KR20150011303A - Adhesive composition - Google Patents

Abstract

The present invention relates to an adhesive composition and, more specifically, to an adhesive composition which contains an acrylic copolymer including an acrylate-based monomer having an amino alcohol group, and an ionic antistatic agent, thereby having excellent durability and antistatic properties by avoiding such as separation, air bubbles, and peeling caused by surface transition of the antistatic agent, and effectively controlling corrosion of a metal layer without containing an additional anticorrosion agent.

Description

[0001] ADHESIVE COMPOSITION [0002]

The present invention relates to a pressure-sensitive adhesive composition capable of simultaneously improving durability, antistatic property and corrosion-preventive property by suppressing bleed-out of an antistatic agent by increasing the compatibility of an antistatic agent and 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.

The present invention provides a pressure-sensitive adhesive composition which is excellent in durability as well as antistatic property due to no phenomenon of lifting, bubbling and peeling due to surface migration of an antistatic agent and which can effectively inhibit corrosion of a metal layer without containing a corrosion inhibitor component separately The purpose is to provide.

In order to achieve the above object, the present invention provides an adhesive composition comprising an acrylic copolymer and an ionic antistatic agent prepared by copolymerizing monomers containing an acrylate monomer having an amino alcohol group.

The acrylate-based monomer having an amino alcohol group may be an acrylate-based monomer having a? -Hydroxydialkylamino group (a hydroxy-carbon containing a tertiary amino group at an adjacent carbon).

The acrylate monomer having an amino alcohol group may include a compound represented by the following formula (1) or (2).

Wherein R ₁ is an aliphatic hydrocarbon with or without a heteroatom of N or O having 1 to 12 carbon atoms and R ₂ is an aliphatic or aromatic hydrocarbon with or without a heteroatom of N or O having 1 to 12 carbon atoms hydrocarbons, and, R3 is an aliphatic hydrocarbon group with or without a hetero element of N or O with a carbon number of 1 ~ 6, R4 is hydrogen or a methyl group, and R ₁ and R ₂ is a carbon adjacent to each other 5 ring or 6 < / RTI > ring, and the ring may contain a heteroatom.)

Wherein R ₁ is an aliphatic hydrocarbon with or without a heteroatom of N or O having 1 to 12 carbon atoms and R ₂ is an aliphatic or aromatic hydrocarbon with or without a heteroatom of N or O having 1 to 12 carbon atoms hydrocarbons, and, R3 is an aliphatic hydrocarbon group with or without a hetero element of N or O with a carbon number of 1 ~ 6, R4 is hydrogen or a methyl group, and R ₁ and R ₂ is a carbon adjacent to each other 5 ring or 6 < / RTI > ring, and the ring may contain a heteroatom.)

The acrylate monomer having an amino alcohol group may be at least one selected from the group consisting of the following formulas (3) to (12).

The acrylic copolymer may be prepared by copolymerizing monomers including an acrylate monomer having a (meth) acrylate monomer having an alkyl group of 1-12 carbon atoms and an amino alcohol group.

The acrylate monomer having an amino alcohol group may be contained in an amount of 1 to 10 parts by weight based on 100 parts by weight of the (meth) acrylate monomer having an alkyl group having 1-12 carbon atoms.

Wherein the ionic antistatic agent is 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.

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

The pressure-sensitive adhesive composition of the present invention is free from lifting, bubbling and peeling due to surface migration of an antistatic agent, and has an advantage of being excellent in durability and satisfying antistatic property at the same time.

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.

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, antistatic property and corrosion-preventive property by suppressing bleed-out of an antistatic agent by increasing the compatibility of an antistatic agent and an acrylic copolymer containing no acid .

Hereinafter, the present invention will be described in detail.

The pressure-sensitive adhesive composition of the present invention contains an acrylic copolymer and an ionic antistatic agent prepared by copolymerizing monomers containing an acrylate monomer having an amino alcohol group.

Generally, acrylic acid is used as a monomer in order to improve adhesion to glass and compatibility with an antistatic agent.

Specifically, the carboxylic acid is introduced into the copolymer by acrylic acid, and the introduced carboxylic acid forms a hydrogen bond in the copolymer to improve the cohesive force and forms a hydrogen bond with the silanol group of the glass to improve the adhesion. In addition, the carboxylic acid introduced into the copolymer suppresses the bleeding-out of the antistatic agent by polar interaction with the ionic antistatic agent, thereby improving the durability.

However, in the case of a product including a metal layer such as ITO, since corrosion occurs due to H ₂ O and O ₂ contained in the pressure-sensitive adhesive to form metal oxides, hydroxides, and other corrosive products, an acid-free pressure- Is required. Since such an acid-free pressure-sensitive adhesive composition does not have a carboxyl group, there is a problem that it is difficult to ensure durability because of low adhesion, low aggregation and lack of stabilizing effect of an antistatic agent.

The pressure-sensitive adhesive composition according to the present invention contains an acrylate-based monomer having an amino alcohol group as a monomer for producing an acrylic copolymer. When an acrylate monomer having an amino alcohol group is contained, an ionization tendency such as a carboxylic acid is increased, thereby increasing the interaction with the glass to improve the adhesion, and forming a hydrogen bond in the acrylic copolymer to improve cohesion have. In addition, since the interaction with the antistatic agent is increased to suppress the bleed-out of the antistatic agent, the durability of the pressure-sensitive adhesive is largely improved, while the acid is not generated and the concern about the corrosion of the ITO is small.

The following structural formula shows, for example, the functional relationship between an acrylic acid monomer (structural formula 1) and an acrylate monomer (structural formula 2) having an amino alcohol group of the present invention.

(Structural formula 1)

(Formula 2)

The amine in the molecule functions as a base which removes H ⁺ from the hydroxy group present at a close position and acts as a scavenger for immobilizing the H ⁺ . That is, it is understood that the pressure-sensitive adhesive composition containing the same has the advantages of the polar group possessed by the carboxyl group, and also plays a role in securing the ITO corrosion inhibition at the same time.

The acrylate monomer having an amino alcohol group contained in the acrylic copolymer may be an acrylate monomer having a? -Hydroxydialkylamino group (a hydroxy carbon containing a tertiary amino group at an adjacent carbon).

Preferably, the acrylate monomer having the? -Hydroxydialkylamino group may include a compound represented by the following formula (1) or (2).

[Chemical Formula 1]

Wherein R ₁ is an aliphatic hydrocarbon with or without a heteroatom of N or O having 1 to 12 carbon atoms and R ₂ is an aliphatic or aromatic hydrocarbon with or without a heteroatom of N or O having 1 to 12 carbon atoms hydrocarbons, and, R3 is an aliphatic hydrocarbon group with or without a hetero element of N or O with a carbon number of 1 ~ 6, R4 is hydrogen or a methyl group, and R ₁ and R ₂ is a carbon adjacent to each other 5 ring or 6 < / RTI > ring, and the ring may contain a heteroatom.)

(2)

Wherein R ₁ is an aliphatic hydrocarbon with or without a heteroatom of N or O having 1 to 12 carbon atoms and R ₂ is an aliphatic or aromatic hydrocarbon with or without a heteroatom of N or O having 1 to 12 carbon atoms hydrocarbons, and, R3 is an aliphatic hydrocarbon group with or without a hetero element of N or O with a carbon number of 1 ~ 6, R4 is hydrogen or a methyl group, and R ₁ and R ₂ is a carbon adjacent to each other 5 ring or 6 < / RTI > ring, and the ring may contain a heteroatom.)

More preferably, the acrylate monomer having the amino alcohol group may be at least one selected from the group consisting of the following formulas (3) to (12).

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(7)

[Chemical Formula 8]

[Chemical Formula 9]

[Chemical formula 10]

(11)

[Chemical Formula 12]

The acrylic copolymer of the present invention is preferably prepared by copolymerizing monomers comprising a (meth) acrylate monomer having an alkyl group of 1-12 carbon atoms and an acrylate monomer having an amino alcohol group. In the present invention, (meth) acrylate means acrylate and methacrylate, and the content is based on the solid content.

The (meth) acrylate monomer having an alkyl group having 1 to 12 carbon atoms is preferably selected from the group consisting of 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, decyl (meth) acrylate and lauryl (meth) acrylate. Of these, n-butyl acrylate, 2-ethylhexyl acrylate Or a mixture thereof. These may be used alone or in combination of two or more.

The acrylate monomer having an amino alcohol group is preferably contained in an amount of 1 to 10 parts by weight, more preferably 2 to 7 parts by weight, based on 100 parts by weight of the (meth) acrylate monomer having an alkyl group having 1-12 carbon atoms good. If the content is less than 1 part by weight, the effect of improving durability may be insignificant. If the content is more than 10 parts by weight, it may be difficult to secure other adhesive properties such as reworkability.

The monomer for producing the acrylic copolymer of the present invention may further contain a polymerizable monomer having a crosslinkable functional group in addition to the acrylate monomer having the amino alcohol group.

The 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 monomers having a hydroxy group, monomers having an amide group, monomers having a tertiary amine group, etc. These monomers 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, .

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, a high gel fraction may lower the adhesive strength and cause durability problems.

The monomer for producing the acrylic copolymer of the present invention may further contain other polymerizable monomers other than the above monomers in a range not lowering the adhesive force, for example, 10 parts by weight or less based on the total amount of the 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 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.

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 15 parts by weight, preferably 0.5 to 10 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, and when it is more than 10 parts by weight, it may be difficult to secure durability.

The pressure-sensitive adhesive composition of the present invention may further contain a crosslinking agent.

The crosslinking agent can improve the adhesion and durability, and can maintain the reliability at a high temperature and the shape of the pressure-sensitive adhesive.

The cross-linking agent may be an isocyanate-based, epoxy-based, melamine-based, peroxide-based, metal chelating-based, oxazoline-based, or the like. Preferred is a double isocyanate-based or epoxy-based.

Examples of the isocyanate-based isocyanate include isocyanate-based compounds such as tolylene diisocyanate, xylene diisocyanate, 2,4-diphenylmethane diisocyanate, 4,4-diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, tetramethyl xylene diisocyanate, Diisocyanate compounds such as isocyanate; 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.

The epoxy system may be an ethylene glycol diglycidyl ether, a diethylene glycol diglycidyl ether, a polyethylene glycol diglycidyl ether, a propylene glycol diglycidyl ether, a tripropylene glycol diglycidyl ether, a polypropylene glycol di Hexanediol diglycidyl ether, polytetramethylene glycol diglycidyl ether, glycerol diglycidyl ether, glycerol triglycidyl ether, diethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, Glycerol polyglycidyl ether, polyglycerol polyglycidyl ether, resorcinol diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, trimethylol propane triglycidyl ether, pentaerythritol poly Glycidyl ether, sorbitol polyglycidyl ether, adipic acid diglycidyl ester, phthalic acid diglycidyl ester, tris (glycidyl) isocyanurate N, N, N ', N'-tetraglycidyl-m-hexyldicyclohexyl) isocyanurate, 1,3-bis (N, N-glycidylaminomethyl) cyclohexane, Xylylenediamine, and the like.

Examples of the melamine type include hexamethylol melamine, hexamethoxymethyl melamine, and hexabutoxymethyl melamine.

Such a crosslinking agent may be contained in an amount of 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. If the content is less than 0.1 part by weight, the cohesive strength may be decreased due to insufficient crosslinking, which may deteriorate the durability of the adhesive durability and the cutability. If the content is more than 15 parts by weight, the residual stress due to the excessive crosslinking reaction may be deteriorated.

In addition to the above components, the pressure-sensitive adhesive composition may further contain various additives such as a silane coupling agent, a tackifier resin, an antioxidant, a leveling agent, a surface lubricant, a dye, an antioxidant, and the like in order to control the adhesion, cohesion, viscosity, A pigment, a defoaming agent, a filler, a light stabilizer, and the like.

Such an additive can appropriately control the content within a range that does not impair the effect of the present invention.

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  1>

3중량부로 이루어진 단량체 혼합물을 투입한 후, 용제로 아세톤 100중량부를 투입하였다. 그 다음 산소를 제거하기 위하여 질소가스를 1시간 동안 퍼징한 후, 80℃로 유지하였다. 상기 혼합물을 균일하게 한 후, 반응개시제로 아조비스이소부티로니트릴(AIBN) 0.07중량부를 투입하고, 6시간 동안 반응시켜 중량평균분자량이 약 115만인 아크릴계 공중합체를 제조하였다.
To a 1 L reactor equipped with a cooling device for regulating the temperature of the reflux of nitrogen gas, 96 parts by weight of n-butyl acrylate (BA), 1 part by weight of 4-hydroxybutyl acrylate,

, And 100 parts by weight of acetone as a solvent were added to the mixture. Nitrogen gas was then purged for 1 hour to remove oxygen and then maintained at 80 ° 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 1,150,000.

< Manufacturing example  2>

대신에

을 사용하여 아크릴계 공중합체를 제조하였다.
The procedure of Preparation Example 1 was repeated,

Instead of

To prepare an acrylic copolymer.

< Manufacturing example  3>

대신에

을 사용하여 아크릴계 공중합체를 제조하였다.
The procedure of Preparation Example 1 was repeated,

Instead of

To prepare an acrylic copolymer.

< Manufacturing example  4>

대신에

을 사용하여 아크릴계 공중합체를 제조하였다.
The procedure of Preparation Example 1 was repeated,

Instead of

To prepare an acrylic copolymer.

< Manufacturing example  5>

대신에

을 사용하여 아크릴계 공중합체를 제조하였다.
The procedure of Preparation Example 1 was repeated,

Instead of

To prepare an acrylic copolymer.

< Manufacturing example  6>

대신에

을 사용하여 아크릴계 공중합체를 제조하였다.
The procedure of Preparation Example 1 was repeated,

Instead of

To prepare an acrylic copolymer.

< Manufacturing example  7>

대신에

을 사용하여 아크릴계 공중합체를 제조하였다.
The procedure of Preparation Example 1 was repeated,

Instead of

To prepare an acrylic copolymer.

< Manufacturing example  8>

대신에

을 사용하여 아크릴계 공중합체를 제조하였다.
The procedure of Preparation Example 1 was repeated,

Instead of

To prepare an acrylic copolymer.

< Manufacturing example  9>

1중량부로 이루어진 단량체 혼합물을 사용하여 아크릴계 공중합체를 제조하였다.
The procedure of Preparation Example 1 was repeated, except that 98 parts by weight of n-butyl acrylate (BA), 1 part by weight of 4-hydroxybutyl acrylate,

1 part by weight was used to prepare an acrylic copolymer.

< Manufacturing example  10>

6중량부로 이루어진 단량체 혼합물을 사용하여 아크릴계 공중합체를 제조하였다.
The procedure of Preparation Example 1 was repeated, except that 93 parts by weight of n-butyl acrylate (BA), 1 part by weight of 4-hydroxybutyl acrylate,

6 parts by weight were used to prepare an acrylic copolymer.

< Manufacturing example  11>

10중량부로 이루어진 단량체 혼합물을 사용하여 아크릴계 공중합체를 제조하였다.
Except that 89 parts by weight of n-butyl acrylate (BA), 1 part by weight of 4-hydroxybutyl acrylate,

10 parts by weight were used to prepare an acrylic copolymer.

< Manufacturing example  12>

0.5중량부로 이루어진 단량체 혼합물을 사용하여 아크릴계 공중합체를 제조하였다.
The procedure of Preparation Example 1 was repeated, except that 98.5 parts by weight of n-butyl acrylate (BA), 1 part by weight of 4-hydroxybutyl acrylate,

0.5 part by weight was used to prepare an acrylic copolymer.

< Manufacturing example  13>

15중량부로 이루어진 단량체 혼합물을 사용하여 아크릴계 공중합체를 제조하였다.
The procedure of Preparation Example 1 was repeated, except that 84 parts by weight of n-butyl acrylate (BA), 1 part by weight of 4-hydroxybutyl acrylate,

15 parts by weight were used to prepare an acrylic copolymer.

< Manufacturing example  14>

대신에

을 사용하여 아크릴계 공중합체를 제조하였다.
The procedure of Preparation Example 1 was repeated,

Instead of

To prepare an acrylic copolymer.

<Comparison Manufacturing example  1>

Acrylic copolymer was prepared in the same manner as in Preparation Example 1 except that 99 parts by weight of n-butyl acrylate (BA) and 1 part by weight of 4-hydroxybutyl acrylate were used.

<Comparison Manufacturing example  2>

대신에 아크릴산 (AA)를 사용하여 아크릴계 공중합체를 제조하였다.
The procedure of Preparation Example 1 was repeated,

Acrylic copolymer (AA) was used instead of acrylic acid (AA).

<Comparison Manufacturing example  3>

대신에 디메틸아미노에틸 아크릴레이트를 사용하여 아크릴계 공중합체를 제조하였다.
The procedure of Preparation Example 1 was repeated,

Instead, dimethylaminoethyl acrylate was used to prepare an acrylic copolymer.

< Example  1-19 and Comparative Example  1-3>

An acrylic copolymer, a crosslinking agent, an ionic antistatic agent and a silane coupling agent of Preparation Example were mixed as shown in Table 1 below and then diluted with ethyl acetate to prepare a pressure-sensitive adhesive composition having a solid content concentration of 15%.

division
(Parts by weight) Acrylic copolymer
(100 parts by weight) Cross-linking agent Ionic antistatic agent Silane
Coupling agent A-1 A-2 A-3 A-4 B-1 B-2 B-3 Example 1 Production Example 1 One - - - 2 - - 0.5 Example 2 Production Example 2 One - - - 2 - - 0.5 Example 3 Production Example 3 One - - - 2 - - 0.5 Example 4 Production Example 4 One - - - 2 - - 0.5 Example 5 Production Example 5 One - - - 2 - - 0.5 Example 6 Production Example 6 One - - - 2 - - 0.5 Example 7 Production Example 7 One - - - 2 - - 0.5 Example 8 Production Example 8 One - - - 2 - - 0.5 Example 9 Production Example 9 One - - - 2 - - 0.5 Example 10 Production Example 10 One - - - 2 - - 0.5 Example 11 Production Example 11 One - - - 2 - - 0.5 Example 12 Production Example 12 One - - - 2 - - 0.5 Example 13 Production Example 13 One - - - 2 - - 0.5 Example 14 Production Example 14 One - - - 2 - - 0.5 Example 15 Production Example 1 - One - - 2 - - 0.5 Example 16 Production Example 1 - - One - 2 - - 0.5 Example 17 Production Example 1 - - - One 2 - - 0.5 Example 18 Production Example 1 One - - - - 2 - 0.5 Example 19 Production Example 1 One - - - - - 2 0.5 Comparative Example 1 Comparative Preparation Example 1 One - - - 2 - - 0.5 Comparative Example 2 Comparative Production Example 2 One - - - 2 - - 0.5 Comparative Example 3 Comparative Production Example 3 One - - - 2 - - 0.5 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; KFSI (fluorosulfonylimide potassium salt)
B-2; LiI
B-3; N-octyl-4-methylpyridinium hexafluorophosphate

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 2 below.

1. Adhesive strength (N / 25 mm)

The polarizer with a pressure-sensitive adhesive was cut into a size of 25 mm x 100 mm and the release film was peeled off. The glass substrate (# 1737, Corning) was laminated at a pressure of 0.25 MPa and autoclaved to prepare a specimen.

The initial adhesive strength of the specimens after being left for 24 hours under the conditions of 23 ° C. and 50% RH and the temperature bonding strength after 48 hours at 50 ° C. and 50% RH were measured using a universal tensile tester (UTM, Instron) The peeling speed was 300 mm / min, and the peeling angle was 180 deg. At this time, measurement was carried out under conditions of 23 캜 and 50% RH.

2. 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: ◎

3. 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.

Thereafter, the polarizing plate with a pressure-sensitive adhesive was allowed to stand at 60 DEG C for 24 hours and then measured in the same manner as above.

4. Metal layer Corrosion resistance

After the release film of the polarizing plate with the adhesive was peeled off, the surface of the pressure-sensitive adhesive layer was bonded to the aluminum plate, and the sample was allowed to stand for 250 hours in an atmosphere of 60 ° C and 95% RH.

The pressure-sensitive adhesive layer was peeled from the laminate, and the surface of the aluminum plate in contact with the pressure-sensitive adhesive layer was visually observed to evaluate the presence or absence of corrosion.

<Evaluation Criteria>

Aluminum plate surface does not corrode at all: ◎

The surface of the aluminum plate is slightly corroded but the function of the aluminum plate is maintained: ○

Corrosion of aluminum plate surface: x

division Adhesive force (N / 25mm) durability Surface resistivity
(Ω / □) Corrosion resistance Early Warming Heat resistance Wet heat Example 1 4 8 ◎ ◎ 3X10 ¹⁰ ◎ Example 2 3 6 ◎ ◎ 4X10 ¹⁰ ◎ Example 3 3 6 ◎ ◎ 4X10 ¹⁰ ◎ Example 4 2 5 ◎ ◎ 5X10 ¹⁰ ◎ Example 5 3 6 ◎ ◎ 4X10 ¹⁰ ◎ Example 6 4 9 ◎ ◎ 2X10 ¹⁰ ◎ Example 7 3 7 ◎ ◎ 1X10 ¹⁰ ◎ Example 8 3 6 ◎ ◎ 4X10 ¹⁰ ◎ Example 9 2 5 ○ ◎ 5X10 ¹⁰ ◎ Example 10 6 12 ◎ ◎ 1X10 ¹⁰ ◎ Example 11 7 12 ◎ ○ 8X10 ⁹ ◎ Example 12 1.5 4 △ ◎ 5X10 ¹⁰ ◎ Example 13 8 15 ◎ △ 6X10 ⁹ ◎ Example 14 6 9 ◎ ◎ 2X10 ¹⁰ ◎ Example 15 3 7 ◎ ◎ 3X10 ¹⁰ ◎ Example 16 5 12 ○ ◎ 3X10 ¹⁰ ◎ Example 17 4 10 ○ ◎ 3X10 ¹⁰ ◎ Example 18 6 10 ◎ ○ 4X10 ⁹ ◎ Example 19 1.5 7 ○ ○ 3X10 ¹¹ ◎ Comparative Example 1 1.2 3.7 × × 7X10 ¹⁰ ◎ Comparative Example 2 7 15 ◎ ◎ 9X10 ¹⁰ × Comparative Example 3 1.8 3.1 × △ 5X10 ¹⁰ ◎

As shown in Table 2, the pressure-sensitive adhesive compositions of Examples 1 to 19 according to the present invention exhibited excellent initial and warm-adhesion, durability and antistatic properties as compared with Comparative Examples 1 to 3, It was confirmed that corrosion of the metal layer can be effectively suppressed.

Claims (8)

A pressure-sensitive adhesive composition comprising an acrylic copolymer and an ionic antistatic agent prepared by copolymerizing monomers containing an acrylate monomer having an amino alcohol group.
The pressure-sensitive adhesive composition according to claim 1, wherein the acrylate-based monomer having an amino alcohol group is an acrylate-based monomer having a? -Hydroxydialkylamino group (a hydroxy carbon containing a tertiary amino group at an adjacent carbon).
The pressure-sensitive adhesive composition according to claim 1, wherein the acrylate monomer having amino alcohol group comprises a compound represented by the following formula (1) or (2):
[Chemical Formula 1]

Wherein R ₁ is an aliphatic hydrocarbon with or without a heteroatom of N or O having 1 to 12 carbon atoms and R ₂ is an aliphatic or aromatic hydrocarbon with or without a heteroatom of N or O having 1 to 12 carbon atoms hydrocarbons, and, R3 is an aliphatic hydrocarbon group with or without a hetero element of N or O with a carbon number of 1 ~ 6, R4 is hydrogen or a methyl group, and R ₁ and R ₂ is a carbon adjacent to each other 5 ring or 6 &lt; / RTI &gt; ring, and the ring may contain a heteroatom.)
(2)

Wherein R ₁ is an aliphatic hydrocarbon with or without a heteroatom of N or O having 1 to 12 carbon atoms and R ₂ is an aliphatic or aromatic hydrocarbon with or without a heteroatom of N or O having 1 to 12 carbon atoms hydrocarbons, and, R3 is an aliphatic hydrocarbon group with or without a hetero element of N or O with a carbon number of 1 ~ 6, R4 is hydrogen or a methyl group, and R ₁ and R ₂ is a carbon adjacent to each other 5 ring or 6 &lt; / RTI &gt; ring, and the ring may contain a heteroatom.)
The pressure-sensitive adhesive composition according to claim 3, wherein the acrylate monomer having an amino alcohol group is at least one selected from the group consisting of the following formulas (3) to (12)
(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(7)

[Chemical Formula 8]

[Chemical Formula 9]

[Chemical formula 10]

(11)

[Chemical Formula 12]

The pressure-sensitive adhesive composition according to claim 1, wherein the acrylic copolymer is prepared by copolymerizing monomers comprising an acrylate monomer having a (meth) acrylate monomer having an alkyl group of 1-12 carbon atoms and an amino alcohol group.
The pressure-sensitive adhesive composition according to claim 5, wherein the acrylate monomer having an amino alcohol group is contained in an amount of 1 to 10 parts by weight based on 100 parts by weight of the (meth) acrylate monomer having an alkyl group having 1-12 carbon atoms.
The ionic antistatic composition of claim 1, wherein the ionic antistatic agent is selected from the group consisting of an alkali metal salt, an ammonium salt, a sulfonium salt, and a phosphonium salt;
Is an ionic salt comprising an anion selected from the group consisting of a fluorine-containing inorganic salt, a fluorine-containing organic salt and an iodide ion.
The pressure-sensitive adhesive composition according to claim 1, wherein the pressure-sensitive adhesive composition further comprises a crosslinking agent.