WO2015099283A1 - Novel pyridinium-based compound, method for manufacturing same, and anti-static agent and adhesive composition containing novel pyridinium-based compound - Google Patents

Abstract

The present invention relates to a novel pyridinium-based compound, and an anti-static agent and an adhesive composition containing same, and more specifically, to an anti-static agent having excellent compatibility with an adhesive composition and an adhesive composition capable of maintaining excellent adhesive force even under extreme conditions such as high temperature and high humidity, by containing the pyridinium-based compound represented by chemical formula 1.

Description

Novel pyridinium-based compounds, preparation method thereof, antistatic agent and pressure-sensitive adhesive composition containing same

The present invention relates to a novel pyridinium-based compound and an antistatic agent containing the same.

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 liquid crystal 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 Application Publication No. 2011-0112263 discloses a method of introducing a functional group having excellent compatibility with an antistatic agent in a monomer of an adhesive composition in order to suppress bleeding of the antistatic agent. 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 a novel pyridinium-based compound and an antistatic agent comprising the same, which can produce a pressure-sensitive adhesive composition with significantly improved antistatic function and durability.

1. A pyridinium compound represented by the following 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 the compound represented by Formula 1 is selected from the group consisting of compounds represented by the following formula 2 to 7, pyridinium-based compound:

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

Wherein Y ⁻ is an anionic compound.

3. 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 ⁻ , a pyridinium-based compound.

4. The pyridinium-based compound represented by Formula 1 of the above 1 is prepared by reacting the compound represented by the following formula (8) and the compound represented by the following formula (9), a method for producing a pyridinium-based compound:

[Formula 8]

[Formula 9]

(Wherein R ₁ is a substituent connected to a carbon atom except a nitrogen atom, 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, Z is a halogen atom, X is a halogen atom, 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, straight or branched carbon atoms 1 to 12 An alkyl group of the chain or an aryl group having 6 to 12 carbon atoms.

5. In the above 4, after the reaction step of the compound of formula (8) and the compound of formula (9) further comprises a step of ion exchange and ionic compound the anion of the ionic compound 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 -, (FSO 2) 2 N -, (CF 3 SO 2) (CF 3 CO) N - consisting of ^- and N (SO ₂ F) ₂ At least one selected from the group, Z and the halogen anion in the anion of the ionic compound of formula (9) is not the same, the method for producing a pyridinium-based compound.

6. Antistatic agent comprising a pyridinium-based compound of any one of 1 to 3 above.

7. The antistatic agent, acrylic copolymer and the cross-linking agent of the above 6, pressure-sensitive adhesive composition.

8. according to the above 7, wherein the antistatic agent is included in 0.1 to 10 parts by weight based on 100 parts by weight of the acrylic copolymer, pressure-sensitive adhesive composition.

9. Pressure-sensitive adhesive sheet comprising a pressure-sensitive adhesive layer formed of the pressure-sensitive adhesive composition of the above 7.

10. Polarizing plate having a pressure-sensitive adhesive layer formed of the pressure-sensitive adhesive composition of the above 7 on at least one side.

11. Image display device including the polarizing plate of the above 10.

The antistatic agent containing the novel pyridinium-based compound of the present invention shows a markedly improved antistatic function when used in the pressure-sensitive adhesive composition, and can maintain excellent adhesion even in harsh conditions such as high temperature and high humidity.

The present invention relates to a novel pyridinium-based compound and an antistatic agent comprising the same, and when used in the pressure-sensitive adhesive composition, not only shows excellent antistatic performance, but also shows significantly improved durability, even in harsh conditions such as high temperature and high humidity. The present invention relates to a pyridinium-based compound capable of maintaining excellent adhesion.

Hereinafter, the present invention will be described in detail.

<Pyridinium Compounds>

The pyridinium-based compound of the present invention is represented by the formula (1).

[Formula 1]

Expression from, R ₁ is an alkyl group or a cycloalkyl group having 3 to 12 carbon atoms in the straight-chain or branched-chain hydrogen atoms, having from 1 to 12, 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 anionic compound And n is an integer from 1 to 30.

Compound of the formula (1) of the present invention 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, when used in the pressure-sensitive adhesive composition not only shows excellent antistatic performance Excellent compatibility with the pressure-sensitive adhesive composition, it is possible to provide a pressure-sensitive adhesive composition excellent in durability.

Specific examples of the pyridinium-based compound may be at least one compound selected from the group consisting of the following Chemical Formulas 2 to 7.

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

In the formula, Y ⁻ is an anionic compound and is not particularly limited as long as it has excellent compatibility with the cationic compounds of Formulas 1 to 7 of the present invention. For example, Y ⁻ may be 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 -, N (SO 2 F) 2 - and the like, preferably, PF ₆ ^{- _{, BF 4 -, I -,}} N (SO 2 F) 2 - may be a. These may be used alone or in combination of two or more thereof.

<Method for producing pyridinium compound>

The pyridinium compound represented by Chemical Formula 1 of the present invention is prepared through the reaction of a pyridine compound and a polyethylene glycol halide compound.

First, the pyridine-based compound, polyethylene glycol halide compound and the solvent may be performed by mixing and stirring at 60 to 90 ℃ for 4 to 6 hours.

The pyridine-based compound which is a starting material of the reaction may be a compound represented by the following Chemical Formula 8, wherein R ₁ is a substituent connected to a carbon atom excluding a nitrogen atom, and is a hydrogen atom, a straight chain or branched carbon having 1 to 12 carbon atoms. An alkyl group of the chain or a cycloalkyl group having 3 to 12 carbon atoms.

[Formula 8]

The polyethylene glycol halide compound may be represented by the following formula (9).

[Formula 9]

In the formula, Z means a halogen atom, preferably Cl, X is a halogen atom, 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 linear or branched alkyl group having 1 to 12 carbon atoms, or an aryl group having 6 to 12 carbon atoms.

The polyethyleneglycol halide compound is specifically, 1-chloro-2- (2-methoxyethoxy) ethane, acetic acid 2- (2-chloroethoxy) ethyl ester, 1-chloro-2- (2-chloro Methoxy) ethane, 3- (2-chloroethoxy) propionitrile, and the like.

In the mixing reaction, the pyridine-based compound and the polyethylene glycol halide compound may be mixed and reacted in a 1: 1 molar ratio.

As long as it can dissolve the said reaction substance of the solvent used for the said mixing reaction, it will not specifically limit, For example, toluene, acetonitrile, DMF, 1, 4- dioxane, t-butanol, etc. are mentioned, Preferably it is toluene.

The reaction solution which has undergone the mixing reaction can be directly subjected to a washing action to obtain a product, and an ion exchange step may be further performed before the washing action.

In the ion exchange step, the anionic compound in the reaction solution is exchanged with an anion having excellent antistatic performance, and the ionic compound (M ⁺ N ⁻ ) is added to distilled water and stirred at 60 to 90 ° C. for 5 to 8 hours. It may comprise the step of preparing a sex solution.

The ionic compound (M ⁺ N ^-) anion (N ^-) of the kind 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 -, (FSO 2) 2 _{^{N -, (CF 3 SO 2}} ) (CF 3 CO) N -, N (SO 2 F) 2 - and the like, _{^{preferably, PF 6 -, BF 4 -}} , I -, N (SO 2 F) ₂ ^- which is, the Z of the formula (9) with the anion (N ^good-halogen anion), is characterized in that non-identical.

The kind of the cation (M ⁺ ) of the ionic compound (M ⁺ N ⁻ ) is not particularly limited as long as it is a monovalent cation. Examples thereof include Na ⁺ and K ⁺ .

The reaction solution (or the reaction solution that has undergone the ion exchange reaction) may be cooled to room temperature, and after the organic solvent is separated, a washing step may be performed to remove metal salts remaining in the reaction solution.

The washing step is to use a distilled water to dissolve the metal salts in the reaction solution to separate from the organic layer containing the product, can be carried out two or more times as necessary.

After the washing step, only the obtained organic layer may be extracted, followed by distillation under reduced pressure, and the final product of the reaction may be obtained by removing the solvent and the reaction residue through this step.

Antistatic Agent Containing Pyridinium Compound

The antistatic agent of the present invention includes the pyridinium-based compound of the present invention, and has a polyethylene glycol functional group, an ionic functional group of a cation and an anion in the compound, and exhibits excellent antistatic performance, and when used in an adhesive composition, an ionic compound It not only suppresses the bleed out of the film, but also has excellent compatibility with the substrate, and shows excellent adhesion performance.

<Adhesive Composition>

Moreover, this invention provides the adhesive composition containing an acrylic copolymer, a crosslinking agent, and the antistatic agent of this invention.

By containing the ionic functional group, the acryl-based copolymer has excellent compatibility with the ionic compound contained in the antistatic agent, thereby suppressing bleed out of the ionic compound and further improving the durability of the pressure-sensitive 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 antistatic agent containing a pyridinium compound according to the present invention is excellent in compatibility with the pressure-sensitive adhesive composition can significantly increase the durability of the pressure-sensitive adhesive composition.

The antistatic agent is not particularly limited in content. For example, the 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 performance may be insignificant. If it is more than 10 parts by weight, the content of the antistatic agent in the composition is excessive, easily bleed out may occur peeling failure under heat conditions.

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, for example, hexamethyrolmelamine, hexamethoxymethylmelamine, hexabutoxymethylmelamine, and the like, may be added together. Can be used.

 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.

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>

Pyridine (70g, 1mol) and 1-Chloro-2- (2-methoxy-ethoxy) -ethane (139g, 1mol) were dissolved in 300g of toluene, heated to 80 ° C, stirred for 5 hours, and then dissolved in NaPF in distilled water (300g). ₆ (168 g, 1 mol) was slowly added to the solution, the mixture was stirred for an additional 6 hours at the same temperature, the reaction solution was cooled to room temperature, and separated using a separatory funnel to separate the toluene layer. Thereafter, washing was repeated three times with 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. Confirmed.

NMR (400 MHz, CDCl3): 8.75-8.74 (2H), 8.47-8.43 (1H), 7.99-7.95 (2H), 4.53-4.49 (2H), 3.54 (4H), 3.47 (2H), 3.24 (3H) .

2-2. Synthesis of Compounds of Formulas A-2 to 10

<Scheme 2>

<Production method>

Instead of pyridine (70g, 1mol), using the 3-methylpyridine (93g, 1mol) in the same manner as in Preparation Example 2-1, to obtain A-2, it was confirmed by the NMR analysis that the formula A-2.

NMR (400 MHz, CDCl 3): 8.75 (1H), 8.70 (1H), 8.35 (1H), 7.85 (1H), 4.50 (2H), 3.54 (4H), 3.45 (2H), 3.24 (3H).

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

<Scheme 3>

<Production method>

Instead of pyridine (70g, 1mol), 4-methylpyridine (93g, 1mol) was used in the same manner as in Preparation Example 2-1, to obtain A-3, and NMR analysis confirmed that it was Chemical Formula A-3.

NMR (400 MHz, CDCl 3): 8.99 (2H), 7.99 (2H), 4.48 (2H), 3.54 (4H), 3.42 (2H), 3.24 (3H).

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

<Scheme 4>

<Production method>

Preparation Example 2- using Acetic acid 2- (2-chloro-ethoxy) -ethyl ester (166 g, 1 mol) instead of 1-Chloro-2- (2-methoxy-ethoxy) -ethane (139 g, 1 mol) Proceed in the same manner as 3, to obtain A-4, and NMR analysis to confirm that it is a chemical formula A-4.

NMR (400 MHz, CDCl 3): 8.99 (2H), 7.99 (2H), 4.48 (2H), 4.25 (2H), 3.65 (2H), 3.45 (2H), 2.01 (3H).

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

Scheme 5

<Production method>

Instead of 1-Chloro-2- (2-methoxy-ethoxy) -ethane (139g, 1mol), instead of 1-Chloro-2- (2-chloro-ethoxy) -ethane (715g, 5mol) In the same manner as in Preparation Example 2-3, using A) to obtain A-5, and NMR analysis to confirm that it is Chemical Formula A-5.

NMR (400 MHz, CDCl 3): 8.59 (2H), 7.59 (2H), 4.48 (2H), 4.25 (2H), 3.65 (2H), 3.55 (2H), 3.42 (2H).

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

<Scheme 6>

<Production method>

Instead of 1-Chloro-2- (2-methoxy-ethoxy) -ethane (139g, 1mol), the same as in Preparation Example 2-3 using 3- (2-Chloro-ethoxy) -propionitrile (133g, 1mol) To proceed, to obtain A-6, it was confirmed by the NMR analysis that the formula A-6.

NMR (400 MHz, CDCl 3): 8.99 (2H), 7.99 (2H), 4.48 (2H), 3.74 (2H), 3.42 (2H), 2.58 (2H).

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

Scheme 7

<Production method>

Instead of NaPF ₆ (168g, 1mol), KI (166g, 1mol) was carried out in the same manner as in Preparation Example 2-3 to obtain A-7, and NMR analysis confirmed that it is Chemical Formula A-7.

NMR (400 MHz, CDCl 3): 8.39 (2H), 7.39 (2H), 4.48 (2H), 3.54 (4H), 3.42 (2H), 3.24 (3H).

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

Scheme 8

<Production method>

Instead of NaPF ₆ (168g, 1mol), using K (FSO ₂ ) ₂ N (219g, 1mol) in the same manner as in Preparation Example 2-3, to obtain A-8, and NMR analysis to the formula A- It was confirmed that 8.

NMR (400 MHz, CDCl 3): 8.66 (2H), 7.68 (2H), 4.48 (2H), 3.54 (4H), 3.42 (2H), 3.24 (3H).

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

Scheme 9

<Production method>

Instead of NaPF ₆ (168g, 1mol), using NaBF ₄ (110g, 1mol) in the same manner as in Preparation Example 2-3, to obtain A-9, and NMR analysis to confirm that the formula A-9.

NMR (400 MHz, CDCl 3): 8.43 (2H), 7.47 (2H), 4.48 (2H), 3.54 (4H), 3.42 (2H), 3.24 (3H).

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 the corning glass, and subjected to autoclave treatment, and then left at 60 ° C. for 500 hours at 90% humidity, 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

△: 5 or more bubbles or peeling

(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 pyridinium-based compound of the present invention, not only shows 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.

However, in Examples 6 and 7, the content of the antistatic agent in a small amount, it was confirmed that the antistatic function is slightly lower than the other examples.

In addition, the content of the antistatic agent is included in the content range of the present invention, but in the case of Example 8 included in a slightly excess than the preferred content range, the antistatic function was excellent, but the heat resistance was lower than other embodiments, the present invention In the case of Example 9 contained in a slightly excess than the range of, the content of the anionic compound in the pressure-sensitive adhesive composition is excessive, it was confirmed that the bleed out easily occurs, the heat resistance and the heat and humidity heat resistance slightly decreased.

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 formula A-11 instead of the antistatic agent of the present invention was slightly reduced antistatic performance, do not contain a polyethylene glycol derivative in the molecule, the compatibility with the pressure-sensitive adhesive composition can be confirmed that the heat resistance is lowered there was. However, the heat-and-moisture resistance showed the same excellent effect as that of the Example.

Claims (11)

1. A pyridinium compound represented by Formula 1 below:

   [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 , and R ₂ , R ₃ , R ₄ and R ₅ are each independently a hydrogen atom, straight or branched carbon atoms 1 to 12 An alkyl group of the chain 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 pyridinium compound of claim 1, wherein the compound represented by Chemical Formula 1 is selected from the group consisting of compounds represented by the following Chemical Formulas 2 to 7:

   [Formula 2]

   

   [Formula 3]

   

   [Formula 4]

   

   [Formula 5]

   

   [Formula 6]

   

   [Formula 7]

   

   Wherein Y ⁻ is an anionic compound.
3. 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 ^- pyridinium-based compound selected from the group consisting of.
4. A pyridinium-based compound represented by Formula 1 of claim 1 is prepared by reacting a compound represented by the following formula (8) with a compound represented by the following formula (9):

   [Formula 8]

   

   [Formula 9]

   

   (Wherein, R ₁ is a substituent connected to a carbon atom except a nitrogen atom, and 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,

   Z is a halogen atom,

   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).
5. The method according to claim 4, after the reaction step of the compound of formula (8) compound with the formula (9) of the anion of the ionic further comprising an ion exchange step with the compound, wherein the ionic compound 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 -, (FSO 2) 2 N -, (CF 3 SO 2) (CF 3 CO) N - and N (SO ₂ F) ₂ ^- in the group consisting of At least one selected, Z and the halogen anion in the anion of the ionic compound of the formula (9) is not the same, the method for producing a pyridinium-based compound.
6. Antistatic agent containing the pyridinium compound of any one of Claims 1-3.
7. The adhesive composition containing the antistatic agent of Claim 6, an acryl-type copolymer, and a crosslinking agent.
8. The pressure-sensitive adhesive composition of claim 7, wherein the antistatic agent is included in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the acrylic copolymer.
9. The adhesive sheet containing the adhesive layer formed from the adhesive composition of Claim 7.
10. The polarizing plate provided with the adhesion layer formed from the adhesive composition of Claim 7 on at least one surface.
11. An image display device comprising the polarizing plate of claim 10.