KR20140139403A - 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 having an amino group and an acrylic copolymer having a carboxylic group, thereby reducing the content of non-crosslinked copolymers and improving cohesive force of the adhesive composition. Therefore, the adhesive composition can maintain adhesion even when exposed to high temperature or high temperature and high humidity environment, and have excellent reworkability.

Description

[0001] ADHESIVE COMPOSITION [0002]

The present invention relates to a pressure-sensitive adhesive composition having improved cohesion.

When a sheet containing an organic material is adhered to an adherend such as glass, ceramics and metal through a pressure-sensitive adhesive, an undesirable situation occurs in which the end portion of the sheet peels off or is released over time come.

In order to solve this problem, a strongly adhe- sive material having improved adhesion by increasing the molecular weight or crosslinking density of the components constituting the pressure-sensitive adhesive is generally used.

Specifically, Japanese Patent Laid-Open No. 2002-169017 discloses a pressure-sensitive adhesive in which an acryl-based polymer having a monomer unit of an alkyl (meth) acrylate as a main skeleton and containing a monomer unit having a carboxyl group is crosslinked with a polyfunctional metal chelate. The pressure-sensitive adhesive improves the pressure-sensitive adhesive performance, but under various high-temperature and high-humidity conditions, it can not keep up with changes in shape caused by shrinkage or swelling of the sheet containing the organic material of the pressure-sensitive adhesive, resulting in various problems.

When a polarizing plate is attached to an optical component such as a liquid crystal cell in a manufacturing process of a liquid crystal display device or the like, the polarizing plate may be peeled to reuse the expensive liquid crystal cell after a predetermined time has elapsed from the attachment. Accordingly, there is a demand for a pressure-sensitive adhesive that can relatively easily peel off from the liquid crystal cell even after a certain period of time has elapsed after being adhered to the liquid crystal cell through the pressure-sensitive adhesive applied to the polarizing plate.

Korean Unexamined Patent Publication No. 2007-76469 discloses a pressure-sensitive adhesive comprising two kinds of acrylic copolymers and an active energy ray-curable compound, wherein the active energy ray-curable compound is used as a crosslinking agent to improve cohesion. Korean Patent Laid-Open Nos. 2014-0013916 and 2014-0013917 disclose (meta) acrylic acid ester monomers having an alkyl group having a carbon number of C4 to C10, a copolymerizable monomer containing a hydroxyl group, and a copolymerizable monomer containing a carboxyl group Discloses a pressure-sensitive adhesive composition further comprising an isocyanate compound having three or more functional groups, which further comprises an antistatic agent, which is an ionic compound having an melting point of 30 to 80 캜 and is an acrylic polymer. However, the above techniques have a disadvantage in that cohesion is improved and adhesive durability is excellent and re-peeling is possible even after a lapse of a predetermined time (reworkability). However, it is difficult to ensure sufficient durability due to recent enlargement of the polarizing plate.

An object of the present invention is to provide a pressure-sensitive adhesive composition in which the cohesive force is increased by covalent bonding between an acrylic copolymer and a crosslinking agent and ionic bonding reaction between acrylic copolymers.

Another object of the present invention is to provide a pressure-sensitive adhesive composition which is excellent in durability due to the above-mentioned cohesive force, and which can be re-peeled after a lapse of a predetermined time.

In order to achieve the above object, the present invention provides a pressure-sensitive adhesive composition comprising an acrylic copolymer and a crosslinking agent, wherein the acrylic copolymer contains an acrylic copolymer having an amino group and an acrylic copolymer having a carboxyl group.

The acrylic copolymer may contain 10 to 90% by weight of an acrylic copolymer having an amino group and 10 to 90% by weight of an acrylic copolymer having a carboxyl group.

The monomer for producing the acrylic copolymer having an amino 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 (1) to (5).

(Wherein R ₁ is hydrogen or a methyl group, and R ₂ and R ₃ are each independently hydrogen, an alkyl group having 1 to 4 carbon atoms, or a trialkylamine group having 1 to 6 carbon atoms)

(Wherein R ₁ is hydrogen or a methyl group, R ₂ and R ₃ are each independently hydrogen or an alkyl group having 1 to 4 carbon atoms, R ₄ is a hydroxyl group or an alkoxy group having 1 to 3 carbon atoms, M is an integer of 0 or 1,

(Wherein R ₁ is hydrogen or a methyl group, and X is O or N substituted with an alkyl group having 1 to 3 carbon atoms)

(Wherein R ₁ is hydrogen or a methyl group, and R ₂ and R ₃ are each independently hydrogen or an alkyl group having 1 to 4 carbon atoms)

(Wherein R ₁ is hydrogen or a methyl group, R ₄ is a hydroxy group or an alkoxy group having 1 to 3 carbon atoms, and R ₅ is hydrogen, an aliphatic hydrocarbon group having 1 to 4 carbon atoms, a halogen, an alkoxy group having 1 to 4 carbon atoms, An alkylamino group having 1 to 4 carbon atoms, n is an integer of 1 to 12, and m is 0 or an integer of 1)

The at least one monomer selected from the group consisting of the above formulas (1) to (5) may contain 1 to 20 parts by weight based on 100 parts by weight of the (meth) acrylate monomer having an alkyl group having 1-12 carbon atoms.

The monomer for producing the acrylic copolymer having a carboxyl 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 (6) to (14).

The at least one monomer selected from the group consisting of the above-mentioned formulas (6) to (14) may be contained in an amount of 0.1 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 pressure-sensitive adhesive composition of the present invention improves cohesion of the pressure-sensitive adhesive composition by covalent bonding between the acryl-based copolymer and the crosslinking agent and ion-bonding reaction between the acrylic copolymer. It is possible to exhibit the same workability as in the prior art while having excellent durability capable of maintaining the adhesive strength even when exposed to high temperature or high temperature and high humidity environment due to the above cohesive force.

The present invention relates to a pressure-sensitive adhesive composition having improved cohesion.

Hereinafter, the present invention will be described in detail.

The pressure-sensitive adhesive composition of the present invention comprises an acrylic copolymer and a crosslinking agent, wherein the acrylic copolymer contains an acrylic copolymer having an amino group and an acrylic copolymer having a carboxyl group.

The pressure-sensitive adhesive composition of the present invention can exhibit excellent durability by improving the cohesion of the pressure-sensitive adhesive composition by simultaneously performing covalent bonding between the crosslinking agent and the acrylic copolymer and ionic bonding between the acrylic copolymer.

At this time, the acrylic copolymer may contain 10 to 90% by weight of an acrylic copolymer having an amino group and 10 to 90% by weight of an acrylic copolymer having a carboxyl group.

When the content of the acrylic copolymer having an amino group is less than 10% by weight or more than 90% by weight, the effect of improving the cohesive force is insufficient and it may not be easy to achieve a sufficient adhesive durability (heat resistance and resistance to moisture and humidity).

(Moving Forward) Monomers for producing an acrylic copolymer having an amino group of the present invention include (meth) acrylate monomers having an alkyl group of 1-12 carbon atoms and at least one monomer selected from the group consisting of the following formulas (1) to can do. In the present invention, (meth) acrylate means acrylate and methacrylate, and the content of each component is based on the solid content.

[Chemical Formula 1]

(Wherein R ₁ is hydrogen or a methyl group, and R ₂ and R ₃ are each independently hydrogen, an alkyl group having 1 to 4 carbon atoms, or a trialkylamine group having 1 to 6 carbon atoms)

(2)

(Wherein R ₁ is hydrogen or a methyl group, R ₂ and R ₃ are each independently hydrogen or an alkyl group having 1 to 4 carbon atoms, R ₄ is a hydroxyl group or an alkoxy group having 1 to 3 carbon atoms, M is an integer of 0 or 1,

(3)

(Wherein R ₁ is hydrogen or a methyl group, and X is O or N substituted with an alkyl group having 1 to 3 carbon atoms)

[Chemical Formula 4]

(Wherein R ₁ is hydrogen or a methyl group, and R ₂ and R ₃ are each independently hydrogen or an alkyl group having 1 to 4 carbon atoms)

[Chemical Formula 5]

(Wherein R ₁ is hydrogen or a methyl group, R ₄ is a hydroxy group or an alkoxy group having 1 to 3 carbon atoms, and R ₅ is hydrogen, an aliphatic hydrocarbon group having 1 to 4 carbon atoms, a halogen, an alkoxy group having 1 to 4 carbon atoms, An alkylamino group having 1 to 4 carbon atoms, n is an integer of 1 to 12, and m is 0 or an integer of 1)

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

The at least one monomer selected from the group consisting of the above-mentioned formulas (1) to (5) preferably contains 1 to 20 parts by weight, more preferably 2 to 20 parts by weight, per 100 parts by weight of the (meth) acrylate monomer having an alkyl group having 1 to 12 carbon atoms. To 10 parts by weight. If the content is less than 1 part by weight, the effect of improving the cohesive strength may be insufficient. If the content is more than 20 parts by weight, the hydrophilicity may be excessively increased to lower the moisture resistance, the peeling force of the release film may be excessively increased, And other physical properties of the pressure-sensitive adhesive can be deteriorated.

Monomers for producing the acrylic copolymer having an amino group of the present invention include (meth) acrylate monomers having an alkyl group of 1-12 carbon atoms and monomers having a hydroxy group in addition to at least one monomer selected from the group consisting of the above formulas ≪ / RTI >

The monomer having a hydroxyl group serves to reinforce the cohesive strength or adhesive strength of the pressure-sensitive adhesive composition by chemical bonding, thereby imparting durability and cutability.

Specifically, the monomer having a hydroxy group may be at least one monomer selected from the group consisting of 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, Hydroxyethyl (meth) acrylate, 2-hydroxypropylene glycol (meth) acrylate, hydroxyalkylene having 2 to 4 carbon atoms in the alkylene group (Meth) acrylate, 4-hydroxybutyl vinyl ether, 5-hydroxypentyl vinyl ether, 6-hydroxyhexyl vinyl ether, 7-hydroxyheptyl vinyl ether, 8-hydroxyoctyl vinyl ether, 4-hydroxybutyl vinyl ether, and 2-hydroxybutyl vinyl ether. Of these, 4-hydroxybutyl vinyl ether is preferable.

The monomer having a hydroxy group is preferably contained in an amount of 0.05 to 10 parts by weight, more preferably 0.1 to 8 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 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.

In addition, the acrylic copolymer having an amino group of the present invention may further contain other polymerizable monomers other than the monomers in an amount not lowering the adhesive force, for example, 10 parts by weight or less based on the total amount.

The production method of the acrylic copolymer having an amino group is not particularly limited and can be produced by a method such as bulk polymerization, solution polymerization, emulsion polymerization or suspension polymerization 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 having an amino group preferably has a weight average molecular weight (polystyrene conversion, Mw) of 50,000 to 2,000,000, more preferably 400,000 to 200,000, as measured by Gel Permeation Chromatography (GPC) It is good to be all alone. When the weight-average molecular weight is less than 50,000, cohesion between co-polymers may be insufficient, which may cause problems in adhesion durability. If the weight average molecular weight is more than 2,000,000, a large amount of a diluting solvent may be required in order to ensure fairness in coating.

The monomer for producing the acrylic copolymer having a carboxyl group of the present invention preferably contains 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 (6) to (14) .

[Chemical Formula 6]

(7)

[Chemical Formula 8]

[Chemical Formula 9]

[Chemical formula 10]

(11)

[Chemical Formula 12]

[Chemical Formula 13]

[Chemical Formula 14]

The at least one monomer selected from the group consisting of the above formulas (6) to (14) is preferably contained in an amount of 0.1 to 10 parts by weight, more preferably 2 to 10 parts by weight per 100 parts by weight of the (meth) acrylate monomer having an alkyl group having 1 to 12 carbon atoms To 6 parts by weight. When the content is less than 0.1 part by weight, the effect of improving the cohesive strength may be insufficient. When the content is more than 10 parts by weight, the hydrophilicity may be excessively increased and the moisture resistance and heat resistance may be lowered.

The acrylic copolymer having a carboxyl group of the present invention may contain a monomer having a hydroxyl group in addition to one or more monomers selected from the group consisting of the above formulas (6) to (14).

The kind of the (meth) acrylate monomer having the alkyl group having 1-12 carbon atoms, the kind and content of the monomer having a hydroxy group, the method of producing the copolymer, the weight average molecular weight of the copolymer, .

INDUSTRIAL APPLICABILITY The present invention can improve the durability deterioration due to the bleed-out of the low-molecular-weight copolymer due to the low content of uncross-linked low-molecular-weight copolymers due to the crosslinking reaction (ionic bonding) between the acrylic copolymers, The cohesive force is improved and durability can be ensured.

The crosslinking agent is used for improving cohesion and improving durability, and is particularly used for satisfying both heat resistance and heat resistance.

In wet heat conditions, water may be absorbed and hydrogen bonds or ionic bonds between the polymers may be broken. Therefore, a crosslinking agent is used to prevent this.

The crosslinking agent is capable of reacting with a hydroxyl group or a carboxyl group, and isocyanate-based or epoxy-based can be used alone or in combination of two or more.

Examples of the isocyanate crosslinking agent 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 crosslinking agent include ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene Glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, polytetramethylene glycol diglycidyl ether, glycerol diglycidyl ether, glycerol triglycidyl ether , Diglycerol polyglycidyl ether, polyglycerol polyglycidyl ether, resorcinol diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, trimethylol propane triglycidyl ether, pentaerythritol (Glycidyl) isobutyrate, glycidyl glycidyl ether, sorbitol polyglycidyl ether, adipic acid diglycidyl ester, phthalic acid diglycidyl ester, tris (N, N-glycidylaminomethyl) cyclohexane, N, N, N ', N'-tetraglycidyl-m - xylylenediamine, and the like.

Such a crosslinking agent may be contained in an amount of 0.1 to 5 parts by weight, preferably 0.2 to 1.0 part by weight based on 100 parts by weight of the total amount of the acrylic copolymer having an amino group and the acrylic copolymer having a carboxyl group. If the content of the crosslinking agent is less than 0.1 parts by weight, the effect of improving the cohesive strength may be insufficient. If the content of the crosslinking agent is more than 5 parts by weight, the cohesive strength may be excessively increased.

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

The double silane coupling agent serves to improve the adhesion between the pressure-sensitive adhesive and the substrate. Therefore, it is preferable that the double silane coupling agent contains an alkoxysilane containing an amino group, an epoxy group, an acetoacetyl group, a polyalkylene glycol group, an acryl group, Can be used.

Such an additive can be appropriately controlled within a range that does not impair the effects of the present invention. For example, the silane coupling agent may be added to the total amount of the acrylic copolymer having an amino group and the acrylic copolymer having a carboxyl group in consideration of adhesion and durability 0.01 to 2 parts by weight, preferably 0.1 to 0.5 parts by weight, based on 100 parts by weight of the resin composition. If the content is less than 0.01 parts by weight, the adhesion may be deteriorated. If the content is more than 2 parts by weight, peeling may occur under heat-resistant conditions.

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  1: Acrylic copolymer having an amino group

Manufacturing example  1-1

90 parts by weight of n-butyl acrylate (BA), 7 parts by weight of methyl acrylate (MA), and 3 parts by weight of dimethylaminoethyl acrylate were charged in a 1 L reactor equipped with a cooling device to regulate the temperature of the nitrogen gas, After the monomer mixture was added, 100 parts by weight of ethyl acetate (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 an amino group having a weight average molecular weight of about 1,000,000.

Manufacturing example  1-2

Acrylic copolymer having an amino group was prepared in the same manner as in Preparation Example 1-1, but using acryloyloxypolyol in place of dimethylaminoethyl acrylate.

Manufacturing example  1-3

10중량부를 이용하여 아미노기를 갖는 아크릴계 공중합체를 제조하였다.
Except that 83 parts by weight of n-butyl acrylate (BA), 7 parts by weight of methyl acrylate (MA), 10 parts by weight of dimethylaminoethyl acrylate

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

Manufacturing example  1-4

10중량부를 이용하여 아미노기를 갖는 아크릴계 공중합체를 제조하였다.
Except that 83 parts by weight of n-butyl acrylate (BA), 7 parts by weight of methyl acrylate (MA), 10 parts by weight of dimethylaminoethyl acrylate

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

Manufacturing example  1-5

20중량부를 이용하여 아미노기를 갖는 아크릴계 공중합체를 제조하였다.
Except that 73 parts by weight of n-butyl acrylate (BA), 7 parts by weight of methyl acrylate (MA), 10 parts by weight of dimethylaminoethyl acrylate

20 parts by weight were used to prepare an acrylic copolymer having an amino group.

Manufacturing example  1-6

Except that 68 parts by weight of n-butyl acrylate (BA), 7 parts by weight of methyl acrylate (MA), and 25 parts by weight of dimethylaminoethyl acrylate were used in place of the acrylic copolymer .

Manufacturing example  1-7

10중량부를 이용하여 아미노기를 갖는 아크릴계 공중합체를 제조하였다.Except that 83 parts by weight of n-butyl acrylate (BA), 7 parts by weight of methyl acrylate (MA), 10 parts by weight of dimethylaminoethyl acrylate

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

Manufacturing example  1-8

10중량부를 이용하여 아미노기를 갖는 아크릴계 공중합체를 제조하였다.
Except that 83 parts by weight of n-butyl acrylate (BA), 7 parts by weight of methyl acrylate (MA), 10 parts by weight of dimethylaminoethyl acrylate

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

Manufacturing example  2: Carboxy group  Acrylic copolymer

Manufacturing example  2-1

(화학식 6) 3.0중량부, 4-히드록시부틸아크릴레이트 (4HBA) 1.0중량부로 이루어진 단량체 혼합물을 투입한 후, 용제로 아세톤 100중량부를 투입하였다. 그 다음 산소를 제거하기 위하여 질소가스를 1시간 동안 퍼징한 후, 62℃로 유지하였다. 상기 혼합물을 균일하게 한 후, 반응개시제로 아조비스이소부티로니트릴(AIBN) 0.07중량부를 투입하고, 6시간 동안 반응시켜 중량평균분자량이 약 100만인 카르복시기를 갖는 아크릴계 공중합체를 제조하였다.
89 parts by weight of n-butyl acrylate (BA), 7.0 parts by weight of methyl acrylate (MA), and 0.1 part by weight of n-butyl acrylate (BA) were placed in a 1 L reactor equipped with a cooling device,

, 3.0 parts by weight of a monomer represented by the following general formula (6) and 1.0 part by weight of 4-hydroxybutyl acrylate (4HBA) were added thereto, and 100 parts by weight of acetone was added thereto 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 carboxyl group having a weight average molecular weight of about 1,000,000.

Manufacturing example  2-2

(화학식 6) 대신에

(화학식 7)을 사용하여 카르복시기를 갖는 아크릴계 공중합체를 제조하였다.
The procedure of Preparation Example 2-1 was repeated,

(6) instead of

(Formula 7), an acrylic copolymer having a carboxyl group was prepared.

Manufacturing example  2-3

(화학식 6) 대신에

(화학식 8)을 사용하여 카르복시기를 갖는 아크릴계 공중합체를 제조하였다.
The procedure of Preparation Example 2-1 was repeated,

(6) instead of

(Formula 8), an acrylic copolymer having a carboxyl group was prepared.

Manufacturing example  2-4

(화학식 6) 대신에

(화학식 9)을 사용하여 카르복시기를 갖는 아크릴계 공중합체를 제조하였다.
The procedure of Preparation Example 2-1 was repeated,

(6) instead of

(Formula 9), an acrylic copolymer having a carboxyl group was prepared.

Manufacturing example  2-5

(화학식 6) 대신에

(화학식 10)을 사용하여 카르복시기를 갖는 아크릴계 공중합체를 제조하였다.
The procedure of Preparation Example 2-1 was repeated,

(6) instead of

(Formula 10) was used to prepare an acrylic copolymer having a carboxyl group.

Manufacturing example  2-6

(화학식 6) 대신에

(화학식 11)을 사용하여 카르복시기를 갖는 아크릴계 공중합체를 제조하였다.
The procedure of Preparation Example 2-1 was repeated,

(6) instead of

(Formula 11), an acrylic copolymer having a carboxyl group was prepared.

Manufacturing example  2-7

(화학식 6) 대신에

(화학식 12)을 사용하여 카르복시기를 갖는 아크릴계 공중합체를 제조하였다.
The procedure of Preparation Example 2-1 was repeated,

(6) instead of

(Formula 12), an acrylic copolymer having a carboxyl group was prepared.

Manufacturing example  2-8

(화학식 6) 대신에

(화학식 13)을 사용하여 카르복시기를 갖는 아크릴계 공중합체를 제조하였다.
The procedure of Preparation Example 2-1 was repeated,

(6) instead of

(Formula 13), an acrylic copolymer having a carboxyl group was prepared.

Manufacturing example  2-9

(화학식 6) 대신에

(화학식 14)을 사용하여 카르복시기를 갖는 아크릴계 공중합체를 제조하였다.
The procedure of Preparation Example 2-1 was repeated,

(6) instead of

(Formula 14), an acrylic copolymer having a carboxyl group was prepared.

Manufacturing example  2-10

(화학식 6) 1.0중량부와 히드록시에틸아크릴레이트 1.0중량부를 사용하여 카르복시기를 갖는 아크릴계 공중합체를 제조하였다.
Except that 91 parts by weight of n-butyl acrylate (BA), 7.0 parts by weight of methyl acrylate (MA)

(Formula 6) and 1.0 part by weight of hydroxyethyl acrylate were used to prepare an acrylic copolymer having a carboxyl group.

Manufacturing example  2-11

(화학식 6) 10.0중량부와 히드록시에틸아크릴레이트 1.0중량부를 사용하여 카르복시기를 갖는 아크릴계 공중합체를 제조하였다.
The procedure of Preparation Example 2-1 was repeated, except that 82 parts by weight of n-butyl acrylate (BA), 7.0 parts by weight of methyl acrylate (MA)

10.0 parts by weight of the compound (6) and 1.0 part by weight of hydroxyethyl acrylate were used to prepare an acrylic copolymer having a carboxyl group.

Manufacturing example  2-12

(화학식 6) 15.0중량부와 히드록시에틸아크릴레이트 1.0중량부를 사용하여 카르복시기를 갖는 아크릴계 공중합체를 제조하였다.
Except that 77 parts by weight of n-butyl acrylate (BA), 7.0 parts by weight of methyl acrylate (MA)

15.0 parts by weight of the compound (6) and 1.0 part by weight of hydroxyethyl acrylate were used to prepare an acrylic copolymer having a carboxyl group.

Example  1-18 and Comparative Example  1-2

And then diluted with ethyl acetate to prepare a pressure-sensitive adhesive composition having a solid content concentration of 15%. 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.

division
(Parts by weight) Acrylic copolymer Cross-linking agent Silane coupling agent Amino group Carboxy group Example 1 Production Example 1-1 (50) Production Example 2-1 (50) 0.5 0.5 Example 2 Production Example 1-1 (50) Production Example 2-2 (50) 0.5 0.5 Example 3 Production Example 1-1 (50) Production Example 2-3 (50) 0.5 0.5 Example 4 Production Example 1-1 (50) Production Example 2-4 (50) 0.5 0.5 Example 5 Production Example 1-1 (50) Production Example 2-5 (50) 0.5 0.5 Example 6 Production Example 1-1 (50) Production Example 2-6 (50) 0.5 0.5 Example 7 Production Example 1-1 (50) Production Example 2-7 (50) 0.5 0.5 Example 8 Production Example 1-1 (50) Production Example 2-8 (50) 0.5 0.5 Example 9 Production Example 1-1 (50) Production Example 2-9 (50) 0.5 0.5 Example 10 Production Example 1-1 (50) Production Example 2-10 (50) 0.5 0.5 Example 11 Production Example 1-1 (50) Production Example 2-11 (50) 0.5 0.5 Example 12 Production Example 1-2 (50) Production Example 2-1 (50) 0.5 0.5 Example 13 Production Example 1-3 (50) Production Example 2-1 (50) 0.5 0.5 Example 14 Production Example 1-4 (50) Production Example 2-1 (50) 0.5 0.5 Example 15 Production Example 1-5 (50) Production Example 2-1 (50) 0.5 0.5 Example 16 Production Example 1-7 (50) Production Example 2-1 (50) 0.5 0.5 Example 17 Production Example 1-8 (50) Production Example 2-1 (50) 0.5 0.5 Example 18 Production Example 1-1 (70) Production Example 2-1 (30) 0.5 0.5 Example 19 Production Example 1-1 (90) Production Example 2-1 (10) 0.5 0.5 Example 20 Production Example 1-6 (70) Production Example 2-12 (30) 0.5 0.5 Example 21 Production Example 1-1 (95) Production Example 2-1 (5) 0.5 0.5 Example 22 Production Example 1-1 (10) Production Example 2-1 (90) 0.5 0.5 Example 23 Production Example 1-1 (5) Production Example 2-1 (95) 0.5 0.5 Comparative Example 1 Production Example 1-1 (100) - 1.0 0.5 Comparative Example 2 - Production Example 2-1 (100) 1.0 0.5 Crosslinking agent: Coronate-L (CORONATE-L, Japan Urethane Industry)
Silane coupling agent: KBM-403 (Shin-Etsu)

Test Example

The physical properties of 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. Heat resistance / Humidity Durability

The release film of the polarizing plate with a pressure-sensitive adhesive was removed and bonded to the surface of the pressure-sensitive adhesive layer and Corning glass, and then left for 300 hours at 80 ° C and 60 ° C / 90RH%, respectively.

<Evaluation Criteria>

Bubbles and peeling phenomena More than 3 poisoned: ×

Bubbles and peeling phenomena Less than 2 poised: ○

Bubbles and peeling phenomenon are observed: ◎

2. Re-workability

The polarizing plate with a pressure-sensitive adhesive was cut to a size of 25 mm in width and 100 mm in length. The releasing film was peeled off and laminated to Corning # 1737 glass at a pressure of 0.25 MPa and autoclave was performed for 20 minutes under conditions of 5 atm and 50 캜 To prepare an evaluation sample. After putting it in an oven at 50 ° C for 5 hours, it was taken out at room temperature for 120 hours and then peeled at a rate of 1.3 cm / s. In addition, it was placed in an oven at 60 DEG C and 90RH% in a humid condition, taken out after 4 hours, left at room temperature for 120 hours, and peeled at a rate of 1.3 cm / s.

<Evaluation Criteria>

- No adhesive residue on the glass substrate in both conditions and cleanly peeled off without tearing of the polarizer: ○

- Adhesive remains on the panel under either condition, or the polarizer tears during peeling: x

division Heat resistance Humidity Durability Re-workability Example 1 ◎ ◎ ○ Example 2 ◎ ◎ ○ Example 3 ◎ ◎ ○ Example 4 ◎ ◎ ○ Example 5 ◎ ◎ ○ Example 6 ◎ ◎ ○ Example 7 ◎ ◎ ○ Example 8 ◎ ◎ ○ Example 9 ◎ ◎ ○ Example 10 ○ ◎ ○ Example 11 ◎ ○ ○ Example 12 ◎ ◎ ○ Example 13 ◎ ◎ ○ Example 14 ◎ ◎ ○ Example 15 ○ ○ ○ Example 16 ◎ ◎ ○ Example 17 ◎ ◎ ○ Example 18 ◎ ◎ ○ Example 19 ○ ◎ ○ Example 20 ○ ○ ○ Example 21 ○ ○ ○ Example 22 ○ ◎ ○ Example 23 ○ ○ ○ Comparative Example 1 × × ○ Comparative Example 2 × × ○

The pressure-sensitive adhesive compositions of Examples 1 to 23 containing an acrylic copolymer having an amino group and an acrylic copolymer having a carboxyl group according to the present invention as an acrylic copolymer as shown in Table 2 above were compared with Comparative Examples 1 and 2, It was confirmed that the heat resistance and the humid heat resistance were excellent while maintaining the properties.

Claims (6)

An acrylic copolymer and a cross-linking agent,
Wherein the acrylic copolymer contains an acrylic copolymer having an amino group and an acrylic copolymer having a carboxyl group. The pressure-sensitive adhesive composition according to claim 1, wherein the acrylic copolymer contains 10 to 90% by weight of an acrylic copolymer having an amino group and 10 to 90% by weight of an acrylic copolymer having a carboxyl group. The acrylic copolymer according to claim 1, wherein the monomer for producing the acrylic copolymer having an amino group is selected from the group consisting of 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 &Lt; tb &gt;
[Chemical Formula 1]

(Wherein R ₁ is hydrogen or a methyl group, and R ₂ and R ₃ are each independently hydrogen, an alkyl group having 1 to 4 carbon atoms, or a trialkylamine group having 1 to 6 carbon atoms)
(2)

(Wherein R ₁ is hydrogen or a methyl group, R ₂ and R ₃ are each independently hydrogen or an alkyl group having 1 to 4 carbon atoms, R ₄ is a hydroxyl group or an alkoxy group having 1 to 3 carbon atoms, M is an integer of 0 or 1,
(3)

(Wherein R ₁ is hydrogen or a methyl group, and X is O or N substituted with an alkyl group having 1 to 3 carbon atoms)
[Chemical Formula 4]

(Wherein R ₁ is hydrogen or a methyl group, and R ₂ and R ₃ are each independently hydrogen or an alkyl group having 1 to 4 carbon atoms)
[Chemical Formula 5]

(Wherein R ₁ is hydrogen or a methyl group, R ₄ is a hydroxy group or an alkoxy group having 1 to 3 carbon atoms, and R ₅ is hydrogen, an aliphatic hydrocarbon group having 1 to 4 carbon atoms, a halogen, an alkoxy group having 1 to 4 carbon atoms, An alkylamino group having 1 to 4 carbon atoms, n is an integer of 1 to 12, and m is 0 or an integer of 1). The pressure-sensitive adhesive composition according to claim 3, wherein the at least one monomer selected from the group consisting of Formulas 1 to 5 contains 1 to 20 parts by weight per 100 parts by weight of the (meth) acrylate monomer having an alkyl group having 1-12 carbon atoms . The acrylic copolymer according to claim 1, wherein the monomer for producing the acrylic copolymer having a carboxyl group is a copolymer of a (meth) acrylate monomer having an alkyl group of 1-12 carbon atoms and at least one monomer selected from the group consisting of the following formulas &Lt; tb &gt;
[Chemical Formula 6]

(7)

[Chemical Formula 8]

[Chemical Formula 9]

[Chemical formula 10]

(11)

[Chemical Formula 12]

[Chemical Formula 13]

[Chemical Formula 14]

The pressure-sensitive adhesive composition according to claim 5, wherein the at least one monomer selected from the group consisting of Formulas (6) to (14) contains 0.1 to 10 parts by weight per 100 parts by weight of the (meth) acrylate monomer having an alkyl group having 1-12 carbon atoms .