WO2015099279A1 - Adhesive composition containing ionic anti-static agent - Google Patents

Abstract

The present invention relates to an adhesive composition containing an ionic anti-static agent, and more specifically, to an adhesive composition comprising an acrylic copolymer, a cross-linking agent, and the ionic anti-static agent represented by chemical formula 1, thereby exhibiting excellent anti-static performance, significantly improved durability, and maintaining excellent adhesive force in extreme conditions such as high temperature and high humidity.

Description

Pressure-sensitive adhesive composition containing an ionic antistatic agent

The present invention relates to an adhesive composition comprising an ionic antistatic agent.

The image display device is composed of a liquid crystal cell containing a liquid crystal and a polarizing plate, which is mainly bonded by forming an adhesive layer on one surface of the polarizing plate. In addition, in order to improve the function of the image display device, a surface protection film such as a retardation plate, a wide viewing angle compensation plate, and brightness enhancement is additionally attached to the polarizing plate through an adhesive or the like.

Since the optical members such as the surface protection film and the polarizing plate are made of a plastic material, static electricity is generated during friction and peeling, and when voltage is applied to the liquid crystal while the static electricity remains, the orientation of the liquid crystal molecules is lost or the panel is defective. This can happen. Therefore, various antistatic treatments are performed to prevent such defects.

For example, there is a method of adding an at least one surfactant to the adhesive and transferring the surfactant to the adherend to perform an antistatic function, but in this case, the surfactant is easy to bleed on the surface of the adhesive, when applied to a protective film, There was a problem of contamination of the adherend.

In addition, there is a method of adding an antistatic agent composed of a polyether polyol and an alkali metal salt to the acrylic adhesive, but in this case, bleeding of the antistatic agent occurs, and the durability after the curing of the adhesive is significantly reduced, and when applied to a protective film, Bleed out easily occurs under high temperature conditions, and there is a problem that contamination occurs in the adherend.

Korean Patent Publication No. 2011-0112263 discloses a method of introducing a functional group having excellent compatibility with an antistatic agent in a monomer of the pressure-sensitive adhesive composition to suppress bleeding of the antistatic agent. However, durability is deteriorated under high temperature and high humidity conditions. Did not solve.

[Preceding technical literature]

[Patent Documents]

(Patent Document 1) Korean Patent Publication No. 2011-0112263

An object of the present invention is to provide an adhesive composition with remarkably improved antistatic properties and durability.

1.A pressure-sensitive adhesive composition comprising an acrylic copolymer, a crosslinking agent and an ionic antistatic agent represented by the following general formula (1):

[Formula 1]

(Wherein R ₁ is a hydrogen atom, a straight or branched chain alkyl group having 1 to 12 carbon atoms, or a cycloalkyl group having 3 to 12 carbon atoms, X is a halogen atom, a cyano group, -OR ₂ , -OCOR ₃ , or- NR ₄ R ₅ , R ₂ , R ₃ , R ₄ and R ₅ are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and Y ⁻ is an anion. Acid compound, n is an integer from 1 to 30).

2. In the above 1, wherein Y ^- is ^{Cl -, Br -, I -} , AlCl 4 -, Al 2 Cl 7 -, BF 4 -, PF 6 -, ClO 4 -, NO 3 -, CH 3 COO - _{^{, CF 3 COO -, CH 3}} SO 3 -, CF 3 SO 3 -, (CF 3 SO 2) 2 N - (CF 3 SO 2) 3 C -, AsF 6 -, SbF 6 -, NbF 6 -, TaF _{^{6 -, (CN) 2 N}} -, C 4 F 9 SO 3 -, (C 2 F 5 SO 2) 2 N -, C 3 F 7 COO -, (CF 3 SO 2) (CF 3 CO) N - And N (SO ₂ F) ₂ ⁻ , the pressure-sensitive adhesive composition.

3. In the above 1, wherein the ionic antistatic agent represented by Formula 1 is at least one selected from the group consisting of Formula 2 to 9, the pressure-sensitive adhesive composition:

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

4. according to the above 1, wherein the ionic antistatic agent of Formula 1 is included in 0.1 to 10 parts by weight based on 100 parts by weight of the acrylic copolymer, pressure-sensitive adhesive composition.

5. The pressure-sensitive adhesive sheet comprising an adhesive layer formed of the pressure-sensitive adhesive composition of any one of the above 1 to 4.

6. A polarizing plate having a pressure-sensitive adhesive layer formed of the pressure-sensitive adhesive composition of any one of the above 1 to 4 on at least one side.

7. Image display device including the polarizing plate of the above six.

The pressure-sensitive adhesive composition of the present invention exhibits markedly improved antistatic properties and durability, and thus can maintain excellent adhesion even in harsh conditions such as high temperature and high humidity.

The present invention relates to a pressure-sensitive adhesive composition comprising an acrylic copolymer, a crosslinking agent, and an ionic antistatic agent, and exhibits not only excellent antistatic performance, but also markedly improved durability, and can maintain excellent adhesion even in harsh conditions such as high temperature and high humidity. Pressure-sensitive adhesive composition.

Hereinafter, the present invention will be described in detail.

<Adhesive Composition>

The pressure-sensitive adhesive composition of the present invention includes an acrylic copolymer, a crosslinking agent and an ionic antistatic agent.

The ionic antistatic agent of the present invention is represented by the following general formula (1), and contains a polyethylene glycol derivative in the molecule, stabilizes the cation in the molecule and at the same time improves the freedom of movement of the anion, it shows only excellent antistatic performance In addition, it is excellent in compatibility with the pressure-sensitive adhesive composition, it is possible to prevent the bleed out of the ionic compound to provide a pressure-sensitive adhesive composition excellent in durability.

[Formula 1]

Expression from, R ₁ is a cycloalkyl group and a hydrogen atom, an alkyl group of straight or branched chain of 1 to 12 carbon atoms, or having from 3 to 12, X is a halogen atom, a cyano _{group, -OR 2, -OCOR 3, -NR} 4 R ₅ , R ₂ , R ₃ , R _4, and R ₅ are each independently a hydrogen atom, a straight or branched chain alkyl group having 1 to 12 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and n is 1 to 30 Is an integer.

Y ^- is an anionic compound ^{Cl -, Br -, I -} , AlCl 4 -, Al 2 Cl 7 -, BF 4 -, PF 6 -, ClO 4 -, NO 3 -, CH 3 COO -, CF 3 COO _{^{-, CH 3 SO 3 -,}} CF 3 SO 3 -, (CF 3 SO 2) 2 N - (CF 3 SO 2) 3 C -, AsF 6 -, SbF 6 -, NbF 6 -, TaF 6 -, ( _{^{CN) 2 N -, C 4}} F 9 SO 3 -, (C 2 F 5 SO 2) 2 N -, C 3 F 7 COO -, (CF 3 SO 2) (CF 3 CO) N - and N (SO ₂ F) an anionic compound consisting of ₂ ⁻ .

Specific examples of the ionic antistatic agent may be at least one compound selected from the group consisting of the following Chemical Formulas 2 to 9.

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

The content of the ionic antistatic agent is not particularly limited. For example, the ionic antistatic agent may be included in an amount of 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the acrylic copolymer. If the content is less than 0.1 parts by weight, the antistatic function may be insufficient. If the content is more than 10 parts by weight, the content of the anionic compound in the composition is excessive, easily bleed out may occur peeling failure under heat conditions.

By containing an ionic functional group, the acrylic copolymer of this invention can suppress the bleed out of an ionic compound with the outstanding compatibility with the ionic compound of an antistatic agent, and can further improve durability of an adhesive composition.

The acrylic copolymer may be polymerized including a (meth) acrylate monomer having an alkyl group having 1 to 12 carbon atoms and a polymerizable monomer having a crosslinkable functional group, wherein the (meth) acrylate is an acrylate and a methacrylate. Means all.

As a (meth) acrylate monomer which has a C1-C12 alkyl group, n-butyl (meth) acrylate, 2-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) Acrylate, ethyl (meth) acrylate, methyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, pentyl (meth) acrylate, n-octyl (meth) acrylate, Isooctyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, and the like, among which n-butyl acrylate, 2-ethylhexyl acrylate or Mixtures of these are preferred. These can be used individually or in mixture of 2 or more types.

The content and mixing ratio of the (meth) acrylate monomer having an alkyl group having 1 to 12 carbon atoms is not particularly limited. For example, the content may be 85 to 99.9 parts by weight based on 100 parts by weight of the total monomers, based on solid content. Preferably it is 90 to 95 parts by weight. If the content is less than 85 parts by weight, sufficient adhesion cannot be exerted, and if it exceeds 99.9 parts by weight, the cohesion may be lowered.

The polymerizable monomer having a crosslinkable functional group is a component for reinforcing the cohesive force or adhesive strength of the pressure-sensitive adhesive composition by chemical bonding and imparting durability and cutting property, such as a monomer having a carboxyl group, a monomer having a hydroxy group, a monomer having an amide group, The monomer etc. which have a tertiary amine group are mentioned, These can be used individually or in mixture of 2 or more types, It is preferable not to contain acrylic acid from the viewpoint of corrosion prevention improvement.

As a monomer which has a carboxy group, Monovalent acids, such as (meth) acrylic acid and a crotonic acid; Diacids such as maleic acid, itaconic acid and fumaric acid, and monoalkyl esters thereof; 3- (meth) acryloylpropionic acid; Succinic anhydride ring-opening adduct of 2-hydroxyalkyl (meth) acrylate with 2-3 carbon atoms of an alkyl group, Succinic anhydride ring opening adduct of hydroxyalkylene glycol (meth) acrylate with 2-4 carbon atoms of an alkylene group And a compound obtained by ring-opening addition of succinic anhydride to a caprolactone adduct of 2-hydroxyalkyl (meth) acrylate having 2 or 3 carbon atoms of an alkyl group, and among these, (meth) acrylic acid is preferable.

As a monomer which has a hydroxyl group, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 2-hydroxyethylene glycol (meth) acrylate, 2-hydroxypropylene glycol (meth) acrylate, hydroxyalkylene glycol having 2 to 4 carbon atoms of an alkylene group ( Meta) acrylate, 4-hydroxybutyl vinyl ether, 5-hydroxypentyl vinyl ether, 6-hydroxyhexyl vinyl ether, 7-hydroxyheptyl vinyl ether, 8-hydroxyoctyl vinyl ether, 9-hydroxynonyl Vinyl ether, 10-hydroxydecyl vinyl ether, etc. are mentioned, Among these, 4-hydroxybutyl vinyl ether is preferable.

Examples of the monomer having an amide group include (meth) acrylamide, N-isopropylacrylamide, N-tert-butylacrylamide, 3-hydroxypropyl (meth) acrylamide, 4-hydroxybutyl (meth) acrylamide, 6 -Hydroxyhexyl (meth) acrylamide, 8-hydroxyoctyl (meth) acrylamide, 2-hydroxyethylhexyl (meth) acrylamide, etc. are mentioned, Among these, (meth) acrylamide is preferable.

Monomers having a tertiary amine group include N, N- (dimethylamino) ethyl (meth) acrylate, N, N- (diethylamino) ethyl (meth) acrylate, and N, N- (dimethylamino) propyl ( Meth) acrylate, etc. are mentioned.

The content and mixing ratio of the polymerizable monomer having a crosslinkable functional group are not particularly limited. For example, the polymerizable monomer may be included in an amount of 0.1 to 15 parts by weight, preferably 0.5 to 8 parts by weight, based on 100 parts by weight of the total monomers. Madam is good. If the content is less than 0.1 parts by weight, the cohesive force of the pressure-sensitive adhesive may be lowered, the durability may be lowered. If the content is more than 15 parts by weight, the adhesive strength is lowered and durability may be lowered by a high gel fraction.

The acrylic copolymer may further include a polymerizable monomer known in the art in addition to the above monomers in a range that does not lower the adhesive strength, such as 10 wt% or less of the total weight of the monomers.

The production method of the copolymer is not particularly limited, and may be prepared using a method such as bulk polymerization, solution polymerization, emulsion polymerization or suspension polymerization, which are commonly used in the art, and solution polymerization is preferable. In addition, a solvent, a polymerization initiator, a chain transfer agent for molecular weight control, and the like, which are usually used in the polymerization, may be used.

The acrylic copolymer preferably has a weight average molecular weight (polystyrene equivalent, Mw) measured by gel permeation chromatography (GPC) of 50,000 to 2 million, more preferably 400,000 to 2 million. If the weight average molecular weight is less than 50,000, there is a lack of cohesion between the copolymers may cause problems in adhesion durability, if the weight average molecular weight is more than 2 million may require a large amount of dilution solvent to ensure fairness during coating.

The crosslinking agent is a component for appropriately crosslinking the copolymer to improve cohesion, and the kind thereof is not particularly limited. For example, an isocyanate type, an epoxy type, or the like may be used, and these may be used alone or in combination of two or more thereof. have.

Isocyanate type crosslinking agent specifically, tolylene diisocyanate, xylene diisocyanate, 2, 4- diphenylmethane diisocyanate, 4, 4- diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, tetramethylene xylene diisocyanate, Diisocyanate compounds such as naphthalene diisocyanate, adducts of polyhydric alcohol-based compounds such as diisocyanate and trimethanol propane, isocyanurates obtained by self-condensing diisocyanates, biuret bodies condensed with diisocyanates in diisocyanate urea, and tri The polyfunctional isocyanate compound containing three functional groups, such as phenylmethane triisocyanate and methylene bistriisocyanate, etc. are mentioned.

Epoxy type crosslinking agent specifically, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene Glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, polytetramethylene glycol diglycidyl ether, glycerol diglycidyl ether, glycerol triglycidyl ether , Diglycerol polyglycidyl ether, polyglycerol polyglycidyl ether, resorcin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, trimethylol propane triglycidyl ether, pentaerythrate Lithol polyglycidyl ether, sorbitol polyglycidyl ether, adipic acid diglycidyl ester, phthalic acid diglycidyl ester, tris (glycidyl) Isocyanurate, tris (glycidoxyethyl) isocyanurate, 1,3-bis (N, N-glycidylaminomethyl) cyclohexane, N, N, N ', N'-tetraglycidyl- m-xylylenediamine etc. are mentioned.

Further, in addition to the isocyanate-based crosslinking agent and the epoxy-based crosslinking agent, at least one crosslinking agent selected from the group consisting of melamine derivatives such as hexamethyrolmelamine, hexamethoxymethylmelamine, hexabutoxymethylmelamine and the like may be further added. Can be used together

Commercially available examples of the crosslinking agent include Cor-L (Japan Polyurethane Industry Co., Ltd.).

The content of the crosslinking agent is not particularly limited within the range capable of performing its function, for example, 0.1 to 15 parts by weight, preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the acrylic copolymer. Can be. If the content is less than 0.1 parts by weight, the cohesive force may be reduced due to insufficient crosslinking degree, thereby impairing the adhesive durability and the cutting property. If the content is more than 15 parts by weight, problems may occur in relieving residual stress due to an excessive crosslinking reaction.

The pressure-sensitive adhesive composition of the present invention may further include a silane coupling agent.

The silane coupling agent covalently bonds to the adherend surface polar group, thereby improving adhesion.

A silane coupling agent will not be specifically limited if it contains functional groups, such as an amino group, an epoxy group, an acetoacetyl group, a polyalkylene glycol group, an acryl group, and an alkyl group, For example, vinyl trimethoxysilane, vinyl triethoxysilane, vinyl Tris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-amino Propyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmeth Toxyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glyci Doxypropyldimethoxymethylsilane, 3-glycidoxypropylethoxydimethylsil Column; and the like. These can be used individually or in mixture of 2 or more types.

Commercially available examples of silane coupling agents include KBM-403 (Shin-Etsu Co., Ltd.).

The content of the silane coupling agent is not particularly limited. For example, the silane coupling agent may be included in an amount of 0.1 to 2 parts by weight, preferably 0.1 to 0.5 parts by weight, based on 100 parts by weight of the acrylic copolymer. When the content is less than 0.1 parts by weight, the adhesion to the substrate may be insufficient, so that peeling may occur under moisture-resistant heat conditions. When the content is more than 2 parts by weight, the cohesion may be excessively increased, and thus the durability may be lowered as the adhesive properties such as adhesive strength are lowered. have.

In addition, the pressure-sensitive adhesive composition of the present invention may further include additives such as antioxidants, corrosion inhibitors, antifoaming agents, fillers, antistatic agents, and the like, which are commonly used in the art, without departing from the object of the present invention.

<Adhesive sheet>

In addition, the present invention provides a pressure-sensitive adhesive sheet comprising a pressure-sensitive adhesive layer formed of the pressure-sensitive adhesive composition.

The thickness of the adhesive layer is not particularly limited, and may be, for example, 3 to 100 μm, preferably 10 to 100 μm.

The adhesive sheet of the present invention includes an adhesive layer formed on at least one surface of the release film.

The pressure-sensitive adhesive layer can be formed by coating the pressure-sensitive adhesive composition on at least one surface of the release film. The coating method is not particularly limited, and methods known in the art may be used. For example, methods such as a bar coater, air knife, gravure, reverse roll, kiss roll, spray, blade, die coater, casting, and spin coating may be used. It is available.

The release film is not particularly limited, and a release film commonly used in an adhesive sheet may be used, for example, polyester resins such as polyethylene terephthalate, polybutyrene terephthalate, polyethylene naphthalate, and polybutylene naphthalate; Polyimide resins; Acrylic resins; Styrene resins such as polystyrene and acrylonitrile-styrene; Polycarbonate resins; Polylactic acid resins; Polyurethane resins; Polyolefin resins such as polyethylene, polypropylene, ethylene-propylene copolymers; Vinyl resins such as polyvinyl chloride and polyvinylidene chloride; Polyamide resins; Sulfone resins; Polyether ether ketone resins; Allyl resins; Or it may be formed of a mixture of the resin.

The thickness of the release film is not particularly limited, and may be, for example, 5 to 500 μm, and preferably 10 to 100 μm.

<Polarizing plate>

In addition, the present invention provides a polarizing plate including a pressure-sensitive adhesive layer formed on at least one surface of the pressure-sensitive adhesive composition.

The polarizing plate of the present invention includes a polarizer, a protective film bonded to at least one surface of the polarizer, and an adhesive layer formed of the pressure-sensitive adhesive composition on the protective film.

The polarizer may be a polarizer known in the art, and for example, may be manufactured by swelling, dyeing, crosslinking, stretching, washing, drying, and the like of a polyvinyl alcohol-based film.

The protective film is not particularly limited as long as the film is excellent in transparency, mechanical strength, thermal stability, moisture shielding, and isotropy. Specifically, polyester film, such as polyethylene terephthalate, polyethylene isophthalate, polybutylene terephthalate; Cellulose films such as diacetyl cellulose and triacetyl cellulose; Polycarbonate film; Acrylic films such as polymethyl (meth) acrylate and polyethyl (meth) acrylate; Styrene films such as polystyrene and acrylonitrile-styrene copolymers; Polyolefin-based film; Vinyl chloride film; Polyamide films such as nylon and aromatic polyamides; Imide film; Sulfone film; Polyether ketone film; Sulfided polyphenylene-based films; Vinyl alcohol film; Vinylidene chloride-based film; Vinyl butyral film; Allylate film; Polyoxymethylene film; Urethane film; Epoxy film; Silicone film etc. are mentioned. Among these, especially the cellulose type film which has the surface saponified by saponification by alkali etc. is preferable in consideration of polarization characteristic or durability. In addition, the protective film may have a function of the optical layer.

The adhesive layer may be directly coated on the protective film, or may be formed by attaching the adhesive sheet to the protective film.

<Image display device>

In addition, the present invention provides an image display device including the polarizing plate.

The image display apparatus of the present invention may further include a configuration known in the art in addition to the polarizing plate.

Hereinafter, preferred examples are provided to aid the understanding of the present invention, but these examples are merely illustrative of the present invention and are not intended to limit the scope of the appended claims, which are within the scope and spirit of the present invention. It is apparent to those skilled in the art that various changes and modifications can be made to the present invention, and such modifications and changes belong to the appended claims.

Hereinafter, the present invention will be described in detail with reference to Examples.

Preparation Example 1 Preparation of Acrylic Copolymer

Nitrogen gas is refluxed, 90 parts by weight of n-butyl acrylate, 7 parts by weight of methacrylate, 2 parts by weight of 2-hydroxyethyl acrylate, 1 weight of acrylic acid in a 1 L reactor equipped with a cooling device for easy temperature control After adding a monomer mixture consisting of parts, 100 parts by weight of ethyl acetate was added as a solvent. Nitrogen gas was then purged for 1 hour to remove oxygen and then held at 62 ° C. After the mixture was uniformly mixed, 0.07 parts by weight of azobisisobutyronitrile (AIBN) was added as a reaction initiator, and reacted for 8 hours to prepare an acrylic copolymer (a weight average molecular weight of about 1 million).

Preparation Example 2 Synthesis of Antistatic Agent

2-1. Synthesis of Compound of Formula A-1

<Scheme 1>

<Production method>

N-methylimidazole (82g, 1mol) and 1-Chloro-2- (2-methoxy-ethoxy) -ethane (139g, 1mol) were dissolved in 300g of toluene, heated to 80 ° C, stirred for 12 hours, and then distilled water Slowly add a solution of NaPF6 (168g, 1mol) in (300g), stir for an additional 6 hours at the same temperature, cool the reaction solution to room temperature, separate the toluene layer using a separatory funnel, and add Washing was repeated three times using 300 g of distilled water to remove metal salts, and the obtained organic layer was distilled under reduced pressure to remove the solvent and the remaining reactants to obtain Chemical Formula A-1.

2-2. Synthesis of Compound of Formula A-2

<Scheme 2>

<Production method>

In the same manner as in Preparation Example 2-1, except that KI (166g, 1mol) was used instead of NaPF6 (168g, 1mol), Formula A-2 was obtained.

2-3. Synthesis of Compound of Formula A-3

<Scheme 3>

<Production method>

In the same manner as in Preparation Example 2-1, except that NaBF4 (108g, 1mol) was used instead of NaPF6 (168g, 1mol), Formula A-3 was obtained.

2-4. Synthesis of Compounds of Formula A-4

<Scheme 4>

<Production method>

In the same manner as in Preparation Example 2-1, except that K (FSO2) 2 (136 g, 1 mol) was used instead of NaPF6 (168 g, 1 mol), Formula A-4 was obtained.

2-5. Synthesis of Compound of Formula A-5

Scheme 5

<Manufacturing method>

Instead of N-methylimidazole (82 g, 1 mol), it proceeded in the same manner as in Preparation Example 2-1 using N-ethylimidazole (96 g, 1 mol) to obtain a chemical formula A-5.

2-6. Synthesis of Compound of Formula A-6

<Scheme 6>

<Production method>

Instead of 1-Chloro-2- (2-methoxy-ethoxy) -ethane (139g, 1mol), using 1-Chloro-2- (2-chloroethoxy) ethane (715g, 5mol) and the Preparation Example 2-1 Proceeds in the same manner to obtain the formula (A-6). The reason for using excess 1-Chloro-2- (2-chloroethoxy) ethane is to suppress the occurrence of dimer as much as possible.

2-7. Synthesis of Compound of Formula A-7

Scheme 7

<Production method>

Instead of 1-Chloro-2- (2-methoxy-ethoxy) -ethane (139g, 1mol), using 3- (2-Chloro-ethoxy) -propionitrile (133g, 1mol), and Preparation Example 2-1 Proceeds in the same manner to obtain the formula (A-7).

2-8. Synthesis of Compound of Formula A-8

Scheme 8

<Production method>

The above preparation, except that Acetic acid 2- (2-chloro-ethoxy) -ethyl ester (167 g, 1 mol) was used instead of 1-Chloro-2- (2-methoxy-ethoxy) -ethane (139 g, 1 mol). Proceed as in Example 2-1, to obtain the general formula (A-8).

2-9. Synthesis of Compound of Formula A-10

Scheme 9

<Manufacturing method>

In the same manner as in Preparation Example 2-1, except that chlorohexane (121 g, 1 mol) was used instead of 1-Chloro-2- (2-methoxy-ethoxy) -ethane (139 g, 1 mol), the chemical formula A- 10 was obtained.

Example

To prepare a pressure-sensitive adhesive composition having the composition and content shown in Table 1. After the preparation, the silicone release agent was coated on the film, and dried at 100 ° C. for 1 minute to form a pressure-sensitive adhesive layer having a thickness of 25 μm. Thereafter, a release film was laminated on the pressure-sensitive adhesive layer to prepare a pressure-sensitive adhesive sheet.

After peeling the release film of the prepared pressure-sensitive adhesive sheet, a pressure-sensitive adhesive layer was laminated on an iodine polarizing plate containing a TAC protective film of 185㎛ thickness to prepare a polarizing plate with pressure-sensitive adhesive.

Table 1

Experimental Example

The pressure-sensitive adhesive compositions of Examples and Comparative Examples were applied on a release film coated with a silicone release agent so as to have a thickness of 25 μm, and dried at 100 ° C. for 1 minute to form an adhesive layer.

Subsequently, the adhesive layer prepared above was laminated on the iodine-based polarizing film (total thickness 185 μm) to which a triacetyl cellulose protective film was bonded on both sides, to prepare a polarizing plate. The prepared polarizing plate was stored for 7 days under the condition of 23 ° C., 60% RH.

(1) heat resistance evaluation

The release film of the polarizing plate prepared above was removed, bonded to the corning glass, subjected to autoclave treatment, and allowed to stand for 500 hours at a temperature of 80 ° C., followed by evaluation of the occurrence of bubbles or peeling. Evaluation was performed after standing for 24 hours at room temperature immediately before the evaluation after the heat treatment.

<Evaluation Criteria>

Ⓞ: no bubbles or peeling

○: 2 or more bubbles or peelings less than 5

(Triangle | delta): 5 or more of bubble or peeling is less than 10

×: 10 or more bubbles or peelings

(2) Moisture resistance test

The release film of the polarizing plate prepared above was removed, bonded to a corning glass, and subjected to autoclave treatment, and then left for 500 hours at a temperature and humidity of 60 ° C. 90%, followed by evaluation of the occurrence of bubbles or peeling. Evaluation was performed after standing for 24 hours at room temperature immediately before the evaluation after the heat treatment.

<Evaluation Criteria>

Ⓞ: no bubbles or peeling

○: 2 or more bubbles or peelings less than 5

(Triangle | delta): 5 or more of bubble or peeling is less than 10

×: 10 or more bubbles or peelings

 (3) antistatic evaluation

The surface resistivity of the prepared polarizing plate was measured.

<Evaluation Criteria>

Ⓞ: Surface resistivity less than 5.0Ⅹ10 ¹⁰

(Circle): When surface specific resistance value is 5.0 or more ¹⁰ <^10> or less than 1.0 < ¹⁰ > ¹¹

△: When the surface resistivity value of less than ¹¹ or more 1.0Ⅹ10 1Ⅹ10 ¹²

X: surface resistivity value of 1.0Ⅹ10 ¹² or more

TABLE 2

As can be seen from Table 2, in the case of the pressure-sensitive adhesive composition using the antistatic agent containing the novel polyethylene glycol derivative compound of the present invention, not only exhibits excellent antistatic properties, but also it can be confirmed that peeling does not occur easily even under high temperature and high humidity conditions. there was.

In Examples 5 and 6 in which the amount of the antistatic agent was included in a small amount, the antistatic function was slightly lowered, and in Example 7 included in the scope of the present invention but included slightly in excess of the preferred range, the heat resistance was lowered. It could be confirmed.

In the case of Example 8 contained slightly in excess of the scope of the present invention, the antistatic function was excellent, but the content of the anionic compound in the pressure-sensitive adhesive composition is excessive, easily bleed out occurs, the heat resistance and moisture heat resistance slightly decreased I could confirm it.

In the case of Comparative Example 1 using NaPF ₆ instead of the antistatic agent of the present invention, the degree of freedom of movement of the anion was reduced, the antistatic performance was deteriorated, and the polyethylene glycol derivative was not included in the molecule. .

Comparative Example 2 using the chemical formula A-10 instead of the antistatic agent of the present invention is slightly reduced antistatic performance, do not contain a polyethylene glycol derivative in the molecule, the compatibility with the pressure-sensitive adhesive composition is lowered, the adhesive strength is slightly reduced at high temperature conditions It could be confirmed. However, the heat-and-moisture resistance showed the same excellent effect as that of the Example.

Claims (7)

1. A pressure-sensitive adhesive composition comprising an acrylic copolymer, a crosslinking agent and an ionic antistatic agent represented by the following general formula (1):

   [Formula 1]

   

   (In formula, R <_1> is a hydrogen atom, a C1-C12 linear or branched alkyl group, or a C3-C12 cycloalkyl group,

   X is a halogen atom, cyano group, -OR ₂ , -OCOR ₃ , or -NR ₄ R ₅ ,

   R ₂ , R ₃ , R ₄ and R ₅ are each independently a hydrogen atom, a straight or branched chain alkyl group having 1 to 12 carbon atoms, or an aryl group having 6 to 12 carbon atoms,

   Y ^- is an anionic compound,

   n is an integer from 1 to 30).
2. The method according to claim 1, wherein Y ^- is ^{Cl -, Br -, I -} , AlCl 4 -, Al 2 Cl 7 -, BF 4 -, PF 6 -, ClO 4 -, NO 3 -, CH 3 COO -, CF _{^{3 COO -, CH 3 SO 3}} -, CF 3 SO 3 -, (CF 3 SO 2) 2 N - (CF 3 SO 2) 3 C -, AsF 6 -, SbF 6 -, NbF 6 -, TaF 6 - ^{_{, (CN) 2 N -,}} C 4 F 9 SO 3 -, (C 2 F 5 SO 2) 2 N -, C 3 F 7 COO -, (CF 3 SO 2) (CF 3 CO) N - and N (SO ₂ F) ₂ ^-The pressure-sensitive adhesive composition selected from the group consisting of.
3. The pressure-sensitive adhesive composition of claim 1, wherein the ionic antistatic agent represented by Chemical Formula 1 is at least one selected from the group consisting of Chemical Formulas 2 to 9.

   [Formula 2]

   

   [Formula 3]

   

   [Formula 4]

   

   [Formula 5]

   

   [Formula 6]

   

   [Formula 7]

   

   [Formula 8]

   

   [Formula 9]

   
4. The pressure-sensitive adhesive composition of claim 1, wherein the ionic antistatic agent of Formula 1 is included in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the acrylic copolymer.
5. The adhesive sheet containing the adhesion layer formed from the adhesive composition of any one of Claims 1-4.
6. The polarizing plate provided with the adhesion layer formed from the adhesive composition of any one of Claims 1-4 on at least one surface.
7. An image display device comprising the polarizing plate of claim 6.