KR20150025838A - Acrylic copolmer and adhesive composition containing threrof - Google Patents

Abstract

The present invention relates to an acrylic copolymer and an adhesive composition and, more specifically, to an acrylic copolymer having an epoxy group and an adhesive composition which uses the acrylic copolymer containing one or more kinds of compounds selected from a group consisting of following chemical formula 1 to 3, thereby improving adhesive durability by an ionic functional group applied to the copolymer and effectively controlling corrosion of a metal layer without containing an additional component of an anti-corrosion agent. Here, R_1, R_2, R_3, R_4, and R_5 in chemical formula 1 to 3 are independently an alkyl group of C_1-C_6 or an aromatic hydrocarbon group of C_5-C_8, and X^(-) is a fluorine-containing organic salt, a fluorine-containing inorganic salt, or an iodide ion.

Description

TECHNICAL FIELD [0001] The present invention relates to an acrylic copolymer, and a pressure-sensitive adhesive composition containing the same. BACKGROUND ART [0002]

The present invention relates to a pressure-sensitive adhesive composition capable of simultaneously improving durability and corrosion resistance by introducing an ionic functional group and using an acrylic copolymer containing no acid.

2. Description of the Related Art Generally, a liquid crystal display device (LCD) is provided with a liquid crystal cell containing a liquid crystal and a polarizer, and a suitable adhesive layer is used to bond the liquid crystal cell. As the pressure-sensitive adhesive, an acrylic pressure-sensitive adhesive based on an acrylic copolymer having excellent tackiness and transparency is often used.

When the releasing film is peeled off from the pressure-sensitive adhesive layer in the process of attaching the polarizing plate to the liquid crystal cell, static electricity is generated, and the generated static electricity affects the orientation of the liquid crystal to cause defects or to be introduced between the liquid crystal cell and the pressure- It causes pollution by foreign matter.

To improve this, an ionic antistatic agent is mixed in a pressure-sensitive adhesive composition. However, bleed-out phenomenon precipitated on the surface of the ionic antistatic agent may cause lifting, bubbling and peeling. In particular, such problems can be exacerbated by exposure to high temperature or high temperature and high humidity environments.

Further, in a liquid crystal cell including a metal layer such as ITO, corrosion is generated by H ₂ O and O ₂ contained in the pressure-sensitive adhesive, and metal oxides, hydroxides, and other corrosive products are formed. These may lower the electrical or mechanical stability of the liquid crystal display device, and may cause problems in securing visibility and reliability.

There is a tendency to exclude the use of a hydrogen ion generating monomer (e.g., a monomer having a carboxyl group), which is essentially used for improving the durability of the pressure-sensitive adhesive composition, in order to improve the corrosion resistance of the metal.

As described above, in recent years, there has been a growing demand for a pressure-sensitive adhesive composition that is excellent in antistatic property and durability without using hydrogen ion generating monomers.

In this connection, there has been proposed a method of using an acrylic copolymer in which an amine group or a polyethylene glycol group is introduced to increase the compatibility with an antistatic agent while eliminating the hydrogen ion generating monomer (Korean Patent Publication No. 2009-132564 2011-136760).

However, the above-mentioned method has a considerably insufficient effect to improve the durability deterioration due to the bleeding-out phenomenon.

An object of the present invention is to provide a pressure-sensitive adhesive composition which is excellent in durability and antistatic property by ionic functional groups introduced into a copolymer, and which can effectively inhibit corrosion of a metal layer without containing a corrosion inhibitor component separately.

In order to achieve the above object, the present invention provides an acrylic copolymer containing an epoxy group-containing acrylic copolymer and at least one compound selected from the group consisting of the following formulas (1) to (3).

(Wherein R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are each independently a C ₁ to C ₆ alkyl group or a C ₅ to C ₈ aromatic hydrocarbon group, and X ^- is a fluorine-containing An organic salt, a fluorine-containing inorganic salt, or an iodine ion).

The at least one compound selected from the group consisting of the compounds represented by the formulas (1) to (3) may be at least one selected from the group consisting of the following 4 to 8.

The acrylic copolymer having an epoxy group may contain a (meth) acrylate monomer having an alkyl group having 1-12 carbon atoms and at least one monomer selected from the group consisting of the following formulas (9) to (12).

The at least one monomer selected from the group consisting of the above formulas (9) to (12) may contain 1 to 10 parts by weight per 100 parts by weight of the (meth) acrylate monomer having an alkyl group having 1-12 carbon atoms.

The at least one monomer selected from the group consisting of Formulas 1 to 3 may be contained in an amount of 1 to 5 parts by weight based on 100 parts by weight of the acrylic copolymer having an epoxy group.

The present invention also provides a pressure-sensitive adhesive composition containing the acrylic copolymer.

The pressure-sensitive adhesive composition may further contain a crosslinking agent.

The pressure-sensitive adhesive composition may further contain an antistatic agent.

Also, the present invention relates to a process for producing an acrylic-based copolymer having an epoxy group by polymerizing 100 parts by weight of a (meth) acrylate monomer having an alkyl group of 1-12 carbon atoms and at least one monomer selected from the above- 100 parts by weight of the acrylic copolymer having the epoxy group and 1 to 5 parts by weight of at least one monomer selected from the group consisting of the following formulas 1 to 3 to prepare an acrylic copolymer And a method for producing the acrylic copolymer.

The pressure-sensitive adhesive composition of the present invention has an advantage in that the pressure-sensitive durability can be improved by the ionic functional group introduced into the copolymer.

In addition, the pressure-sensitive adhesive composition of the present invention has an advantage that it can effectively inhibit the corrosion of the metal layer without containing any corrosion inhibitor component.

Further, the pressure-sensitive adhesive composition of the present invention has an advantage of being excellent in durability and satisfying antistatic property because there is no phenomenon of lifting, bubbling and peeling due to surface migration of the antistatic agent.

Therefore, it is expected that the above-mentioned pressure-sensitive adhesive composition will be highly utilized for the purpose of avoiding static electricity in the fields of plastic products, especially electric / electronic devices, where static electricity is easily generated.

The present invention relates to a pressure-sensitive adhesive composition capable of simultaneously improving durability and corrosion resistance by introducing an ionic functional group and using an acrylic copolymer containing no acid.

Hereinafter, the present invention will be described in detail.

The acrylic copolymer of the present invention contains an acrylic copolymer having an epoxy group and at least one compound selected from the group consisting of the following formulas (1) to (3).

[Chemical Formula 1]

(2)

(3)

(Wherein R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are each independently a C ₁ to C ₆ alkyl group or a C ₅ to C ₈ aromatic hydrocarbon group, and X ^- is a fluorine-containing An organic salt, a fluorine-containing inorganic salt, or an iodine ion).

At least one compound selected from the group consisting of the above-mentioned formulas (1) to (3) is a monomer having an ionic functional group and is introduced into the acrylic copolymer by reaction of an epoxy group of the acrylic copolymer having an epoxy group with a thiol group. The ionic functional groups introduced into the copolymer cause an increase in adhesion due to polar-polar interaction with the glass.

In addition, the ionic functional group forms a strong ionic bond with the ionic antistatic agent, and the bleed out phenomenon in which the antistatic agent component migrates to the surface due to the ionic bond and is deposited is suppressed, and the durability is excellent. This phenomenon can be suppressed even under high temperature or high temperature / high humidity environment, and excellent durability can be maintained.

The composition of the present invention is an acid-free pressure-sensitive adhesive composition which does not generate an acid at the same time as adhesion durability and thus has less concern about corrosion of ITO.

The acrylic copolymer having an epoxy group of the present invention preferably contains a (meth) acrylate monomer having an alkyl group having 1-12 carbon atoms and an acrylate monomer having an epoxy group. In the present invention, (meth) acrylate means acrylate and methacrylate, and the content is based on the solid content

Examples of the (meth) acrylate monomer having an alkyl group having 1-12 carbon atoms include (meth) acrylates derived from an aliphatic alcohol having 1 to 12 carbon atoms, such as methyl acrylate, ethyl acrylate, propyl acrylate, (meth) acrylate, n-butyl (meth) acrylate, 2-butyl (meth) acrylate, t- (Meth) acrylate, decyl (meth) acrylate, and lauryl (meth) acrylate. These may be used alone or in combination of two or more. Of these, n-butyl acrylate, 2-ethylhexyl acrylate or a mixture thereof is preferable.

The acrylate monomer having an epoxy group may be at least one selected from the group consisting of the following formulas (9) to (12).

[Chemical Formula 9]

[Chemical formula 10]

(11)

[Chemical Formula 12]

The acrylate monomer having such an epoxy group may contain 1 to 10 parts by weight, preferably 2 to 5 parts by weight, based on 100 parts by weight of the (meth) acrylate monomer having an alkyl group having 1-12 carbon atoms. When the content is less than 1 part by weight, the adhesive strength improving effect and the bleed-out inhibiting effect of the antistatic agent are insufficient. When the amount exceeds 10 parts by weight, the remaining epoxy groups participate in the crosslinking reaction and the gel fraction excessively increases. .

The acrylic copolymer having an epoxy group of the present invention may further contain a polymerizable monomer having a crosslinkable functional group in addition to an acrylate monomer having an epoxy group. The added polymerizable monomer having a crosslinkable functional group can impart durability and cutability by reinforcing the cohesive strength or adhesive strength of the pressure-sensitive adhesive composition by chemical bonding, and a component that does not generate hydrogen ions (H ⁺ ) is used .

Examples of the polymerizable monomer having a crosslinkable functional group include a monomer having a hydroxy group, a monomer having an amide group, and a monomer having a tertiary amine group, and these may be used alone or in combination of two or more.

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 polymerizable monomer having such a crosslinkable functional group is preferably contained in an amount of 0.05 to 10 parts by weight, more preferably 0.1 to 8 parts by weight, per 100 parts by weight of the (meth) acrylate monomer having an alkyl group having 1-12 carbon atoms good. When the content is less than 0.05 part by weight, the cohesive force of the pressure-sensitive adhesive becomes small and durability may be deteriorated. When the content is more than 10 parts by weight, the adhesive strength may be lowered and the durability may be deteriorated due to a high gel fraction.

The acrylic copolymer having an epoxy group of the present invention may further contain other polymerizable monomers other than the above monomers in a range that does not lower the adhesive force, for example, 10 parts by weight or less based on the total amount.

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 of the present invention contains the above acrylic copolymer having an epoxy group and at least one monomer selected from the above-mentioned formulas (1) to (3).

), TFSI(

), FSI(

) 등이 사용될 수 있다.The anion X of said ^monomer is a fluorinated organic salt, inorganic salt or the fluorine-containing and iodine ions can be used, in consideration of durability and antistatic property at the same time, an organic salt and an iodine salt containing fluorine are preferred. Examples of the fluorine-containing organic salt include OTF (

), TFSI (

), FSI

) May be used.

Preferably, at least one compound selected from the group consisting of Formulas 1 to 3 may be at least one compound selected from the group consisting of the following 4 to 8.

 [Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(7)

[Chemical Formula 8]

The at least one compound selected from the group consisting of Formulas 1 to 3 may contain 1 to 5 parts by weight, preferably 1 to 3 parts by weight, based on 100 parts by weight of the acrylic copolymer having an epoxy group. If the content is less than 1 part by weight, the adhesive strength improving effect may be insufficient. If the content is more than 5 parts by weight, the remaining thiol group may react with the cross-linking agent to lower the gel fraction to cause lack of cohesive force, .

As described above, the process for producing an acrylic copolymer according to the present invention is characterized in that 100 parts by weight of a (meth) acrylate monomer having an alkyl group having from 1 to 12 carbon atoms and at least one monomer selected from the group consisting of the following formulas (9) to And 1 to 5 parts by weight of at least one compound selected from the group consisting of the following general formulas (1) to (3) are reacted in the presence of a catalyst to produce an acrylic copolymer having an epoxy group, To prepare an acrylic copolymer.

Further, the present invention is characterized by a pressure-sensitive adhesive composition containing the acrylic copolymer. The pressure-sensitive adhesive composition may further contain a crosslinking agent.

The crosslinking agent is a component for reinforcing the cohesive force of the pressure-sensitive adhesive by properly crosslinking the copolymer, and the kind thereof is not particularly limited. Examples thereof include isocyanate compounds and epoxy compounds, which may be used alone or in combination of two or more. Isocyanate-based compounds are preferable in view of improvement in adhesion and durability.

Examples of the isocyanate compound include tolylene diisocyanate, xylene diisocyanate, 2,4-diphenylmethane diisocyanate, 4,4-diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, tetramethyl xylene diisocyanate , Diisocyanate compounds such as naphthalene diisocyanate; An adduct obtained by reacting 3 moles of a diisocyanate compound with 1 mole of a polyhydric alcohol compound such as trimethylolpropane, an isocyanurate compound in which 3 moles of a diisocyanate compound is self-condensed, a diisocyanate obtained from 2 moles of 3 moles of a diisocyanate compound And multifunctional isocyanate compounds containing three functional groups such as burette, triphenylmethane triisocyanate and methylene bistriisocyanate in which the remaining one mole of diisocyanate is condensed in urea.

Examples of the epoxy compound include ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol Hexanediol diglycidyl ether, polytetramethylene glycol diglycidyl ether, glycerol diglycidyl ether, glycerol triglycidyl ether, glycerol diglycidyl ether, glycerol diglycidyl ether, Diglycerol polyglycidyl ether, polyglycerol polyglycidyl ether, resorcinol diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, trimethylol propane triglycidyl ether, pentaerythritol Polyglycidyl ether, sorbitol polyglycidyl ether, adipic acid diglycidyl ester, phthalic acid diglycidyl ester, tris (glycidyl) isocyanurate N, N ', N'-tetraglycidyl-m-glycidoxyethyl isocyanurate, 1,3-bis (N, N-glycidylaminomethyl) cyclohexane, Xylylenediamine, and the like.

In addition, an isocyanate compound, an epoxy compound, and a melamine compound may be used alone or in admixture of two or more.

Examples of the melamine-based compound include hexamethylol melamine, hexamethoxymethyl melamine, and hexabutoxymethyl melamine.

The crosslinking agent is preferably contained in an amount of 0.1 to 15 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the copolymer based on the solid content. When the content is less than 0.1 parts by weight, the cohesive force becomes small due to insufficient crosslinking, resulting in deterioration of durability such as peeling and deterioration of cutability. If the content is more than 15 parts by weight, excessive crosslinking reaction may cause a problem of relaxation of residual stress have.

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

The kind of the silane coupling agent is not particularly limited, and examples thereof include vinylchlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3- 3-glycidoxypropyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, Acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-acryloxypropyltrimethoxysilane , N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) Methyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethylbutylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3- Dimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis (triethoxysilylpropyl) tetrasulfide, 3-isocyanatepropyltriethoxysilane, and the like. These may be used alone or in combination of two or more.

The silane coupling agent may be contained in an amount of 0 to 10 parts by weight, preferably 0.005 to 5 parts by weight, based on 100 parts by weight of the copolymer based on the solid content. If the content exceeds 10 parts by weight, the durability may be lowered.

Further, the pressure-sensitive adhesive composition may further contain an antistatic agent, and an ionic antistatic agent is preferable. The ionic antistatic agent is an ionic salt composed of an anion and a cation, and is not particularly limited as long as it can impart ionic conductivity to the adhesive. In addition, ionic antistatic agents that do not contain a thiol group are preferable in order to prevent a lack of cohesive force due to a decrease in the gel fraction.

A cation selected from the group consisting of an alkali metal salt, an ammonium salt, a sulfonium salt and a phosphonium salt; An ionic salt consisting of an anion selected from the group consisting of a fluorine-containing inorganic salt, a fluorine-containing organic salt and an iodide ion.

Such an ionic antistatic agent may be contained in an amount of 0.1 to 5 parts by weight, preferably 0.5 to 3 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. When the content is more than 5 parts by weight, it may be difficult to secure durability.

In addition, the present invention can play a role as an ionic antistatic agent when one or more monomers selected from the group consisting of the formulas (1) to (3) contained in the acrylic copolymer is contained in an excessive amount, specifically in a reaction equivalent to the epoxy group .

In addition to the above components, the pressure-sensitive adhesive composition may further contain additives such as a tackifier resin, an antioxidant, a corrosion inhibitor, a leveling agent, a surface lubricant, a dye, a pigment, and the like in order to control adhesion, cohesion, viscosity, , Defoaming agents, fillers, light stabilizers, and the like.

The pressure-sensitive adhesive composition of the present invention can be used particularly as a pressure-sensitive adhesive for a polarizing plate or a pressure-sensitive adhesive for a surface protective film for bonding with a liquid crystal cell. It can be used not only as a protective film, a reflective sheet, a structural adhesive sheet, a photographic adhesive sheet, a lane marking adhesive sheet, an optical adhesive product, an electronic component adhesive, but also a general commercial adhesive sheet product.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the present invention. Such variations and modifications are intended to be within the scope of the appended claims.

Manufacturing example  : Acrylic copolymer preparation

Manufacturing example  One

85 parts by weight of n-butyl acrylate (BA), 10 parts by weight of methyl acrylate (MA), 2 parts by weight of 2-hydroxyethyl acrylate 2 , And 3 parts by weight of glycidoxypropylmethacrylate (GMA) were put in a flask, and 100 parts by weight of acetone 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 homogenized, 0.07 part by weight of azobisisobutyronitrile (AIBN) was added as a reaction initiator and reacted for 6 hours to prepare an acrylic copolymer having a weight average molecular weight of about 1,000,000.

Manufacturing example  2

An acrylic copolymer having a weight average molecular weight of about 1,000,000 was prepared by charging glycidoxybutyl acrylate (4HBAGE) in place of 3 parts by weight of glycidoxypropyl methacrylate (GMA) in the same manner as in Preparation Example 1.

Manufacturing example  3-10

After completion of the same operations as in Preparation Example 1, monomers were added as shown in the following Table 1 while maintaining the same temperature and reacted for 4 hours to prepare an acrylic copolymer.

division Acrylic copolymer Monomer type (parts by weight) Production Example 3 Production Example 1 (4), 1 part by weight Production Example 4 Production Example 1 (5), 1 part by weight Production Example 5 Production Example 1 (6), 1 part by weight Production Example 6 Production Example 1 (7), 1 part by weight Production Example 7 Production Example 2 Formula 8, 1 part by weight Production Example 8 Production Example 1 (4), 3 parts by weight Production Example 9 Production Example 1 (4), 5 parts by weight Production Example 10 Production Example 1 (4), 7 parts by weight

화학식 5:

화학식 6:

화학식 7:

화학식 8:

(4)

(5)

(6)

(7)

(8)

Manufacturing example  11

Except that 83 parts by weight of n-butyl acrylate (BA), 10 parts by weight of methyl acrylate (MA), 2 parts by weight of 2-hydroxyethyl acrylate, 2 parts by weight of glycidoxypropyl methacrylate GMA), and 1 part by weight of the structural formula (4) were used to prepare an acrylic copolymer.

Manufacturing example  12

Except that 78 parts by weight of n-butyl acrylate (BA), 10 parts by weight of methyl acrylate (MA), 2 parts by weight of 2-hydroxyethyl acrylate, glycidoxypropyl methacrylate ( GMA) and 1 part by weight of the structural formula (4) were used to prepare an acrylic copolymer.

Manufacturing example  13

Except that 76 parts by weight of n-butyl acrylate (BA), 10 parts by weight of methyl acrylate (MA), 2 parts by weight of 2-hydroxyethyl acrylate, 2 parts by weight of glycidoxypropyl methacrylate GMA) (12 parts by weight) and 1 part by weight of the structural formula (4) were used to prepare an acrylic copolymer.

Example  1-19 and Comparative Example  1-5

As shown in Table 2, the acrylic copolymer, crosslinking agent, ionic antistatic agent and silane coupling agent of Preparation Example were mixed and diluted with ethyl acetate to prepare a pressure-sensitive adhesive composition having a solid content concentration of 15%.

division
(Parts by weight) Acrylic
Copolymer
(Production example, content) Crosslinking agent (A) Ionic antistatic agent Silane
Coupling agent One 2 3 4 Example 1 2, 100 One - - - B-10, 2 0.5 Example 2 3, 100 One - - - B-10, 2 0.5 Example 3 4, 100 One - - - B-10, 2 0.5 Example 4 5, 100 One - - - B-10, 2 0.5 Example 5 6, 100 One - - - B-10, 2 0.5 Example 6 7, 100 One - - - B-10, 2 0.5 Example 7 8, 100 One - - - B-10, 2 0.5 Example 8 9, 100 One - - - B-10, 2 0.5 Example 9 10,100 One - - - B-10, 2 0.5 Example 10 11,100 One - - - B-10, 2 0.5 Example 11 12,100 One - - - B-10, 2 0.5 Example 12 13,100 One - - - B-10, 2 0.5 Example 13 2, 100 - One - - B-10, 2 0.5 Example 14 2, 100 - - One - B-10, 2 0.5 Example 15 2, 100 - - - One B-10, 2 0.5 Example 16 2, 100 One - - - B-1, 1 + B-10, 1 0.5 Example 17 2, 100 One - - - B-2, 1 + B-10, 1 0.5 Example 18 2, 100 One - - - B-3, 1 + B-10, 1 0.5 Example 19 2, 100 One - - - B-4, 1 + B-10, 1 0.5 Example 20 2, 100 One - - - B-5, 1 + B-10, 1 0.5 Comparative Example 1 1, 100 One - - - B-6, 2 0.5 Comparative Example 2 1, 100 One - - - B-7, 2 0.5 Comparative Example 3 1, 100 One - - - B-8, 2 0.5 Comparative Example 4 1, 100 One - - - B-9, 2 0.5 Comparative Example 5 1, 100 One - - - B-10, 2 0.5

B-2:

B-3:

B-4:

B-5:

B-6:

B-7:

B-8:

B-9: NaPF₆
B-10: LiTFSI
실란커플링제:KBM-403(신에츠사)A-1: Coronate-L (TDI crosslinking agent, CORONATE-L, Japan Urethane Industry)
A-2: Isocyanate art of TDI (Urethane Japan)
A-3: Coronate-HXR (isocyanurate of HDI, Urethane Company of Japan)
A-4: Takenate-110N (XDI crosslinking agent, TAKENATE-110N Mitsui Chemicals
B-1:

B-2:

B-3:

B-4:

B-5:

B-6:

B-7:

B-8:

B-9: NaPF₆
B-10: LiTFSI
Silane coupling agent: KBM-403 (Shin-Etsu)

The pressure-sensitive adhesive composition prepared above was applied on a release film coated with silicone release agent to a thickness of 25 탆 and dried at 100 캜 for 1 minute to form an adhesive layer.

The pressure-sensitive adhesive layer prepared above was laminated to an iodine-based polarizing plate having a thickness of 185 μm by pressure-sensitive adhesive processing to produce a polarizer with a pressure-sensitive adhesive. The prepared polarizing plate was stored for 20 days under conditions of 23 캜 and 60% RH.

Test Example

The properties of the pressure-sensitive adhesive composition and the polarizer with a pressure-sensitive adhesive prepared in the above Examples and Comparative Examples were measured by the following methods, and the results are shown in Table 3 below.

1. Heat resistance / Humidity Durability

The release film of the polarizing plate with a pressure-sensitive adhesive was peeled off, and the surface of the pressure-sensitive adhesive layer was bonded with Corning glass. After leaving for 300 hours at 80 캜 (heat resistance) / 60 캜 and 90RH% (humidity and humidity resistance), appearance was confirmed.

<Evaluation Criteria>

Bubbles and peeling were visibly very visible: x

Bubbles and peeling phenomenon were observed: △

Bubble or peeling phenomenon is slightly observed, but polarizer performance is maintained: ○

Bubbles and peeling phenomenon are observed: ◎

2. Surface resistivity (Ω / □)

The prepared polarizer plate with a pressure-sensitive adhesive was measured 10 times at three points of the pressure-sensitive adhesive layer using a surface resistance meter (MCP-HT450, Mitsubishi Chemical Co., Ltd.) and expressed as an average value thereof.

division durability Surface resistivity
(Ω / □) Heat resistance Wet heat Example 1 ◎ ◎ 2X10 ¹⁰ Example 2 ◎ ◎ 2X10 ¹⁰ Example 3 ◎ ◎ 2X10 ¹⁰ Example 4 ◎ ◎ 8X10 ¹⁰ Example 5 ◎ ◎ 5X10 ¹⁰ Example 6 ◎ ◎ 9X10 ⁹ Example 7 ◎ ○ 5X10 ⁹ Example 8 ◎ ◎ 3X10 ⁹ Example 9 ○ ◎ 3X10 ¹⁰ Example 10 ◎ ◎ 4X10 ¹⁰ Example 11 ○ ◎ 5X10 ¹⁰ Example 12 ○ ○ 6X10 ¹⁰ Example 13 ◎ ◎ 2X10 ¹⁰ Example 14 ○ ◎ 1X10 ¹⁰ Example 15 ◎ ◎ 2X10 ¹⁰ Example 16 ○ ◎ 3X10 ¹⁰ Example 17 ○ ◎ 3X10 ¹⁰ Example 18 ◎ ◎ 1X10 ¹⁰ Example 19 ○ ◎ 5X10 ¹⁰ Example 20 ○ ◎ 3X10 ¹⁰ Comparative Example 1 × △ 7X10 ¹⁰ Comparative Example 2 × × 9X10 ¹⁰ Comparative Example 3 × △ 6X10 ¹⁰ Comparative Example 4 × × 9X10 ¹⁰ Comparative Example 5 × △ 5X10 ¹⁰

The pressure-sensitive adhesive compositions of Examples 1 to 20 using an acrylic copolymer having an epoxy group and an acrylic copolymer containing a specific ionic compound according to the present invention, as shown in Table 3, It was confirmed that the durability and surface resistivity of wet heat resistance and the like were excellent at the same time.

Claims (9)

An acrylic copolymer having an epoxy group, and at least one compound selected from the group consisting of the following formulas (1) to (3):
[Chemical Formula 1]

(2)

(3)

(Wherein R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are each independently a C ₁ to C ₆ alkyl group or a C ₅ to C ₈ aromatic hydrocarbon group, and X ^- is a fluorine-containing An organic salt, a fluorine-containing inorganic salt, or an iodine ion).
The acrylic copolymer according to claim 1, wherein the at least one compound selected from the group consisting of the compounds represented by formulas (1) to (3) is at least one selected from the group consisting of the following 4 to 8:
[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(7)

[Chemical Formula 8]

The acrylic copolymer according to claim 1, wherein the acrylic copolymer having an epoxy group contains a (meth) acrylate monomer having an alkyl group having 1-12 carbon atoms and at least one monomer selected from the group consisting of the following formulas (9) to :
[Chemical Formula 9]

[Chemical formula 10]

(11)

[Chemical Formula 12]

The acrylic copolymer according to claim 3, wherein the at least one monomer selected from the group consisting of the above-mentioned formulas (9) to (12) contains 1 to 10 parts by weight per 100 parts by weight of the (meth) acrylate monomer having an alkyl group having 1-12 carbon atoms. coalescence.
The acrylic copolymer according to claim 1, wherein the at least one monomer selected from the group consisting of Formulas 1 to 3 contains 1 to 5 parts by weight based on 100 parts by weight of the acrylic copolymer having an epoxy group.
A pressure-sensitive adhesive composition containing the acrylic copolymer according to any one of claims 1 to 5.
The pressure-sensitive adhesive composition according to claim 6, wherein the pressure-sensitive adhesive composition further comprises a crosslinking agent.
The pressure-sensitive adhesive composition according to claim 6, wherein the pressure-sensitive adhesive composition further contains an antistatic agent.
100 parts by weight of a (meth) acrylate monomer having an alkyl group having 1-12 carbon atoms and at least one compound selected from the group consisting of the following formulas (9) to (12) are polymerized in an amount of 1 to 10 parts by weight to prepare an acrylic copolymer having an epoxy group Wow,
100 parts by weight of the acrylic copolymer having an epoxy group and 1 to 5 parts by weight of at least one monomer selected from the group consisting of the following formulas 1 to 3 are reacted to prepare an acrylic copolymer :
[Chemical Formula 1]

(2)

(3)

Wherein R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are each independently a C ₁ to C ₆ alkyl group and X ^- is a fluorine-containing organic salt, a fluorine-containing inorganic salt or an iodide ion being).
[Chemical Formula 9]

[Chemical formula 10]

(11)

[Chemical Formula 12]