KR20150075986A - Adhesive composition containing ionic antistatic agent - Google Patents

Abstract

The present invention relates to an adhesive composition including an ionic antistatic agent and, more specifically to an adhesive composition not only presenting excellent antistatic performances, but also presenting significantly improved durability, and maintaining excellent adhesion even under a significant condition such as high temperature and high humidity by including an acrylic copolymer, a crosslinking agent, and an ionic antistatic agent presented by chemical formula 1.

Description

ADHESIVE COMPOSITION CONTAINING IONIC ANTISTATIC AGENT [0001] This invention relates to a pressure-

The present invention relates to a pressure-sensitive adhesive composition comprising an ionic antistatic agent.

An image display device is composed of a liquid crystal cell containing a liquid crystal and a polarizing plate, which are mainly bonded together 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 protective film such as a retardation plate, a wide viewing angle compensating plate and a brightness enhancement is additionally attached to a polarizing plate through an adhesive or the like.

Since such optical members such as the surface protective film and the polarizing plate are made of a plastic material, static electricity is generated at the time of friction and peeling, and when a voltage is applied to the liquid crystal in a state where static electricity remains, the orientation of the liquid crystal molecules is lost, Can occur. Therefore, various antistatic treatments have been carried out to prevent such defects.

For example, there is a method in which at least one surfactant is added to a pressure-sensitive adhesive to transfer the surfactant to the adherend to perform an antistatic function. In this case, when the surfactant is easy to bleed on the surface of the pressure- There has been a problem that contamination of the adherend is liable to occur.

Further, there is a method of adding an antistatic agent composed of a polyether polyol and an alkali metal salt to an acrylic pressure-sensitive adhesive. However, in this case, bleeding of an antistatic agent occurs and the durability after the curing of the pressure- There is a problem that bleeding out easily occurs under a high temperature condition and contamination is caused in the adherend.

Korean Patent Publication No. 2011-0112263 discloses a method of introducing a functional group having excellent compatibility with an antistatic agent into a monomer of a pressure-sensitive adhesive composition in order to suppress the bleeding of an antistatic agent, but the problem that durability is lowered under high temperature and high humidity conditions .

Korea Patent Publication No. 2011-0112263

An object of the present invention is to provide a pressure-sensitive adhesive composition which is remarkably improved in antistatic property and durability.

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

[Chemical Formula 1]

Wherein R ₁ is a linear or branched alkyl group having 1 to 12 carbon atoms or a cycloalkyl group having 3 to 12 carbon atoms and the alkyl group and the cycloalkyl group may be independently substituted with an aryl group having 6 to 12 carbon atoms and m is the two different R ₁ connected to a second or less, and can form a ring, the ring may be a heterocycle, X is a halogen atom, a cyano group, -OR _2, -OCOR _3, or -NR ₄ R ₅ a, R _2, R _3, R ₄ and R ₅ are each independently a hydrogen atom, an alkyl group of straight or branched chain of 1 to 12 carbon atoms, or an aryl group having 6 to 12, Y ^- is Cl ^-, Br ^- , I ^- , AlCl ₄ ^- , Al ₂ Cl ₇ ^- , BF ₄ ^- , PF ₆ ^- , ClO ₄ ^- , NO ₃ ^- , AsF ₆ ^- , SbF ₆ ^- , NbF ₆ ^- , TaF ₆ ^- (SO ₂ F) ₂ ^- , n is an integer from 1 to 30, and m is an integer from 1 to 4).

2. The pressure-sensitive adhesive composition according to 1 above, wherein the ionic antistatic agent represented by the formula (1) is at least one selected from the group consisting of the following formulas (2) to (11)

(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(7)

[Chemical Formula 8]

[Chemical Formula 9]

[Chemical formula 10]

(11)

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

4. A pressure-sensitive adhesive sheet comprising an adhesive layer formed from the pressure-sensitive adhesive composition according to any one of 1 to 3 above.

5. A polarizing plate comprising at least one side of the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition of any one of items 1 to 3 above.

6. An image display device comprising the polarizing plate of 5 above.

INDUSTRIAL APPLICABILITY The pressure-sensitive adhesive composition of the present invention exhibits remarkably improved electrification design and durability, so that it is possible to maintain an excellent adhesive force even under 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, which not only exhibits excellent antistatic performance but also exhibits remarkably improved durability and can maintain excellent adhesion even under severe conditions such as high temperature and high humidity To a pressure-sensitive adhesive composition.

Hereinafter, the present invention will be described in detail.

≪ Pressure sensitive 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 improves the degree of freedom of movement of the anion. But is excellent in compatibility with the pressure-sensitive adhesive composition, and it is possible to provide a pressure-sensitive adhesive composition having excellent durability by blocking the bleed-out of the ionic compound.

[Chemical Formula 1]

Wherein R ₁ is a linear or branched alkyl group having 1 to 12 carbon atoms or a cycloalkyl group having 3 to 12 carbon atoms and the alkyl group and the cycloalkyl group may be independently substituted with an aryl group having 6 to 12 carbon atoms, 2 or less, two different R < ₁ > may be connected to form a ring, which may be a heterocyclic ring containing an oxygen atom, a nitrogen atom or a sulfur atom in the ring, and X represents a halogen atom, a cyano group, -OR ₂ , -OCOR ₃ , or -NR ₄ R ₅ , and R ₂ , R ₃ , R _4, and R ₅ are each independently a hydrogen atom, a straight or branched alkyl group having 1 to 12 carbon atoms, 12 is an aryl group, Y ^- is ^{Cl -, Br -, I -} , AlCl 4 -, Al 2 Cl 7 -, BF 4 -, PF 6 -, ClO 4 -, NO 3 -, AsF 6 -, SbF 6 ^- , NbF ₆ ^- , TaF ₆ ^- , or N (SO ₂ F) ₂ ^- , n is an integer from 1 to 30, and m is an integer from 1 to 4.

The ionic antistatic agent of the present invention is an anionic compound (Y < ^- >) which is superior in compatibility with a pressure-sensitive adhesive as compared with the case of using an organic compound, Excellent effect can be obtained.

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 (11).

(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(7)

[Chemical Formula 8]

[Chemical Formula 9]

[Chemical formula 10]

(11)

The content of the ionic antistatic agent is not particularly limited and may be, for example, 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. When the content is less than 0.1 part by weight, the antistatic property may be insufficient. If the content is more than 10 parts by weight, bleeding out easily occurs and peeling failure may occur in a heat-resistant condition.

Since the acrylic copolymer of the present invention contains an ionic functional group, it has excellent compatibility with an ionic antistatic agent and can suppress the bleed-out of the ionic compound, thereby further improving the durability of the pressure-sensitive adhesive composition.

The acrylic copolymer may be a polymer obtained by polymerizing 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 .

Examples of the (meth) acrylate monomer having an alkyl group having 1 to 12 carbon atoms include n-butyl (meth) acrylate, 2-butyl (meth) acrylate, (Meth) acrylate, ethyl (meth) acrylate, methyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (Meth) acrylate, nonyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate and lauryl (meth) acrylate. Of these, n-butyl acrylate, Mixtures of these are preferred. These may be used alone or in combination of two or more.

The content and the mixing ratio of the (meth) acrylate monomer having an alkyl group of 1 to 12 carbon atoms are not particularly limited and may be, for example, 85 to 99.9 parts by weight based on 100 parts by weight of the total monomer based on the solid content, Preferably 90 to 95 parts by weight. When the content is less than 85 parts by weight, sufficient adhesion can not be exhibited, and when it exceeds 99.9 parts by weight, the cohesive strength may be lowered.

The polymerizable monomer having a crosslinkable functional group is a component for imparting durability and cutability by reinforcing the cohesive force or adhesive strength of the pressure-sensitive adhesive composition by chemical bonding, and examples thereof include monomers having a carboxyl group, monomers having a hydroxy group, monomers having an amide group, And tertiary amine groups. These monomers may be used singly or in admixture of two or more. In view of the improvement of corrosion resistance, those containing no acrylic acid are preferable.

Examples of the monomer having a carboxyl group include monovalent acids such as (meth) acrylic acid and crotonic acid; Dicarboxylic acids such as maleic acid, itaconic acid, and fumaric acid, and monoalkyl esters thereof; 3- (meth) acryloylpropionic acid; A succinic anhydride ring-opening addition adduct of 2-hydroxyalkyl (meth) acrylate in which the alkyl group has 2 to 4 carbon atoms, anhydrous succinic ring opening adduct of a hydroxyalkylene glycol (meth) acrylate having 2 to 4 carbon atoms in the alkylene group , And compounds obtained by ring-opening addition of succinic anhydride to a caprolactone adduct of 2-hydroxyalkyl (meth) acrylate having 2 or 3 carbon atoms in the alkyl group. Of these, (meth) acrylic acid is preferable.

Examples of the monomer having a hydroxy group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl Hydroxypropyleneglycol (meth) acrylate, hydroxyalkylene glycol having 2 to 4 carbon atoms in the alkylene group (e.g., methoxyethyl (meth) acrylate, Hydroxybutyl vinyl ether, 8-hydroxyoctyl vinyl ether, 9-hydroxynonyl (meth) acrylate, 4-hydroxybutyl vinyl ether, Vinyl ether, and 10-hydroxydecyl vinyl ether, among which 4-hydroxybutyl vinyl ether is preferable.

Examples of the monomer having an amide group include (meth) acrylamide, N-isopropyl acrylamide, N-tertiary butyl acrylamide, 3-hydroxypropyl (meth) acrylamide, 4-hydroxybutyl (Meth) acrylamide, 8-hydroxyoctyl (meth) acrylamide, and 2-hydroxyethylhexyl (meth) acrylamide. Of these, (meth) acrylamide is preferable.

Examples of the monomer having a tertiary amine group include N, N- (dimethylamino) ethyl (meth) acrylate, N, N- (diethylamino) ethyl (meth) Methacrylate, and the like.

The content and the mixing ratio of the polymerizable monomer having a crosslinkable functional group are not particularly limited and may be, for example, 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, Wife is good. If the content is less than 0.1 part by weight, the cohesive strength of the pressure-sensitive adhesive may be lowered and durability may be deteriorated. If the content is more than 15 parts by weight, the adhesive strength may be lowered and durability may be deteriorated due to a high gel fraction.

The acrylic copolymer may further contain, in addition to the above monomers, polymeric monomers known in the art to such an extent as not to deteriorate the adhesive strength, for example, 10% by weight or less based on the total weight of the total monomers.

The method for producing the copolymer is not particularly limited and can be produced by methods 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 polymerization can be used.

The acrylic copolymer preferably has a weight average molecular weight (polystyrene conversion, Mw) of 50,000 to 2,000,000, more preferably 400,000 to 2,000,000 as measured by Gel Permeation Chromatography (GPC). When the weight-average molecular weight is less than 50,000, cohesion between co-polymers may be insufficient, which may cause problems in adhesion durability. If the weight average molecular weight is more than 2,000,000, a large amount of a diluting solvent may be required in order to ensure fairness in coating.

The crosslinking agent is a component for appropriately crosslinking the copolymer to improve the cohesive force, and the kind thereof is not particularly limited. For example, an isocyanate-based or epoxy-based crosslinking agent may be used. These crosslinking agents may be used alone or in combination have.

Examples of the isocyanate-based crosslinking agent include 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 diisocyanate and polyhydric alcohol compounds such as trimethanol propane, isocyanurate compounds in which diisocyanate is self-condensed, burettes in which diisocyanate urea is condensed with diisocyanate, tri And polyfunctional isocyanate compounds containing three functional groups such as phenylmethane triisocyanate and methylene bistriisocyanate.

Examples of the epoxy crosslinking agent include 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, resorcinol diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, trimethylol propane triglycidyl ether, pentaerythritol Sorbitol polyglycidyl ether, adipic acid diglycidyl ester, phthalic acid diglycidyl ester, tris (glycidyl) (N, N-glycidylaminomethyl) cyclohexane, N, N, N ', N'-tetraglycidyl-isocyanurate, m-xylylenediamine, and the like.

In addition to the isocyanate crosslinking agent and the epoxy crosslinking agent, at least one crosslinking agent selected from the group consisting of melamine derivatives such as hexamethylol melamine, hexamethoxymethyl melamine, and hexabutoxymethyl melamine is further added Can be used.

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

The content of the cross-linking agent is not particularly limited within a range where the function of the cross-linking agent can be accomplished. 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, . When the content is less than 0.1 part by weight, the cohesive force becomes small due to insufficient crosslinking, which may deteriorate the durability of the adhesive durability and the cutability. If the content exceeds 15 parts by weight, the residual stress due to the excessive crosslinking reaction may occur.

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

The silane coupling agent is covalently bonded to the surface polar group of the adherend to improve the adhesion.

The silane coupling agent is not particularly limited as long as it contains a functional group such as an amino group, an epoxy group, an acetoacetyl group, a polyalkylene glycol group, an acryl group or an alkyl group, and examples thereof include vinyltrimethoxysilane, vinyltriethoxysilane, vinyl Tris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3- Propyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyl 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, Isopropyldimethoxymethylsilane, 3-glycidoxypropylethoxydimethylsilane And the like. These may be used alone or in combination of two or more.

A commercially available example of the silane coupling agent is KBM-403 (Shin-Etsu).

The content of the silane coupling agent is not particularly limited and may be, for example, 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 based on the solid content. When the content is less than 0.1 parts by weight, the adhesion to the substrate may be insufficient and peeling may occur under the conditions of moist heat resistance. If the content is more than 2 parts by weight, the cohesive strength may be excessively increased to deteriorate the adhesive properties such as adhesion, have.

The pressure-sensitive adhesive composition of the present invention may further contain additives such as an antioxidant, a corrosion inhibitor, a defoaming agent, a filler and the like which are commonly used in the art within the scope of the present invention.

<Adhesive sheet>

The present invention also provides a pressure-sensitive adhesive sheet comprising a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition.

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

The pressure sensitive adhesive sheet of the present invention comprises an adhesive layer formed on at least one surface of a 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 a method known in the art may be used. For example, a method such as bar coater, air knife, gravure, reverse roll, kiss roll, spray, blade, die coater, casting, Can be used.

The releasing film is not particularly limited, and a releasing film commonly used for the pressure-sensitive adhesive sheet can be used. Examples of the releasing film include polyester resins such as polyethylene terephthalate, polybutylene terephthalide, polyethylene naphthalate and polybutylene naphthalate; Polyimide resin; Acrylic resin; Styrene-based resins such as polystyrene and acrylonitrile-styrene; Polycarbonate resin; Polylactic acid resin; Polyurethane resin; Polyolefin resins such as polyethylene, polypropylene and ethylene-propylene copolymer; Vinyl resins such as polyvinyl chloride and polyvinylidene chloride; Polyamide resins; Sulfonic resin; Polyether-ether ketone resin; Allylate series resin; Or a mixture of these resins.

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

<Polarizer>

The present invention also provides a polarizing plate comprising an adhesive layer formed on at least one side of the pressure-sensitive adhesive composition.

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

The polarizer may be a polarizer well-known in the art, for example, a polyvinyl alcohol film produced through a process such as swelling, dyeing, crosslinking, stretching, washing, drying and the like.

The protective film is not particularly limited as long as it is a film excellent in transparency, mechanical strength, thermal stability, moisture barrier property, isotropy, and the like. Specifically, polyester films such as polyethylene terephthalate, polyethylene isophthalate and polybutylene terephthalate; Cellulose-based films such as diacetylcellulose and triacetylcellulose; Polycarbonate-based films; Acrylic films such as polymethyl (meth) acrylate and polyethyl (meth) acrylate; Styrene-based films such as polystyrene and acrylonitrile-styrene copolymer; Polyolefin films; Vinyl chloride film; Polyamide-based films such as nylon and aromatic polyamide; Imidazole film; Sulfone based films; Polyether ketone-based films; A sulfided polyphenylene-based film; Vinyl alcohol film; Vinylidene chloride films; Vinyl butyral film; Allylate-based films; Polyoxymethylene-based films; Urethane-based films; Epoxy-based films; Silicone-based films, and the like. Among them, a cellulose-based film having a surface saponified (saponified) by alkali or the like is preferable in consideration of polarization characteristics or durability. In addition, the protective film may have the function of an optical layer.

The adhesive layer may be coated directly on the protective film, or may be formed by adhering an 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.

It is to be understood that both the foregoing general description and the following detailed description of the present invention are exemplary and explanatory and are intended to be illustrative of the invention and are not intended to limit the scope of the claims. It will be apparent to those skilled in the art that such variations and modifications are within the scope of the appended claims.

Manufacturing example  1: Preparation of acrylic copolymer

Nitrogen gas was refluxed and a 1 L reactor equipped with a cooling device for easy temperature control was charged with 90 parts by weight of n-butyl acrylate, 7 parts by weight of methacrylate, 2 parts by weight of 2-hydroxyethyl acrylate, , And 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 maintained at 62 ° C. After the mixture was homogeneously mixed, 0.07 part by weight of azobisisobutyronitrile (AIBN) was added as a reaction initiator and reacted for 8 hours to prepare an acrylic copolymer (weight average molecular weight: about 1,000,000).

Manufacturing example  2: Synthesis of Antistatic Agent

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

<Reaction Scheme 1>

<Manufacturing Method>

300 g of toluene was dissolved in 185 g (1 mol) of tributylamine and 139 g (1 mol) of 1-Chloro-2- (2-methoxy-ethoxy) to put in a solution of NaPF ₆ (168g, 1mol) slowly, it was further stirred for 6 hours at the same temperature. Thereafter, the reaction solution was cooled to room temperature, the toluene layer was separated by using a separating funnel, and further washed three times with 300 g of distilled water to remove metal salts. The obtained organic layer was distilled under reduced pressure, The reactants were removed to give formula (A-1).

2-2. (A- 2 of  Synthesis of compounds

<Reaction Scheme 2>

<Manufacturing Method>

(715 g, 5 mol) was used instead of 1-Chloro-2- (2-methoxy-ethoxy) -ethane (139 g, -1, thereby obtaining a compound of formula (A-2). The reason for using excessive amount of 1-Chloro-2- (2-chloro-ethoxy) -ethane is to suppress the generation of dimer as much as possible.

2-3. (A- 3 of  Synthesis of compounds

<Reaction Scheme 3>

<Manufacturing Method>

A-3 was obtained in the same manner as in Preparation Example 2-1, except that NaBF ₄ (108 g, 1 mol) was used instead of NaPF ₆ (168 g, 1 mol).

2-4. (A- 4 of  Synthesis of compounds

<Reaction Scheme 4>

<Manufacturing Method>

Except that acetic acid 2- (2-chloro-ethoxy) -ethyl ester (167 g, 1 mol) was used in place of 1-Chloro-2- (2- methoxy- Proceeding in the same manner as in Example 2-1, a compound of the formula A-4 was obtained.

2-5. (A- 5 of  Synthesis of compounds

<Reaction Scheme 5>

<Manufacturing Method>

The procedure of Preparation Example 2-1 was repeated, except that KI (166 g, 1 mol) was used instead of NaPF ₆ (168 g, 1 mol) to obtain a compound of Formula A-5.

2-6. (A- 6 of  Synthesis of compounds

<Reaction Scheme 6>

<Manufacturing Method>

A-6 was obtained in the same manner as in Preparation Example 2-1, except that K (FSO ₂ ) ₂ (136 g, 1 mol) was used instead of NaPF ₆ (168 g, 1 mol).

2-7. (A- 7's  Synthesis of compounds

<Reaction Scheme 7>

<Manufacturing Method>

Except that 278 g of 2-chloro-2- (2-methoxy-ethoxy) -ethane was used instead of tributylamine (185 g, 1 mol) Proceeding in the same manner as in Production Example 2-1, a compound of the formula A-7 was obtained.

2-8. (A- 8 of  Synthesis of compounds

<Reaction Scheme 8>

<Manufacturing Method>

The procedure of Preparation Example 2-1 was repeated except that tributylamine (185 g, 1 mol) was replaced by N-methylmorpholine (101 g, 1 mol) to obtain the compound of Formula A-8.

2-9. (A- 9 of  Synthesis of compounds

<Reaction Scheme 9>

<Manufacturing Method>

Except that benzyl-methyl-amine (121 g, 1 mol) was used instead of tributylamine (185 g, 1 mol) and 278 g, 2 mol of 1-Chloro-2- (2-methoxy- Proceeding in the same manner as in Production Example 2-1, a compound of the formula A-9 was obtained.

2-10. (A- Ten  Synthesis of compounds

<Reaction formula 10>

<Manufacturing Method>

The procedure of Preparation Example 2-1 was repeated except that tributylamine (185 g, 1 mol) was replaced by N-methylpiperidine (99 g, 1 mol) to obtain a compound of Formula A-10.

2-11. (A- 12 of  Synthesis of compounds

<Reaction Scheme 11>

<Manufacturing Method>

The procedure of Preparation Example 2-1 was repeated except that chlorohexane (121 g, 1 mol) was used instead of 1-Chloro-2- (2-methoxy-ethoxy) 12.

2-12. (A- Thirteen  Synthesis of compounds

<Reaction Scheme 12>

<Manufacturing Method>

A-13 was obtained in the same manner as in Preparation Example 2-1, except that NaOAc (82 g, 1 mol) was used instead of NaPF ₆ (168 g, 1 mol).

2-13. (A- 14 of  Synthesis of compounds

<Reaction Scheme 13>

<Manufacturing Method>

A-14 was obtained in the same manner as in Preparation Example 2-1, except that NaOTs (sodium tosylate) (194 g, 1 mol) was used instead of NaPF ₆ (168 g, 1 mol).

Example

A pressure-sensitive adhesive composition having the composition and content shown in Table 1 was prepared. And then coated on a film coated with a silicone release agent and dried at 100 DEG C for 1 minute to form a pressure-sensitive adhesive layer of 25 mu m. Thereafter, a release film was laminated on the pressure-sensitive adhesive layer to produce a pressure-sensitive adhesive sheet.

After the release film of the pressure sensitive adhesive sheet thus prepared was peeled off, a pressure sensitive adhesive layer was laminated on an iodine polarizing plate including a TAC protective film having a thickness of 185 탆 to prepare a polarizer with a pressure-sensitive adhesive.

division
(Parts by weight) Antistatic agent
(A) The acrylic copolymer (B) Cross-linking agent
(C) Silane coupling agent
(D) Example 1 A-1 2 100 One 0.5 Example 2 A-2 2 100 One 0.5 Example 3 A-3 2 100 One 0.5 Example 4 A-4 2 100 One 0.5 Example 5 A-5 2 100 One 0.5 Example 6 A-6 2 100 One 0.5 Example 7 A-7 0.05 100 One 0.5 Example 8 A-8 0.3 100 One 0.5 Example 9 A-9 6 100 One 0.5 Example 10 A-10 12 100 One 0.5 Comparative Example 1 A-11 2 100 One 0.5 Comparative Example 2 A-12 2 100 One 0.5 Comparative Example 3 - - 100 One 0.5 Comparative Example 4 A-13 2 100 One 0.5 Comparative Example 5 A-14 2 100 One 0.5 A: Antistatic agent of Production Example 2
A-11: NaPF ₆
B: The acrylic copolymer of Production Example 1
C: Cor-L (Japan Polyurethane Industry Co., Ltd.)
D: KBM-403 (Shin-Etsu)

Experimental Example

The pressure-sensitive adhesive compositions of Examples and Comparative Examples were cured on a releasing film coated with a silicone release agent, and then coated to a thickness of 25 占 퐉 and dried at 100 占 폚 for 1 minute to form an adhesive layer.

Thereafter, the pressure-sensitive adhesive layer prepared above was laminated to an iodine-based polarizing film (total thickness 185 μm) bonded on both sides with a triacetylcellulose-based protective film by sticking to produce a polarizing plate. The prepared polarizing plate was stored for 7 days under conditions of 23 캜 and 60% RH.

(1) Evaluation of heat resistance

The release film of the prepared polarizing plate was removed, bonded to Corning glass, autoclaved, left at a temperature of 80 캜 for 500 hours, and then observed for bubbles or peeling. The evaluation was carried out after standing at room temperature for 24 hours immediately before the evaluation after the heat treatment.

<Evaluation Criteria>

Ⓞ: No bubble or peeling

○: Two or more bubbles or peelings and less than five

B: Bubbles or peeling 5 or more and less than 10

X: 10 or more bubbles or peeling

(2) Humidity Durability  evaluation

The prepared release film of the polarizing plate was removed, bonded to a Corning glass, autoclaved, and then allowed to stand at 60 ° C and a temperature and humidity of 90% for 500 hours, and then observed for occurrence of bubbles or peeling was evaluated. The evaluation was carried out after standing at room temperature for 24 hours immediately before the evaluation after the heat treatment.

<Evaluation Criteria>

Ⓞ: No bubble or peeling

○: Two or more bubbles or peelings and less than five

B: Bubbles or peeling 5 or more and less than 10

X: 10 or more bubbles or peeling

(3) Daejeon Preventiveness  evaluation

The surface resistivity of the prepared polarizer was measured.

<Evaluation Criteria>

Ⓞ: When the surface resistivity value is less than 5.0 × ^{10 10}

?: When the surface resistivity value is 5.0 x ^{10 10} or more and 1.0 x ^{10 11} or less

?: When the surface resistivity value is 1.0 x ^{10 11} or more and less than 1 x ^{10 12}

×: When the surface resistivity value is 1.0 × 10 ¹² or more

division Heat resistance Humidity Durability Antistatic property Example 1 ◎ ◎ ◎ Example 2 ◎ ◎ ◎ Example 3 ◎ ◎ ◎ Example 4 ◎ ◎ ◎ Example 5 ◎ ◎ ◎ Example 6 ◎ ◎ ◎ Example 7 ◎ ◎ △ Example 8 ◎ ◎ ○ Example 9 ○ ◎ ◎ Example 10 ○ ○ ◎ Comparative Example 1 × × △ Comparative Example 2 △ ◎ △ Comparative Example 3 ◎ ◎ × Comparative Example 4 × × △ Comparative Example 5 × × △

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 the excellent antistatic property was observed but also the peeling did not occur easily even under the condition of high temperature and high humidity there was.

However, in Examples 7 and 8 in which the content of the antistatic agent was included in a small amount, it was confirmed that the antistatic function was slightly lower than in the other Examples.

In the case of Example 9, which contained the antistatic agent in the content range of the present invention but contained a little over the preferred content range, the antistatic function was excellent, but the heat resistance was lower than in the other Examples, , The content of the anionic compound in the pressure-sensitive adhesive composition was excessive, and bleed-out occurred easily, and it was confirmed that the heat resistance and the heat and humidity resistance were slightly lowered.

In 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 and the antistatic property was lowered. As a result, the polyethylene glycol derivative was not contained in the molecule, .

Comparative Example 2 using the compound of the formula (A-12) instead of the antistatic agent of the present invention showed a somewhat lowered antistatic property and the polyethylene glycol derivative was not contained in the molecule and the compatibility with the pressure-sensitive adhesive composition was lowered, . However, since the heat resistance is evaluated at a relatively low temperature as compared with the heat resistance, the heat and humidity resistance has the same effect as that of the embodiment.

In the case of Comparative Example 4 and Comparative Example 5 using pyridinium compounds (compounds A-13 and 14) containing organic anions, the antistatic function was also lower than that in Examples, and the degree of stabilization of organic anions with respect to the pressure- It was confirmed that bleeding-out occurred and the heat resistance and the heat and humidity resistance were greatly lowered.

Claims (6)

An acrylic copolymer, a crosslinking agent and an ionic antistatic agent represented by the following formula (1):
[Chemical Formula 1]

Wherein R ₁ is a linear or branched alkyl group having 1 to 12 carbon atoms or a cycloalkyl group having 3 to 12 carbon atoms and the alkyl group and the cycloalkyl group may be independently substituted with an aryl group having 6 to 12 carbon atoms and m Is 2 or less, two different R &lt; ₁ &gt; may be connected to form a ring, and the ring may be a heterocyclic ring,
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 alkyl group having 1 to 12 carbon atoms, or an aryl group having 6 to 12 carbon atoms,
Y ^- is ^{Cl -, Br -, I -} , AlCl 4 -, Al 2 Cl 7 -, BF 4 -, PF 6 -, ClO 4 -, NO 3 -, AsF 6 -, SbF 6 -, NbF 6 -, TaF ₆ ^- , or N (SO ₂ F) ₂ ^-
n is an integer of 1 to 30, and m is an integer of 1 to 4).
The pressure-sensitive adhesive composition according to claim 1, wherein the ionic antistatic agent represented by the formula (1) is at least one selected from the group consisting of the following formulas (2) to (11)
(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(7)

[Chemical Formula 8]

[Chemical Formula 9]

[Chemical formula 10]

(11)

The pressure-sensitive adhesive composition according to 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.
A pressure-sensitive adhesive sheet comprising an adhesive layer formed from the pressure-sensitive adhesive composition according to any one of claims 1 to 3.
And a pressure-sensitive adhesive layer formed on at least one side of the pressure-sensitive adhesive composition according to any one of claims 1 to 3.
An image display device comprising the polarizing plate of claim 5.