selected from the group consisting of an isocyanate compound having three or more functional groups and an epoxy compound having two or more functional groups,
Wherein the pressure-sensitive adhesive composition further comprises (H) a monomer type or oligomer type silane coupling agent containing at least one functional group selected from the group consisting of an epoxy group, a mercapto group and an acid anhydride group,
Wherein the antistatic agent is an ionic compound having a melting point of not lower than 25 占 폚, which is composed of a cation and an anion, and the anion is a trifluoromethanesulfonate anion, a pentafluoroethanesulfonate anion, a heptafluoropropanesulfonate anion, A cationic anion, and a cationic anion,
Wherein the antistatic agent is contained in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the acryl-based polymer as an essential component. The method according to claim 1,
The acrylic polymer
(A) at least one alkyl (meth) acrylate monomer having an alkyl group having from 1 to 14 carbon atoms,
(B) at least one copolymerizable vinyl monomer containing a hydroxyl group and / or a carboxyl group,
(C) at least one copolymerizable vinyl monomer containing an aromatic group, wherein the copolymer is an acrylic polymer,
The total amount of at least one copolymerizable vinyl monomer containing a hydroxyl group and / or a carboxyl group (B) in an amount of 0.1 to 5 parts by weight relative to 100 parts by weight of the total of the components (A) and (C) ,
A pressure-sensitive adhesive layer having a thickness of 20 占 퐉 in which the pressure-sensitive adhesive composition was crosslinked was laminated to a polarizing plate having a total thickness of 80 占 퐉. The pressure-sensitive adhesive layer having a thickness of 20 占 퐉 had an adhesive force of 6N / Lt; RTI ID = 0.0 &gt; 105 C &lt; / RTI &gt; x 500 hr. 3. The method according to claim 1 or 2,
Wherein the cation is selected from the group consisting of pyridinium, imidazolium, phosphonium, sulfonium, pyrrolidinium, guanidinium, ammonium, isooronium, thiouronium, piperidinium, parazolium, methylium, lithium, Wherein the pressure-sensitive adhesive composition is a pressure-sensitive adhesive composition. The method according to claim 1 or 2, wherein
Wherein the pressure-sensitive adhesive layer crosslinked with the pressure-sensitive adhesive composition has a surface resistivity of 1.0 x 10 ^& lt ^{; 12} &gt; 3. The method of claim 2,
Wherein the (B) copolymerizable vinyl monomer containing a hydroxyl group and / or a carboxyl group is at least one or more selected from the group consisting of a copolymerizable monomer containing a hydroxyl group and a copolymerizable monomer containing a carboxyl group,
(Meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (Meth) acrylate, N-hydroxy (meth) acrylamide, N-hydroxymethyl (meth) acrylamide and N-hydroxyethyl
Wherein the copolymerizable monomer containing a carboxyl group is at least one selected from the group consisting of (meth) acrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, 2- (meth) acryloyloxyethylhexahydrophthalic acid, 2- (Meth) acryloyloxyethylmaleic acid, 2- (meth) acryloyloxyethylphthalic acid, 2- (meth) acryloyloxyethylsuccinic acid, 2- (meth) acryloyloxyethylmaleic acid, carboxypolycaprolactone Wherein the pressure-sensitive adhesive composition is at least one selected from the group consisting of mono (meth) acrylate and 2- (meth) acryloyloxyethyl tetrahydrophthalic acid. Wherein a pressure-sensitive adhesive layer formed by crosslinking the pressure-sensitive adhesive composition of claim 1 or 2 is laminated on one side of the resin film. An optical film with a pressure-sensitive adhesive layer, wherein a pressure-sensitive adhesive layer formed by crosslinking the pressure-sensitive adhesive composition of claim 1 or 2 is laminated on at least one surface of the optical film. The method according to claim 6,
Wherein an antistatic treatment and an antifouling treatment are carried out on one surface of the resin film opposite to the surface on which the pressure-sensitive adhesive layer is laminated. A pressure-sensitive adhesive film for a polarizing plate, wherein the pressure-sensitive adhesive film of claim 6 is used. Wherein the pressure-sensitive adhesive layer formed by crosslinking the pressure-sensitive adhesive composition of claim 1 or 2 is laminated on one surface of the release film in a thickness of 1 to 25 μm and is constituted of a release film / pressure-sensitive adhesive layer / release film film. A liquid crystal panel characterized in that the optical film with a pressure-sensitive adhesive layer of claim 7 is used.