KR20080047031A - Antistatic pressure sensitive adhesive composition comprising sulfone or sulfoxide, and polarized plate comprising the same - Google Patents

Abstract

An antistatic adhesive composition, a polarizer containing an adhesive layer formed by using the composition, and an LCD device containing the polarizer are provided to lower manufacturing cost and to improve antistatic property. An antistatic adhesive composition comprises 100 parts by weight of an acrylate copolymer having a crosslinkable functional group at the side chain; 1-10 parts by weight of a crosslinking agent; 0.01-1 parts by weight of a silane coupling agent; and 0.5-15 parts by weight of a sulfone or sulfoxide compound. Preferably the sulfone or sulfoxide compound is represented by the formula 1, wherein n is 1 or 2; R1 and R2 are independently an aryl group substituted or unsubstituted with at least one group selected from the group consisting of a halogen atom, a C1-C5 alkyl or alkoxy group substituted or unsubstituted with a halogen atom or a hydroxyl group, a nitro group, a hydroxyl group, an amino group and an azido group, or a C1-C20 hydrocarbon group substituted or unsubstituted with a halogen atom, a hydroxyl group, an amine group, a carboxyl group, an aryl group, an alkoxy group, an alkylthio group or a trialkylsilyl group; or R1 and R2 can be combined to form a ring.

Description

Antistatic pressure-sensitive adhesive composition comprising a sulfone or sulfoxide compound and a polarizing plate comprising the same {Antistatic pressure sensitive adhesive composition comprising sulfone or sulfoxide, and polarized plate comprising the same}

The present invention relates to an antistatic pressure-sensitive adhesive composition and a polarizing plate including the same, and more particularly, to an antistatic pressure-sensitive adhesive composition to which a sulfone or a sulfoxide compound is added to give an antistatic performance to the pressure-sensitive adhesive and a polarizing plate including the same.

In general, in order to manufacture a liquid crystal display device, a liquid crystal cell and a polarizing plate containing a liquid crystal are basically required, and an appropriate adhesive layer or adhesive layer for bonding them should be used. The polarizing plate is stretched in a predetermined direction, and in order to protect both sides of PVA, which is a polarizing film (or polarizer) dyed with an iodine compound or a dichroic polarizing material, one side of a triacetyl cellulose (TAC) -based protection A film is laminated, and an antistatic layer, a reflective ring layer, a hard coating layer, etc. are laminated thereon, and a protective film made of a triacetyl cellulose film or a polymer of a cyclic olefin is formed on the opposite side, and an adhesive layer and a release film are formed thereon. The multilayered structure is laminated.

In manufacturing a liquid crystal display, when the release film is peeled from the pressure-sensitive adhesive layer in the process of attaching the polarizing plate to the liquid crystal cell, static electricity is generated. The generated static electricity affects the alignment of the liquid crystal inside the liquid crystal display, thereby preventing defects. It causes the contamination by foreign matter between the liquid crystal cell and the adhesive by the electrostatic attraction.

In order to solve the problem caused by the static electricity, generally in forming an adhesive layer on the protective film, a method using a conductive adhesive with a conductive material added to the adhesive, an antistatic layer by applying a conductive material between the polarizing plate and the adhesive layer As the method for forming the polymer and the polymer added as the pressure-sensitive adhesive composition, a method using an ionic acrylate copolymer is used.

Hereinafter, a method of imparting antistatic property to the flat plate will be described in detail.

First, a method of imparting antistatic properties by adding a conductive material to the pressure-sensitive adhesive layer is a method of adding a material having a conductive component such as a conductive polymer, metal oxide particles, or carbon particles, an ionic material such as a metal salt or a surfactant. Is added to the pressure-sensitive adhesive (Korean Patent Publication No. 10-1998-0081608, Korean Patent Publication No. 10-1989-00133673, Korean Patent Publication No. 10-2001-0111715, Korean Patent Publication Korean Patent Publication No. 10-2004-0032058, Korean Patent Publication No. 10-2006-0018495, Korean Patent Publication No. 10-2004-0030919, Korean Patent Publication No. 10-2001-0010433, Korean Patent Publication 10-2005-0072576, Japanese Patent Laid-Open No. 2006-111856, Japanese Patent Laid-Open No. 2006-111846, and Japanese Patent Laid-Open No. 2006-104434).

However, when the conductive polymer, the metal oxide or the carbon particles are added, a large amount must be added in order to impart antistatic properties, thereby reducing transparency. In addition, the addition of the surfactant is susceptible to humidity, and has the disadvantage of lowering the adhesive properties by the transfer to the pressure-sensitive adhesive surface. As another method, there have been attempts to add ethylene oxide-modified dioctyl phthalate plasticizer to the inside of the pressure-sensitive adhesive to provide flexibility and to suppress static electricity generation. However, the addition of such a plasticizer alone is not only difficult to suppress the generation of static electricity generated initially, it is also difficult to dissipate the static electricity remaining after peeling off the release film.

Second, a method of forming an antistatic layer by applying a conductive material between the polarizing plate and the pressure-sensitive adhesive layer is a method of depositing an electrically conductive metal powder or metal oxide, coating a conductive polymer or the like. However, such a method requires an additional step of stacking an antistatic layer in imparting antistatic performance to a polarizing plate having a multilayer structure, and thus, there is a problem that the process becomes complicated and causes an increase in unit cost (Korean Patent Publication No. 10). -1997-7002906, Korean Patent Publication No. 10-2005-0036310, Japanese Patent Publication No. 2006-095875, Japanese Patent Publication No. 2006-095874, Japanese Patent Publication No. 2006-076251, Japanese Patent Japanese Patent Laid-Open No. 2005-271573, Japanese Patent Laid-Open No. 2005-238651, Japanese Patent Laid-Open No. 2005-200607, Japanese Patent Laid-Open No. 11-091038, Japanese Patent Laid-Open No. 04-304921, Japanese Patent Laid-Open 10-114886).

Third, in addition to the above two methods, no additional coating process is required, and as a method for preventing the conductive material from bleeding out from the pressure-sensitive adhesive, a method of immobilizing an ionic material in a polymer as the pressure-sensitive adhesive composition has been proposed. Specifically, Korean Patent Publication No. 10-2001-0111715 prepares a polymer containing an epoxy group, adds a tertiary amine to an epoxy group to introduce a quaternary ammonium salt, and a polymer containing a tertiary amine. And a method of introducing quaternary ammonium salts by reacting dimethylsulfate with tertiary amines. However, when an excessive amount of epoxy groups or tertiary amines are introduced into the polymer in order to exhibit sufficient antistatic properties, there is a possibility that the physical properties inherent to the pressure-sensitive adhesive may be damaged.

The method of adding a conductive material to the pressure-sensitive adhesive composition of the above-mentioned methods of imparting antistatic properties to the polarizing plate will be described in more detail. 1) Conductive polymers (polythiophene, polypyrrole, polyamyline) When used, there is a problem of being opaque when using a large amount to improve the antistatic properties in addition to the problem that the added conductive polymer is expensive, 2) when using a metal salt, there is a problem of low solubility in the pressure-sensitive adhesive solution, 3) using organic salts There is also a problem of solubility, and when using a weakly coordinated anion and quaternary ammonium salts, phosphonium salts, sulfonium salts, etc., there is a problem of being expensive. 4) In the case of using a metal oxide, it is difficult to control the size of the dispersed particles, and there is a fear of birefringence, which is not preferable for the polarizing plate.

The present inventors have endeavored to solve the above problems of the prior art, and have completed the present invention by finding a conductive material having low cost and high solubility in the pressure-sensitive adhesive composition.

Therefore, an object of the present invention is to provide a pressure-sensitive adhesive composition having a low manufacturing cost, simple manufacturing, and excellent antistatic performance and a polarizing plate including the same.

The present invention relates to an antistatic pressure-sensitive adhesive composition comprising an acrylate copolymer having a crosslinkable functional group in the side chain, a crosslinking agent, a silane coupling agent and a sulfone or sulfoxide compound.

Preferred embodiments of the sulfone or sulfoxide compound may be represented by the following formula (1).

Wherein n is 1 or 2;

R1 and R2 are each independently selected from the group consisting of C1-C5 alkyl substituted or unsubstituted with halogen, halogen or hydroxy group, C1-C5 alkoxy, nitro, hydroxy, amino and azido groups unsubstituted or substituted with halogen or hydroxy group. Aryl unsubstituted or substituted with one or more substituents selected; Or a C 1-20 hydrocarbon unsubstituted or substituted with halogen, hydroxy, amine, carboxy, aryl, alkoxy, alkylthio or trialkylsilyl; Or R 1 and R 2 combine as substituents as defined above to form a ring.

Preferably, R1 and R2 are each independently substituted or unsubstituted C1-C5 alkyl, substituted or unsubstituted C1-C5 alkyl, halogen or hydroxy-substituted or unsubstituted C1-C5 alkoxy, nitro, hydroxy, amino and azido groups Phenyl unsubstituted or substituted with one or more substituents selected from the group consisting of; Or a C 1 to C 20 hydrocarbon unsubstituted or substituted with halogen, hydroxy, amine, carboxy, aryl, alkoxy, alkylthio or trialkylsilyl, more preferably phenyl or vinyl.)

The sulfone or sulfoxide compound of Formula 1, as represented by the following Formula 2, does not have an ionic bond in the molecule, and is composed of all covalent bonds, and includes a partial positive charge and a partial negative charge, thereby showing conductivity.

The acrylate copolymer having a crosslinkable functional group in the side chain used in the present invention is, for example, an alkyl (meth) acrylate monomer having 4 to 12 carbon atoms, a polymerizable monomer having a crosslinkable functional group in the side chain, and, if necessary, And alkyl (meth) acrylate copolymers containing other monomers.

In the present invention, (meth) acryl refers to methacryl or acryl.

As said C4-C12 alkyl (meth) acrylate monomer, (meth) acrylate derived from a C4-C12 aliphatic alcohol, ie, n-butyl (meth) acrylate and 2-butyl (meth) acryl Late, t-butyl (meth) acrylate, pentyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, Usyl (meth) acrylate, etc., or a mixture thereof is mentioned. Of these, n-butyl acrylate, 2-ethylhexyl acrylate or a mixture thereof is preferred.

The polymerizable monomer which has a crosslinkable functional group in said side chain is a polymerizable monomer which has a carboxylic acid group, for example, monovalent acid, such as (meth) acrylic acid and crotonic acid, divalent acid, such as maleic acid, itaconic acid, and fumaric acid, Monoalkyl ester of such a diacid, 3- (meth) acryloyl propionic acid, a zucchini anhydride ring-opening adduct to 2-hydroxyalkyl (C2-3) (meth) acrylate, polyoxyalkylene (C2-C2) 4) Succinic anhydride ring-opening adduct to glycol mono (meth) acrylate, the compound which ring-opened and added amber acid anhydride to the caprolactone adduct to 2-hydroxyalkyl (C2-3) (meth) acrylate, etc .; Monomer which has a hydroxy group, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, polyoxyalkylene (C2-C2) 4) glycol mono (meth) acrylate and the like; Or a monomer having an amide group, such as (meth) acrylamide or the like; The monomer which has a tertiary amine group, for example, N, N- dimethylamine ethyl (meth) acrylate, etc. are mentioned. Among these, the "monomer which has a carboxylic acid group, the monomer which has a hydroxy group, or the polymerizable monomer which has an amide group is preferable, and acrylic acid, 2-hydroxyethyl (meth) acrylate, or (meth) acrylamide is especially preferable.

In addition, with said other monomer, For example, a C1-C3 alkyl (meth) acrylate monomer, ie, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, etc. Or; Alkyl (meth) acrylate monomers having 13 to 18 carbon atoms, for example, tridecyl (meth) acrylate, stearyl (meth) acrylate, and the like; (Meth) acrylic acid ester monomers derived from cyclic alcohols such as cyclohexyl (meth) acrylate and the like; (Meth) acrylate monomers derived from aromatic alcohols such as benzyl (meth) acrylate and the like; Aromatic monomers such as styrene, vinyltoluene and the like; Allyl compound monomers such as allyl acetate, and the like; Monomers having a nitrile group such as (meth) acrylonitrile, α-chloro (meth) acrylonitrile and the like; Halogen-containing monomers such as vinyl chloride, vinylidene chloride and the like; Vinyl ester monomers such as vinyl acetate, vinyl propionate and vinyl butyrate; Vinyl ether monomers such as vinyl ethyl ether, vinyl propyl ether, vinyl isobutyl ether and the like. In these, methyl (meth) acrylate is preferable.

The weight ratio of the above-mentioned alkyl (meth) acrylate having 4 to 12 carbon atoms, a polymerizable monomer having a crosslinkable functional group in the side chain, or other monomers is usually (80 to 99.9) :( 1 to 10) :( 0 to 10) It is preferably (90 to 95): (1 to 5): (0 to 5).

When the ratio of the alkyl (meth) acrylate having 4 to 12 carbon atoms is less than 80, the adhesive force is insufficient, and when it exceeds 99, the cohesive force is lowered. Cohesion force falls when the ratio of the polymerizable monomer which has a crosslinkable functional group in a side chain is less than 1, and when it exceeds 10, adhesive force falls. Moreover, when the ratio of another monomer exceeds 10, adhesive force falls.

A well-known crosslinking agent can be added to the adhesive composition of this invention in order to strengthen cohesion force. As this crosslinking agent, a melamine derivative, for example, hexametholol melamine, hexamethoxymethyl melamine, hexabutoxymethyl melamine, etc .; Polyisocyanate compounds such as tolylene diisocyanate, xylene diisocyanate, hexamethylene diisocyanate, diisocyanate compounds such as 2,4- or 4,4-diphenylmethane diisocyanate, and trimisol of diisocyanate Adducts to polyhydric alcohol compounds such as propane; Or polyepoxy compounds such as bisphenol A and epichlorohydrin condensed epoxy compounds, polyglycidyl ethers of polyoxyalkylene polyols, glycerin di- or triglycidyl ethers, tetraglycidyl xylenediamines, and the like. Although it is preferable, it is preferable to use polyisocyanate or a polyepoxy compound. Said crosslinking agent can use together 1 type (s) or 2 or more types.

The crosslinking agent contained in the pressure-sensitive adhesive composition of the present invention is preferably used in an amount of 1 to 10 parts by weight, more preferably 1 to 5 parts by weight, based on 100 parts by weight of the acrylate copolymer solid content having a crosslinkable functional group in the side chain. If it exceeds 10 parts by weight, there is a problem in relieving residual stress due to excessive crosslinking reaction, and if it is less than 1 part by weight, the cohesion force becomes small due to insufficient crosslinking degree, resulting in damage to adhesive durability and cutting properties.

A well-known silane coupling agent can be added to the adhesive composition of this invention. As this silane coupling agent, a silane coupling agent containing an epoxy group is preferable. For example, gamma glycidoxy propyltrimethoxysilane may be used. These epoxy groups in the molecule are bonded to a reactive functional group of the polymer, and an alkoxysilane The part strongly bonds with the glass substrate of the liquid crystal cell, and serves to connect the pressure-sensitive adhesive and the liquid crystal cell, thereby improving adhesion stability and further improving heat and moisture resistance characteristics, and in particular, helping to improve adhesion reliability when left for a long time under high temperature and high humidity. Role.

The content of the silane coupling agent is preferably used in an amount of 0.01 to 1 part by weight based on 100 parts by weight of an acrylate copolymer solid content having a crosslinkable functional group in the side chain. If the content of the silane coupling agent is less than 0.01 part by weight, the adhesive strength with the cell is weak. When 1 weight part is exceeded, there exists a problem that rework property is bad.

Specific examples of the sulfone or sulfoxide compound added as an antistatic substance to the pressure-sensitive adhesive composition of the present invention are as follows.

Specific examples of the sulfone compound include ethyl P-tolyl sulfone, allylphenyl sulfone, bis (4-fluoro-3-nitrophenyl) sulfone, bis (4-fluorophenyl) sulfone, 4-hydroxyphenyl sulfone, 4- Chlorophenylsulfone, 4-fluorophenylmethylsulfone, phenylvinylsulfone, ethylsulfone, methylvinylsulfone, chloromethylphenylsulfone, ethylvinylsulfone, methylthiomethylP-tolylsulfone, phenyltrimethylsilylmethylsulfone, allylphenylsulfone, 4 , 4'-diaminodiphenylsulfone, 3,3'-diazidodiphenylsulfone, bromomethylphenylsulfone, benzylsulfone, 4,4'-dichlorodiphenylsulfone, chloromethyl P-tolylsulfone, phenyl2- ( Triethylsilyl) ethylsulfone, P-tolylsulfone, phenyltribromomethylsulfone, phenyltrans-styrylsulfone, methylsulfone, 2-chloroethylphenylsulfone, P-tolyl2- (triethylsilyl) ethynylsulfone, Phenylsulfone, divinylsulfone, thiophenchalsulfone, disulfone-sulfone, pention-sulfone, porat-sulfone, ethylvinylsulfone, phenamifoss-sulfone, 2- Trophenylphenylsulfone, bis (4- (2-hydroxyethoxy) phenyl) sulfone, O-torridinesulfone, 2-hydroxyethylmethylsulfone, 4-chlorophenylmethylsulfone, 4-bromophenyl methylsulfone, Ethylphenylsulfone, L-methionine sulfone, DL-methionine sulfone, methylphenylsulfone, P-toryl (2- (trimethylsilyl) ethynyl) sulfone, 3-aminophenylsulfone, 4-aminophenylsulfone, butadienesulfone, N-2 2-DNP-DL-methionine sulfone, dibenzothiophenesulfone, 4-fluorophenylsulfone, bis (4-fluoro-3-nitrophenyl) sulfone, methylsulfone, L-methionine sulfone, 2-bromoethyl Sulfone, 4-methoxyphenylmethylsulfone, benzyl2-chloroethylsulfone, 3,4-dichlorophenylmethylsulfone, dibutylsulfone, butylethylsulfone, t-butylphenylsulfone, 4-aminophenylmethylsulfone, tetramethylenesulfone And vinyl sulfones.

Specific examples of the sulfoxide compound include ethylethylthiomethyl sulfoxide, 4-chlorophenyl sulfoxide, methyl sulfoxide, dimethyl sulfoxide, phenyl vinyl sulfoxide, chloromethylphenyl sulfoxide, methylphenyl sulfoxide, benzyl sulfoxide, methyl P -Toryl sulfoxide, Aldikalb sulfoxide, Butokalbo sulfoxide, Sulpropos sulfoxide, Porat sulfoxide, Ethiophene sulfoxide, Disulfone sulfoxide, Clobenside sulfoxide, Hairbufosulfoxide, Dode Silmethyl sulfoxide, L-methionine sulfoxide, DL-methionine sulfoxide, methylmethylthiomethyl sulfoxide, phenylvinyl sulfoxide, butyl sulfoxide, phenyl sulfoxide, benzyl sulfoxide, phenamiphosph sulfoxide, resorcinol Sulfoxide, phenylpropyl sulfoxide, tetramethylene sulfoxide, P-tolyl sulfoxide, diphenyl sulfoxide and the like. The.

In the antistatic adhesive composition of the present invention, it is preferable to use a long chain sulfone or sulfoxide compound having 4 to 30 carbon atoms so as to have a high molecular weight and less movement from the inside of the adhesive to the surface. The amount of the sulfone or sulfoxide compound is preferably 0.5 to 15 parts by weight, more preferably 1 to 10 parts by weight, based on 100 parts by weight of the acrylate copolymer solid content having a crosslinkable functional group in the side chain. When the amount of sulfone or sulfoxide is less than 0.5 part by weight, the antistatic property is lowered, and when it exceeds 15 parts by weight, the transparency is deteriorated.

In this invention, the manufacturing method of the alkyl (meth) acrylate type copolymer which has a crosslinkable functional group in a side chain is well-known superposition | polymerization by well-known superposition | polymerization method (block polymerization, solution polymerization, emulsion polymerization, suspension polymerization, etc.). Initiators (azo-based polymerization initiators such as azobisisobutyronitrile and azobisisovaleronitrile, peroxide-based polymerization initiators such as benzoyl peroxide, di-t-butyl peroxide, and lauryl peroxide), and the like Although it can be prepared using a chain transfer agent (mercapto group-containing chain transfer agent) and the like, preferably prepared by solution polymerization method, the molecular weight of the copolymer is weight average molecular weight (polystyrene) by gel gel permeation chromatography (GPC) method In terms of conversion), it is usually 50,000 to 2,000,000, preferably 100,000 to 1,800,000, and particularly preferably 500,000 to 1,500,000.

The adhesive composition of this invention can be mix | blended and used well-known various additives in the range which does not reduce the function made into the objective of this invention, such as antistatic property, non-pollution property, and adhesive characteristics.

 Examples of the additive include tackifying resins [rosin, rosin derivatives or their hydrogenated bodies, polyterpene resins, terpene phenol resins, xylene resins, styrene resins, coumarone-indene resins, C5 petroleum resins, C9 petroleum resins, Etc.], plasticizers [carboxylic acid esters represented by phthalic acid esters, chlorinated paraffins, etc.], ultraviolet light inhibitors [benzophenone ultraviolet light inhibitors, etc.], mildew agents [copper oxide, phenolic compounds and the like], antifoaming agents [alcohols, silicone compounds Etc.] etc. are mentioned.

The adhesive composition of this invention can be apply | coated directly to a base material or by a transfer method using a normal coating apparatus. In the case of direct coating, triacetyl cellulose or cyclic olefin polymer as a protective film of the polarizing plate can be used as a base material, and as a base material which can be used when applying by transfer method, polyethylene, polypropylene, polyethylene terephthalate, soft polyvinyl chloride Silicone and fluorinated release film can be used for various plastic films, resin plates, etc., but it is preferable to use a silicon release-treated substrate on polyethylene terephthalate.

After coating and drying, if necessary curing (approximately 14 days), the curing is completely cured by the crosslinking reaction between the crosslinking agent and the polymer, thereby exhibiting sufficient adhesion characteristics. Curing conditions, for example, usually proceed for 10 to 20 days at room temperature and 3 to 6 days at 40 to 50 ° C, and can be cured under more severe temperature conditions to shorten the curing time.

The pressure-sensitive adhesive composition of the present invention is not only used as a pressure-sensitive adhesive for polarizing plates, but also for surface and protective tapes or sheets such as electrical and electronic component processing tapes such as dicing tapes and carrier tapes, stainless steel sheets, plastic plates, mats, adhesive labels, stickers, tapes, and the like. It can be used suitably as an adhesive.

The present invention also provides a polarizing plate including the pressure-sensitive adhesive composition as an adhesive layer and a liquid crystal display including the polarizing plate.

The polarizing plate is formed by laminating a protective film on one or both sides of a polarizer (polarizing film). The protective film and polarizer (polarizing film) which comprise a polarizing plate are not specifically limited.

Preferably, for example, a film obtained by incorporating a polarizing component such as iodine or a dichroic dye into a film made of polyvinyl alcohol-based resin, and stretching the film, and the thickness of these polarizers are not particularly limited. It can be formed in a conventional thickness. In this case, the polyvinyl alcohol-based resin may be polyvinyl alcohol, polyvinyl formal, polyvinyl acetal and ethylene, saponified vinyl acetate copolymer.

On one or both sides of the polarizer, a cellulose film such as triacetyl cellulose, a polycarbonate film, a polyester film such as polyethylene terephthalate, a polyether sulfone film, polyethylene, polypropylene, a cyclo or norbornene structure The multilayer film etc. which laminated | stacked protective films, such as a polyolefin type film and polyolefin type films, such as an ethylene-propylene copolymer, can be formed. At this time, the thickness of these protective films is also not particularly limited, and may be formed to a conventional thickness.

In the present invention, the method of forming the pressure-sensitive adhesive layer on the polarizing plate is not particularly limited, and a method of applying and drying the pressure-sensitive adhesive using a bar coater or the like directly on the surface of the polarizing plate, or applying the pressure-sensitive adhesive to the surface of the peelable substrate once and drying The method of transferring the adhesive layer formed on the surface of this peelable base material to the surface of a polarizing plate, and then aging can be applied.

In addition, the polarizing plate of the present invention may be laminated with one or more layers that provide additional functions such as a protective layer, a reflective layer, an antiglare layer, a retardation plate, a wide viewing angle compensation film, and a brightness enhancement film.

The polarizing plate to which the pressure-sensitive adhesive of the present invention is applied can be applied to all conventional liquid crystal display devices, and the kind of the liquid crystal panel is not particularly limited. Preferably, the present invention may comprise a liquid crystal display device including a liquid crystal panel obtained by bonding the pressure-sensitive adhesive polarizing plate to one side or both sides of a liquid crystal cell.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the examples and the like. Hereinafter, "part" shows a weight part and "%" shows the weight%.

Production Example  One: On the side chain Crosslinkable A functional group  Having Alkyl (meth) acrylate type  Preparation of Copolymer

A 4-neck jacketed reactor (1 L) was equipped with a stirrer, a thermometer, a reflux condenser, a dropping lot, and a nitrogen gas inlet tube, 164 parts by weight of ethyl acetate, 126 parts by weight of n-butylacrylic acid, and methyl methacrylate. 10 weight part, 4 weight part of acrylic acid, and 5 weight part of # 2-hydroxyethyl acrylic acid were thrown in, and the reactor external temperature was heated up at 50 degreeC. To 10 parts by weight of ethyl acetate was added dropwise a solution in which 0.14 parts by weight of 2,2'-azobisisobutyronitrile (AIBN) was completely dissolved. After the reaction was continued for another 5 hours while maintaining the jacket outside temperature at 50 ° C, 90 g of ethyl acetate was slowly added dropwise using the dropping lot for 1 hour. Furthermore, after 6 hours of additional stirring at the same temperature, 304 g of ethyl acetate was added, followed by stirring for 2 hours, and the solid content concentration was 20% by weight, having an organic acid group on the side chain of about 1.5 million by weight average molecular weight (polystyrene) in terms of GPC method. An alkyl (meth) acrylate copolymer was obtained.

Example  1: Preparation of Antistatic Adhesive Composition

10 weight% ethyl of N, N, N ', N'-tetraglycidyl xylenediamine [TETRAD-X, Mitsubishi Chemical Company] as a crosslinking agent to 100 parts by weight (solid content ratio) of the copolymer prepared in Preparation Example 1 1 part by weight of an acetate solution and 1 part by weight of 10% by weight ethyl acetate solution of Coronate-L [manufactured by Japan Polyurethane Industry Co., Ltd.], gamma glycidoxypropyl trimethoxysilane (KBM-403, manufactured by Shin-Etsu Co., Ltd.) as a silane coupling agent. 0.2 parts by weight was added, 1 part by weight of phenylsulfoxide side (based on 100 parts by weight of copolymer solid content) was added as a conductive material, and stirred for 10 minutes to prepare a uniform mixed solution.

Example  2: Preparation of Antistatic Adhesive Composition

An antistatic adhesive composition was prepared in the same manner as in Example 1 except that 2 parts by weight of phenyl sulfoxide (based on 100 parts by weight of copolymer solid content) was used as the conductive material.

Example  3: Preparation of Antistatic Adhesive Composition

An antistatic adhesive composition was prepared in the same manner as in Example 1 except that 5 parts by weight of phenyl sulfoxide (based on 100 parts by weight of copolymer solid content) was used as the conductive material.

Example  4: Preparation of Antistatic Adhesive Composition

An antistatic adhesive composition was prepared in the same manner as in Example 1 except that 10 parts by weight of phenyl sulfoxide (based on 100 parts by weight of copolymer solid content) was used as the conductive material.

Example  5: Preparation of Antistatic Adhesive Composition

An antistatic adhesive composition was prepared in the same manner as in Example 1 except that 15 parts by weight of phenyl sulfoxide (based on 100 parts by weight of copolymer solid content) was used as the conductive material.

Example  6: Preparation of antistatic adhesive composition

An antistatic adhesive composition was prepared in the same manner as in Example 1 except that 5 parts by weight of butyl sulfoxide (based on 100 parts by weight of copolymer solids) was used as the conductive material.

Example  7: Preparation of antistatic adhesive composition

An antistatic adhesive composition was prepared in the same manner as in Example 1 except that 5 parts by weight of phenylvinyl sulfoxide (based on 100 parts by weight of copolymer solids) was used as the conductive material.

Example  8: Preparation of Antistatic Adhesive Composition

An antistatic adhesive composition was prepared in the same manner as in Example 1 except that 5 parts by weight of p-tolyl sulfoxide (based on 100 parts by weight of copolymer solids) was used as the conductive material.

Example  9: Preparation of Antistatic Adhesive Composition

An antistatic adhesive composition was prepared in the same manner as in Example 1 except that 5 parts by weight of dodecylmethyl sulfoxide (based on 100 parts by weight of copolymer solids) was used as the conductive material.

Example  10: Preparation of Antistatic Adhesive Composition

An antistatic adhesive composition was prepared in the same manner as in Example 1 except that 5 parts by weight of benzyl sulfoxide (based on 100 parts by weight of copolymer solid content) was used as the conductive material.

Example  11: Preparation of antistatic adhesive composition

An antistatic adhesive composition was prepared in the same manner as in Example 1 except that 5 parts by weight of phenylvinyl sulfone (based on 100 parts by weight of copolymer solids) was used as the conductive material.

Example  12: Preparation of Antistatic Adhesive Composition

An antistatic adhesive composition was prepared in the same manner as in Example 1 except that 10 parts by weight of phenylvinyl sulfone (based on 100 parts by weight of copolymer solid content) was used as the conductive material.

Example  13: Preparation of Antistatic Adhesive Composition

An antistatic adhesive composition was prepared in the same manner as in Example 1 except that 5 parts by weight of dibutyl sulfone (based on 100 parts by weight of copolymer solids) was used as the conductive material.

Example  14: Preparation of Antistatic Adhesive Composition

An antistatic adhesive composition was prepared in the same manner as in Example 1 except that 5 parts by weight of 4-hydroxyphenylsulfone (based on 100 parts by weight of copolymer solids) was used as the conductive material.

Example  15: Preparation of Antistatic Adhesive Composition

An antistatic adhesive composition was prepared in the same manner as in Example 1 except that 5 parts by weight of ethyl sulfone (based on 100 parts by weight of copolymer solids) was used as the conductive material.

Example  16: Preparation of Antistatic Adhesive Composition

An antistatic adhesive composition was prepared in the same manner as in Example 1 except that 5 parts by weight of phenylsulfone (based on 100 parts by weight of copolymer solids) was used as the conductive material.

Example  17: Preparation of Antistatic Adhesive Composition

An antistatic adhesive composition was prepared in the same manner as in Example 1 except that 5 parts by weight of ethyl vinyl sulfone (based on 100 parts by weight of copolymer solids) was used as the conductive material.

Example  18: Preparation of Antistatic Adhesive Composition

An antistatic adhesive composition was prepared in the same manner as in Example 1 except that 5 parts by weight of allylphenylsulfone (based on 100 parts by weight of copolymer solids) was used as the conductive material.

Example  19: Preparation of Antistatic Adhesive Composition

An antistatic adhesive composition was prepared in the same manner as in Example 1 except that 5 parts by weight of p-tolylsulfone (based on 100 parts by weight of copolymer solids) was used as the conductive material.

Comparative example  1: Preparation of Antistatic Adhesive Composition

An antistatic adhesive composition was prepared in the same manner as in Example 1 except that no sulfone or sulfoxide was added.

Test Example  1: Measurement of surface resistivity

The pressure-sensitive adhesive composition prepared in Examples 1 to 8 and Comparative Example 1 was coated on a film (15 cm x 15 cm) coated with a silicone release agent to have a dry film thickness of 25 μm, and dried under conditions of 100 ° C. × 2 minutes. Another layer of the release film was laminated on it, and cured at 25 ° C. for 7 days to prepare an adhesive sheet. The release film on one side of the prepared pressure-sensitive adhesive sheet was removed, laminated onto a polarizing plate composed of triacetyl cellulose (protective film) and polyvinyl alcohol (polarizer), the release film was removed, and the surface specific resistance was measured. Burned out.

<Measuring surface resistivity>

Measuring instrument: Surface resistance measuring instrument (MCP-HT450 / MITSUBISHI CHEMICAL)

 Probe (URS, UR100), Probe Checker (for URS, UR 100)

-Measurement method: The three values of the surface were measured 10 times each and the average value was taken.

Example Sulfone or sulfoxide compounds Surface resistivity (Ω / □) Example 1 1 part by weight of phenyl sulfoxide 10 ¹⁴ Example 2 2 parts by weight of phenyl sulfoxide 10 ¹³ Example 3 5 parts by weight of phenyl sulfoxide 10 ¹² Example 4 10 parts by weight of phenyl sulfoxide 10 ¹² Example 5 15 parts by weight of phenyl sulfoxide 10 ¹¹ Example 6 Butyl sulfoxide 5 parts by weight 10 ¹² Example 7 5 parts by weight of phenylvinyl sulfoxide 10 ¹² Example 8 5 parts by weight of p-tolyl sulfoxide 10 ¹³ Example 9 5 parts by weight of dodecylmethyl sulfoxide 10 ¹² Example 10 Benzyl sulfoxide 5 parts by weight 10 ¹³ Example 11 5 parts by weight of phenyl vinyl sulfone 10 ¹² Example 12 10 parts by weight of phenyl vinyl sulfone 10 ¹² Example 13 Dibutyl sulfone 5 parts by weight 10 ¹² Example 14 4-hydroxyphenylsulfone 5 parts by weight 10 ¹² Example 15 5 parts by weight of ethyl sulfone 10 ¹¹ Example 16 5 parts by weight of phenylsulfone 10 ¹² Example 17 5 parts by weight of ethyl vinyl sulfone 10 ¹¹ Example 18 5 parts by weight of allylphenylsulfone 10 ¹² Example 19 5 parts by weight of p-tolylsulfone 10 ¹² Comparative Example 1 - >> 10 ¹⁴

The present invention provides a pressure-sensitive adhesive composition having a low manufacturing cost, a simple manufacturing process, and excellent antistatic performance by using a conductive material having a low cost and high solubility in the pressure-sensitive adhesive composition. In addition, the polarizing plate including the pressure-sensitive adhesive composition of the present invention as an adhesive layer does not exhibit the problem of static electricity, thereby improving the processing performance of the polarizing plate.

Claims (7)

An antistatic pressure-sensitive adhesive composition comprising an acrylate copolymer having a crosslinkable functional group in the side chain, a crosslinking agent, a silane coupling agent and a sulfone or sulfoxide compound. The antistatic adhesive composition according to claim 1, wherein the sulfone or sulfoxide compound is represented by the following Chemical Formula 1:

(One) Wherein n is 1 or 2; R 1 and R 2 are each independently selected from the group consisting of C 1 -C 5 alkyl substituted or unsubstituted with halogen, halogen or hydroxy group, C 1 -C 5 alkoxy, nitro, hydroxy, amino and azido groups unsubstituted or substituted with halogen or hydroxy group. Aryl unsubstituted or substituted with one or more substituents selected; Or a C 1-20 hydrocarbon unsubstituted or substituted with halogen, hydroxy, amine, carboxy, aryl, alkoxy, alkylthio or trialkylsilyl; Or R 1 and R 2 combine as substituents as defined above to form a ring. The method according to claim 1, 1 to 10 parts by weight of the crosslinking agent, 0.01 to 1 part by weight of the silane coupling agent, and 0.5 to 15 parts by weight of the sulfone or sulfoxide compound based on 100 parts by weight of the acrylate copolymer solid content having a crosslinkable functional group in the side chain. An antistatic pressure-sensitive adhesive composition comprising a part. The acrylate copolymer of claim 1, wherein the acrylate copolymer having a crosslinkable functional group in the side chain Alkyl (meth) acrylate monomers having 4 to 12 carbon atoms; A polymerizable monomer having a crosslinkable functional group in a side chain selected from the group consisting of a polymerizable monomer having a carboxylic acid group, a monomer having a hydroxy group, a monomer having an amide group and a monomer having a tertiary amine group; And Having an alkyl (meth) acrylate monomer having 1 to 3 carbon atoms, an alkyl (meth) acrylate monomer having 13 to 18 carbon atoms, a (meth) acrylic acid ester monomer derived from a cyclic alcohol, an aromatic monomer, an allyl compound monomer, and a nitrile group Monomer selected from the group consisting of monomers, halogen-containing monomers, vinyl ester monomers, and vinyl ether monomers It is an alkyl (methyl) acrylate type copolymer containing (80-99.9) :( 1-10) :( 0-10) by weight ratio, The antistatic adhesive composition characterized by the above-mentioned. The antistatic adhesive composition according to claim 1, wherein the crosslinking agent is at least one member selected from the group consisting of melamine derivatives, polyisocyanate compounds, and polyepoxy compounds. The polarizing plate containing the adhesive layer formed using the adhesive composition of any one of Claims 1-5. Liquid crystal display comprising the polarizing plate of claim 6.