KR102051483B1 - Adhesive composition - Google Patents

Adhesive composition Download PDF

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KR102051483B1
KR102051483B1 KR1020130102109A KR20130102109A KR102051483B1 KR 102051483 B1 KR102051483 B1 KR 102051483B1 KR 1020130102109 A KR1020130102109 A KR 1020130102109A KR 20130102109 A KR20130102109 A KR 20130102109A KR 102051483 B1 KR102051483 B1 KR 102051483B1
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weight
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KR20150025019A (en
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최한영
허지혜
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동우 화인켐 주식회사
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/24—Homopolymers or copolymers of amides or imides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks

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  • Organic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
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Abstract

The present invention relates to an adhesive composition, and more particularly, by containing an acrylic copolymer having an alkoxymethylamide group or a carboxymethylamide group and an acrylic copolymer having a carboxyl group, thereby reducing the content of the non-crosslinked copolymer and It is related with the adhesive composition which the cohesion force improves and it can maintain adhesive force even when exposed to high temperature or high temperature and high humidity environment, and was excellent in rework property.

Description

Adhesive composition {ADHESIVE COMPOSITION}

The present invention relates to an adhesive composition with improved cohesion.

When sheets containing organic materials are attached to adherends such as glass, ceramics and metals via an adhesive, an undesirable situation frequently arises in which the sheet end parts are peeled off or heard over time. come.

In order to solve this problem, a strong adhesive material which improves the adhesive performance by increasing the molecular weight of the components constituting the adhesive or increasing the crosslinking density is generally used.

Specifically, Japanese Patent Application Laid-Open No. 2002-169017 discloses an adhesive in which an acrylic polymer made of a monomer unit of alkyl (meth) acrylate as a main skeleton and a monomer unit having a carboxyl group is crosslinked with a multifunctional metal chelate. The pressure-sensitive adhesive improves the adhesive performance, but under high temperature and high humidity conditions, it is impossible to keep up with the shape change caused by shrinkage or swelling of the sheet including the organic material of the pressure-sensitive adhesive, which causes various problems.

In addition, in a manufacturing process such as a liquid crystal display device, when attaching a polarizing plate to an optical component such as a liquid crystal cell, the polarizing plate may be peeled off to reuse an expensive liquid crystal cell after a predetermined time has elapsed after the attachment. Therefore, there is a need for an adhesive that can be easily peeled from the liquid crystal cell even after a certain time has elapsed after being attached to the liquid crystal cell through the adhesive applied to the polarizing plate.

Accordingly, Korean Patent Publication No. 2007-76469 discloses an adhesive containing two acrylic copolymers and an active energy ray-curable compound, and wherein the active energy ray-curable compound is used as a crosslinking agent to improve cohesion. The method has excellent cohesive strength and excellent adhesion durability, and can be re-peeled even after a certain time (reworkability), but it is difficult to secure sufficient durability as the polarizer is recently enlarged.

It is an object of the present invention to provide a pressure-sensitive adhesive composition in which cohesion of a copolymer and a crosslinking agent is increased, and at the same time, cohesion is increased by an ionic bond reaction between an acrylic copolymer.

In addition, an object of the present invention is to provide a pressure-sensitive adhesive composition which is excellent in durability by improving the cohesive force and at the same time capable of re-peeling after a lapse of time.

In order to achieve the above object, the present invention provides an adhesive composition containing an acrylic copolymer having an alkoxymethylamide group or a carboxymethylamide group and an acrylic copolymer having a carboxyl group.

10 to 90% by weight of the acrylic copolymer having an alkoxymethylamide group or carboxymethylamide group and 10 to 90% by weight of the acrylic copolymer having a carboxyl group.

The acrylic copolymer having the alkoxymethylamide group or the carboxymethylamide group may contain a (meth) acrylate monomer having an alkyl group having 1 to 12 carbon atoms and a monomer of the following Chemical Formula 1 or Chemical Formula 2.

Figure 112013078356513-pat00001

Figure 112013078356513-pat00002

(Formula 1 or 2, R 1 is hydrogen or methyl group, R 2 and R 3 are each independently C 1 -C 8 aliphatic hydrocarbon group, halogen-substituted C 1 -C 8 aliphatic hydrocarbon group or C 6 -C 8 aromatic hydrocarbon group).

Preferably, R 1 is hydrogen or a methyl group, R 2 and R 3 may be each independently a C 1 -C 8 alkyl group, a halogen-substituted alkyl group, a benzyl group or a phenyl group.

The monomer of Formula 1 or Formula 2 may be at least one selected from the group consisting of the following Formulas 3 to 12.

Figure 112013078356513-pat00003

Figure 112013078356513-pat00004

Figure 112013078356513-pat00005

Figure 112013078356513-pat00006

Figure 112013078356513-pat00007

Figure 112013078356513-pat00008

Figure 112013078356513-pat00009

Figure 112013078356513-pat00010

Figure 112013078356513-pat00011

Figure 112013078356513-pat00012

The monomer of Formula 1 or Formula 2 may contain 0.1 to 10 parts by weight based on 100 parts by weight of the (meth) acrylate monomer having an alkyl group having 1 to 12 carbon atoms.

The acryl-based copolymer having a carboxyl group may contain a (meth) acrylate monomer having an alkyl group having 1 to 12 carbon atoms and at least one monomer selected from the following Chemical Formulas 13 to 21.

Figure 112013078356513-pat00013

Figure 112013078356513-pat00014

Figure 112013078356513-pat00015

Figure 112013078356513-pat00016

Figure 112013078356513-pat00017

Figure 112013078356513-pat00018

Figure 112013078356513-pat00019

Figure 112013078356513-pat00020

Figure 112013078356513-pat00021

The at least one monomer selected from Formulas 13 to 21 may contain 0.1 to 10 parts by weight based on 100 parts by weight of the (meth) acrylate monomer having an alkyl group having 1 to 12 carbon atoms.

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

In the pressure-sensitive adhesive composition of the present invention, the cohesion of the pressure-sensitive adhesive composition is improved by the covalent bond between the copolymer and the crosslinking agent and at the same time by the ionic bond reaction between the acrylic copolymer. By the improved cohesive force, even when exposed to a high temperature or high temperature and high humidity environment, while having excellent durability to maintain the adhesive force, it can exhibit a reworkability equivalent to that of the conventional.

The present invention relates to an adhesive composition with improved cohesion.

Hereinafter, the present invention will be described in detail.

The pressure-sensitive adhesive composition of the present invention contains an acrylic copolymer having an alkoxymethylamide group or a carboxymethylamide group and an acrylic copolymer having a carboxyl group.

At this time, it may contain 10 to 90% by weight of the acrylic copolymer having an alkoxymethylamide group or carboxymethylamide group, and 10 to 90% by weight of the acrylic copolymer having a carboxyl group. When the content of the acrylic copolymer having the alkoxymethylamide group or the carboxymethylamide group is less than 10% by weight or more than 90% by weight, the effect of improving cohesion is insufficient and it is easy to achieve sufficient adhesive reconstitution (heat resistance and heat and moisture resistance) improvement effect. You can't.

The pressure-sensitive adhesive composition of the present invention may exhibit excellent durability by covalent bonding formed by the nucleophilic substitution reaction between the acrylic copolymer and covalent bond between the crosslinking agent and the acrylic copolymer to improve cohesion of the pressure-sensitive adhesive composition.

The acrylic copolymer having the alkoxymethylamide group or the carboxymethylamide group of the present invention may contain a (meth) acrylate monomer having an alkyl group having 1 to 12 carbon atoms and a monomer of the following formula (1) or (2). In the present invention, (meth) acrylate means acrylate and methacrylate, and the content of each component is based on solid content.

[Formula 1]

Figure 112013078356513-pat00022

[Formula 2]

Figure 112013078356513-pat00023

(Formula 1 or 2, R 1 is hydrogen or methyl group, R 2 and R 3 are each independently C 1 -C 8 aliphatic hydrocarbon group, halogen-substituted C 1 -C 8 aliphatic hydrocarbon group or C 6 -C 8 aromatic hydrocarbon group).

Preferably, R 1 is hydrogen or a methyl group, R 2 and R 3 may be each independently a C 1 -C 8 alkyl group, a halogen-substituted alkyl group, a benzyl group or a phenyl group.

The (meth) acrylate monomer having an alkyl group having 1 to 12 carbon atoms is a (meth) acrylate derived from an aliphatic alcohol having 1 to 12 carbon atoms, for example, methyl acrylate, ethyl acrylate, propyl acrylate, n -Butyl (meth) acrylate, 2-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, Nonyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, etc. are mentioned, These can be used individually or in mixture of 2 or more types. Among these, n-butyl acrylate, 2-ethylhexyl acrylate, or a mixture thereof is preferable.

In consideration of the glass transition temperature, the monomer of Formula 1 or Formula 2 is more preferably one or more selected from the group consisting of the following Formulas 3 to 12.

 [Formula 3]

Figure 112013078356513-pat00024

[Formula 4]

Figure 112013078356513-pat00025

[Formula 5]

Figure 112013078356513-pat00026

[Formula 6]

Figure 112013078356513-pat00027

[Formula 7]

Figure 112013078356513-pat00028

[Formula 8]

Figure 112013078356513-pat00029

[Formula 9]

Figure 112013078356513-pat00030

[Formula 10]

Figure 112013078356513-pat00031

[Formula 11]

Figure 112013078356513-pat00032

[Formula 12]

Figure 112013078356513-pat00033

In consideration of durability such as heat and moisture resistance, Chemical Formulas 9, 11, and 12 are more preferable.

The monomer of Formula 1 or Formula 2 may contain 0.1 to 10 parts by weight, preferably 1 to 5 parts by weight, based on 100 parts by weight of the (meth) acrylate monomer having an alkyl group having 1 to 12 carbon atoms. If the content is less than 0.1 parts by weight, the cohesive force improving effect is insufficient, and if it exceeds 10 parts by weight, a problem of deterioration of adhesion due to excessive crosslink formation may occur.

The acrylic copolymer having an alkoxymethylamide group or carboxymethylamide group of the present invention may contain a monomer having a hydroxy group in addition to the monomer of Formula 1 or Formula 2.

The monomer having a hydroxy group serves to enhance the cohesion or adhesive strength of the pressure-sensitive adhesive composition by chemical bonding to impart durability and cutability.

Specifically 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxy Hexyl (meth) acrylate, 2-hydroxyethylene glycol (meth) acrylate, 2-hydroxypropylene glycol (meth) acrylate, and hydroxyalkylene glycol (meth) acrylate having 2-4 carbon atoms in the alkylene group , 4-hydroxybutyl vinyl ether, 5-hydroxypentyl vinyl ether, 6-hydroxyhexyl vinyl ether, 7-hydroxyheptyl vinyl ether, 8-hydroxyoctyl vinyl ether, 9-hydroxynonyl vinyl ether, and 10-hydroxydecyl vinyl ether, etc. are mentioned, Among these, 4-hydroxybutyl vinyl ether is preferable.

It is preferable that the monomer which has such a hydroxyl group is contained in 0.05-10 weight part with respect to 100 weight part of (meth) acrylate monomers which have a C1-C12 alkyl group, More preferably, it is 0.1-8 weight part. If the content is less than 0.05 parts by weight, the cohesive force of the pressure-sensitive adhesive may be reduced, the durability may be lowered. If the content is more than 10 parts by weight, the adhesive strength is lowered by a high gel fraction may cause problems in durability.

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

The production method of the copolymer is not particularly limited, and may be prepared using a method such as bulk polymerization, solution polymerization, emulsion polymerization or suspension polymerization, which are commonly used in the art, and solution polymerization is preferable. In addition, a solvent, a polymerization initiator, a chain transfer agent for molecular weight control, and the like, which are usually used in the polymerization, may be used.

The acrylic copolymer preferably has a weight average molecular weight (polystyrene equivalent, Mw) measured by gel permeation chromatography (GPC) of 50,000 to 2 million, more preferably 400,000 to 2 million.

The acrylic copolymer having a carboxyl group of the present invention preferably contains a (meth) acrylate monomer having an alkyl group having 1 to 12 carbon atoms and at least one monomer selected from the following formulas (13) to (21).

[Formula 13]

Figure 112013078356513-pat00034

[Formula 14]

Figure 112013078356513-pat00035

[Formula 15]

Figure 112013078356513-pat00036

[Formula 16]

Figure 112013078356513-pat00037

[Formula 17]

Figure 112013078356513-pat00038

[Formula 18]

Figure 112013078356513-pat00039

[Formula 19]

Figure 112013078356513-pat00040

[Formula 20]

Figure 112013078356513-pat00041

[Formula 21]

Figure 112013078356513-pat00042

The at least one monomer selected from the group consisting of Formulas 13 to 21 may contain 0.1 to 10 parts by weight based on 100 parts by weight of the (meth) acrylate monomer having an alkyl group having 1 to 12 carbon atoms. If the content is less than 0.1 parts by weight, additional crosslinking may be insufficient, and if it exceeds 10 parts by weight, a problem of deterioration of adhesive strength may occur due to excessive crosslinking.

The acrylic copolymer having a carboxyl group of the present invention may contain a monomer having a hydroxy group in addition to at least one monomer selected from the group consisting of Formulas 13 to 21.

The type of the (meth) acrylate monomer having an alkyl group having 1 to 12 carbon atoms, the type and content of the monomer having a hydroxy group, the production method of the copolymer, the weight average molecular weight of the copolymer, etc. may be the alkoxymethylamide group or the carboxymethylamide. It is the same as the description in the acryl-type copolymer which has a group.

The present invention has a low content of low-molecular weight copolymer which is not crosslinked by crosslinking reaction between acrylic copolymers, thereby improving durability reduction due to bleed-out of low molecular weight copolymer, and compact crosslinking between copolymers. Cohesion is enhanced by the combination to ensure durability.

In addition, the present invention may further use a crosslinking agent in order to improve the cohesive force to improve durability.

However, it is possible to satisfy the heat resistance enough to play a role as a pressure-sensitive adhesive without the use of a crosslinking agent, but in the case of using a high shrink film such as an acrylic film, which is recently used to lower the cost of the polarizing plate to improve the heat resistance degradation of the film Preference is given to using crosslinking agents.

The crosslinking agent may react with a hydroxyl group or a carboxyl group, and isocyanate or epoxy may be used alone or in combination of two or more thereof.

The isocyanate type is tolylene diisocyanate, xylene diisocyanate, 2,4-diphenylmethane diisocyanate, 4,4-diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, tetramethyl xylene diisocyanate, naphthalenedi Diisocyanate compounds such as isocyanate; Diisocyanate obtained from 2 moles of an adduct obtained by reacting 3 moles of a diisocyanate compound with 1 mole of a polyhydric alcohol compound such as trimethylolpropane, an isocyanurate obtained by self-condensing 3 moles of the diisocyanate compound, and 3 moles of the diisocyanate compound And polyfunctional isocyanate compounds containing three functional groups such as biuret, triphenylmethanetriisocyanate, and methylenebistriisocyanate, in which the remaining 1 mole of diisocyanate is condensed to urea.

The epoxy type is ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol di Glycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, polytetramethylene glycol diglycidyl ether, glycerol diglycidyl ether, glycerol triglycidyl ether, di Glycerol polyglycidyl ether, polyglycerol polyglycidyl ether, resorcin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, trimethylolpropanetriglycidyl ether, pentaerythritol poly Glycidyl ether, sorbitol polyglycidyl ether, adipic acid diglycidyl ester, phthalic acid diglycidyl ester, tris (glycidyl) isocyanuric Tris (glycidoxyethyl) isocyanurate, 1,3-bis (N, N-glycidylaminomethyl) cyclohexane, N, N, N ', N'-tetraglycidyl-m- Xylylenediamine etc. are mentioned.

Such a crosslinking agent may be contained in an amount of 0.1 to 5 parts by weight, preferably 0.2 to 1.0 parts by weight, based on 100 parts by weight of the acrylic copolymer. In the present invention, crosslinking is possible without using a crosslinking agent, but a small amount of the crosslinking agent is added to achieve an improved cohesive effect. Therefore, when the content is less than 0.1 part by weight, the effect of improving cohesion may be insufficient, and when it exceeds 5 parts by weight, the cohesion may be lowered due to excessive increase in cohesion.

In addition to the components as described above, the pressure-sensitive adhesive composition is an antistatic agent, tackifying resin, antioxidant, leveling agent, surface lubricant, dye, pigment in order to adjust the adhesion, cohesion, viscosity, modulus, glass transition temperature, etc. required according to the application It may further contain additives such as antifoaming agent, filler, light stabilizer.

Since the double silane coupling agent plays a role of improving adhesion between the pressure-sensitive adhesive and the base material, it is preferable to contain it, and an alkoxysilane containing functional groups such as amino group, epoxy group, acetoacetyl group, polyalkylene glycol group, acryl group and alkyl group Can be used.

Such additives may be appropriately adjusted in the range not impairing the effects of the present invention, for example, the silane coupling agent is 0.01 to 2 parts by weight, preferably to 100 parts by weight of acrylic copolymer in consideration of adhesion and durability, etc. May contain 0.1 to 0.5 parts by weight. If the content is less than 0.01 parts by weight, the adhesion may be lowered, and if it exceeds 2 parts by weight, peeling may occur under heat-resistant conditions.

In particular, the pressure-sensitive adhesive composition of the present invention can be used as a pressure-sensitive adhesive for polarizing plates and a surface protective film for bonding to liquid crystal cells. In addition, it can be used as a general commercial adhesive sheet product as well 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 adhesive for electronic parts, and the like.

Hereinafter, preferred examples are provided to aid the understanding of the present invention, but the following examples are merely for exemplifying the present invention, and it will be apparent to those skilled in the art that various changes and modifications can be made within the scope and spirit of the present invention. It is natural that such variations and modifications fall within the scope of the appended claims.

Production Example  One: Alkoxymethylamide Group  or Carboxymethylamide Group  Having acrylic copolymer

Production Example  1-1

90 parts by weight of n-butyl acrylate (BA), 7 parts by weight of methyl acrylate (MA) in a 1 L reactor equipped with a refrigeration system to allow nitrogen gas to be refluxed and for easy temperature control,

Figure 112013078356513-pat00043
After the monomer mixture consisting of 3 parts by weight was added, 100 parts by weight of ethyl acetate (acetone) was added as a solvent. Then, after purging nitrogen gas for 1 hour to remove oxygen, it was maintained at 62 ℃. After the mixture was homogenized, 0.07 parts by weight of azobis isobutyronitrile (AIBN) was added as a reaction initiator, and reacted for 6 hours to have an alkoxymethylamide group having a weight average molecular weight of about 1 million. An acrylic copolymer was prepared.

Production Example  1-2

The same as in Preparation Example 1-1,

Figure 112013078356513-pat00044
Instead of
Figure 112013078356513-pat00045
Having an alkoxymethylamide group An acrylic copolymer was prepared.

Production Example  1-3

The same as in Preparation Example 1-1,

Figure 112013078356513-pat00046
Instead of
Figure 112013078356513-pat00047
Having an alkoxymethylamide group An acrylic copolymer was prepared.

Production Example  1-4

The same as in Preparation Example 1-1,

Figure 112013078356513-pat00048
Instead of
Figure 112013078356513-pat00049
Having a carboxymethylamide group An acrylic copolymer was prepared.

Production Example  1-5

In the same manner as in Preparation Example 1-1,

Figure 112013078356513-pat00050
Instead of
Figure 112013078356513-pat00051
Having a carboxymethylamide group An acrylic copolymer was prepared.

Production Example  1-6

In the same manner as in Preparation Example 1-1, 92.5 parts by weight of n-butyl acrylate (BA), 7 parts by weight of methyl acrylate (MA),

Figure 112013078356513-pat00052
Using a monomer mixture consisting of 0.5 parts by weight having an alkoxymethylamide group An acrylic copolymer was prepared.

Production Example  1-7

In the same manner as in Preparation Example 1-1, n-butyl acrylate (BA) 92 parts by weight, methyl acrylate (MA) 7 parts by weight,

Figure 112013078356513-pat00053
Using a monomer mixture consisting of 1 part by weight having an alkoxymethylamide group An acrylic copolymer was prepared.

Production Example  1-8

In the same manner as in Preparation Example 1-1, n-butyl acrylate (BA) 85 parts by weight, methyl acrylate (MA) 7 parts by weight,

Figure 112013078356513-pat00054
8 parts by weight of the monomer mixture having an alkoxymethylamide group An acrylic copolymer was prepared.

Production Example  1-9

In the same manner as in Preparation Example 1-1, n-butyl acrylate (BA) 78 parts by weight, methyl acrylate (MA) 7 parts by weight,

Figure 112013078356513-pat00055
15 parts by weight of the monomer mixture to have an alkoxymethylamide group An acrylic copolymer was prepared.

Production Example  1-10

In the same manner as in Preparation Example 1-1, 89 parts by weight of n-butyl acrylate (BA), 7 parts by weight of methyl acrylate (MA),

Figure 112013078356513-pat00056
3 parts by weight of a monomer mixture consisting of 1 part by weight of hydroxyethyl acrylate (HEA) having an alkoxymethylamide group An acrylic copolymer was prepared.

Production Example  2: Carboxyl group  Having acrylic copolymer

Production Example  2-1

89 parts by weight of n-butyl acrylate (BA), 7.0 parts by weight of methyl acrylate (MA) in a 1 L reactor equipped with a refrigeration system to allow nitrogen gas to be refluxed and to facilitate temperature control.

Figure 112013078356513-pat00057
A monomer mixture consisting of 3.0 parts by weight and 1.0 parts by weight of 4-hydroxybutyl acrylate (4HBA) was added, followed by 100 parts by weight of acetone as a solvent. Then, after purging nitrogen gas for 1 hour to remove oxygen, it was maintained at 62 ℃. After the mixture was homogeneous, 0.07 parts 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 million.

Production Example  2-2

In the same manner as in Preparation Example 2-1,

Figure 112013078356513-pat00058
Instead of
Figure 112013078356513-pat00059
To prepare an acrylic copolymer having a carboxyl group.

Production Example  2-3

In the same manner as in Preparation Example 2-1,

Figure 112013078356513-pat00060
Instead of
Figure 112013078356513-pat00061
To prepare an acrylic copolymer having a carboxyl group.

Production Example  2-4

In the same manner as in Preparation Example 2-1,

Figure 112013078356513-pat00062
Instead of
Figure 112013078356513-pat00063
To prepare an acrylic copolymer having a carboxyl group.

Production Example  2-5

In the same manner as in Preparation Example 2-1,

Figure 112013078356513-pat00064
Instead of
Figure 112013078356513-pat00065
To prepare an acrylic copolymer having a carboxyl group.

Production Example  2-6

In the same manner as in Preparation Example 2-1,

Figure 112013078356513-pat00066
Instead of
Figure 112013078356513-pat00067
To prepare an acrylic copolymer having a carboxyl group.

Production Example  2-7

In the same manner as in Preparation Example 2-1,

Figure 112013078356513-pat00068
Instead of
Figure 112013078356513-pat00069
To prepare an acrylic copolymer having a carboxyl group.

Production Example  2-8

In the same manner as in Preparation Example 2-1,

Figure 112013078356513-pat00070
Instead of
Figure 112013078356513-pat00071
To prepare an acrylic copolymer having a carboxyl group.

Production Example  2-9

In the same manner as in Preparation Example 2-1,

Figure 112013078356513-pat00072
Instead of
Figure 112013078356513-pat00073
To prepare an acrylic copolymer having a carboxyl group.

Production Example  2-10

In the same manner as in Preparation Example 2-1, 90 parts by weight of n-butyl acrylate (BA), 7.0 parts by weight of methyl acrylate (MA),

Figure 112013078356513-pat00074
An acrylic copolymer having a carboxyl group was prepared using 2.0 parts by weight and 1.0 part by weight of hydroxyethyl acrylate.

Production Example  2-11

In the same manner as in Preparation Example 2-1, n-butyl acrylate (BA) 82 parts by weight, methyl acrylate (MA) 7.0 parts by weight,

Figure 112013078356513-pat00075
An acrylic copolymer having a carboxyl group was prepared using 10.0 parts by weight and 1.0 part by weight of hydroxyethyl acrylate.

Production Example  2-12

In the same manner as in Preparation Example 2-1, n-butyl acrylate (BA) 77 parts by weight, methyl acrylate (MA) 7.0 parts by weight,

Figure 112013078356513-pat00076
An acrylic copolymer having a carboxyl group was prepared using 15.0 parts by weight and 1.0 part by weight of hydroxyethyl acrylate.

compare Production Example  One

A monomer mixture consisting of 92 parts by weight of n-butyl acrylate (BA), 7 parts by weight of methyl acrylate (MA) and 1 part by weight of hydroxyethyl acrylate (HEA) was used in the same manner as in Preparation Example 1-1. To have an alkoxymethylamide group An acrylic copolymer was prepared.

Example  1-27 and Comparative example  1-4

After mixing to the composition of Table 1 and diluted in ethyl acetate to prepare a pressure-sensitive adhesive composition of 15% solids concentration. The pressure-sensitive adhesive composition prepared above was applied on a release film coated with a silicone release agent to have a thickness of 25 μm, and dried at 100 ° C. for 1 minute to form an adhesive layer.

A pressure-sensitive adhesive polarizing plate was prepared by laminating the pressure-sensitive adhesive layer prepared above on an iodine-based polarizing plate having a thickness of 185 μm by adhesive processing.

division
(Parts by weight) Acrylic Copolymer Crosslinking agent Silane coupling agent Amide group Carboxyl group Example 1 Preparation Example 1-5 (50) Preparation Example 2-1 (50) 0.5 0.5 Example 2 Preparation Example 1-5 (50) Preparation Example 2-2 (50) 0.5 0.5 Example 3 Preparation Example 1-5 (50) Preparation Example 2-3 (50) 0.5 0.5 Example 4 Preparation Example 1-5 (50) Preparation Example 2-4 (50) 0.5 0.5 Example 5 Preparation Example 1-5 (50) Preparation Example 2-5 (50) 0.5 0.5 Example 6 Preparation Example 1-5 (50) Preparation Example 2-6 (50) 0.5 0.5 Example 7 Preparation Example 1-5 (50) Preparation Example 2-7 (50) 0.5 0.5 Example 8 Preparation Example 1-5 (50) Preparation Example 2-8 (50) 0.5 0.5 Example 9 Preparation Example 1-5 (50) Preparation Example 2-9 (50) 0.5 0.5 Example 10 Preparation Example 1-5 (50) Preparation Example 2-10 (50) 0.5 0.5 Example 11 Preparation Example 1-5 (50) Preparation Example 2-11 (50) 0.5 0.5 Example 12 Preparation Example 1-5 (50) Preparation Example 2-12 (50) 0.5 0.5 Example 13 Preparation Example 1-1 (50) Preparation Example 2-4 (50) 0.5 0.5 Example 14 Preparation Example 1-2 (50) Preparation Example 2-4 (50) 0.5 0.5 Example 15 Preparation Example 1-3 (50) Preparation Example 2-4 (50) 0.5 0.5 Example 16 Preparation Example 1-4 (50) Preparation Example 2-4 (50) 0.5 0.5 Example 17 Preparation Example 1-5 (50) Preparation Example 2-4 (50) 0.5 0.5 Example 18 Preparation Example 1-6 (50) Preparation Example 2-4 (50) 0.5 0.5 Example 19 Preparation Example 1-7 (50) Preparation Example 2-4 (50) 0.5 0.5 Example 20 Preparation Example 1-8 (50) Preparation Example 2-4 (50) 0.5 0.5 Example 21 Preparation Example 1-9 (50) Preparation Example 2-4 (50) 0.5 0.5 Example 22 Preparation Example 1-10 (50) Preparation Example 2-4 (50) 0.5 0.5 Example 23 Preparation Example 1-5 (10) Preparation Example 2-4 (90) 0.5 0.5 Example 24 Preparation Example 1-5 (30) Preparation Example 2-4 (70) 0.5 0.5 Example 25 Preparation Example 1-5 (70) Preparation Example 2-4 (30) 0.5 0.5 Example 26 Preparation Example 1-5 (90) Preparation Example 2-4 (10) 0.5 0.5 Example 27 Preparation Example 1-5 (50) Preparation Example 2-4 (50) - 0.5 Comparative Example 1 Preparation Example 1-5 (100) - 1.0 0.5 Comparative Example 2 - Preparation Example 2-4 (100) 1.0 0.5 Comparative Example 3 Preparation Example 1-5 (50) Comparative Production Example 1 (50) 1.0 0.5 Comparative Example 4 Comparative Production Example 1 (50) Preparation Example 2-4 (50) 1.0 0.5 Crosslinking agent: Coronate-L (CORONATE-L, Japan Urethane Industry)
Silane coupling agent: KBM-403 (Shin-Etsu Corporation)

Test Example

The physical properties of the pressure-sensitive adhesive polarizing plate prepared in Examples and Comparative Examples were measured by the following method, and the results are shown in Table 2 below.

1.Heat resistance / Moisture and Heat Resistance

After removing the release film of the polarizing plate with a pressure-sensitive adhesive, bonded to the surface of the pressure-sensitive adhesive layer and Corning glass, after standing for 300 hours at 80 ℃ and 60 ℃ / 90 RH% conditions, the appearance was confirmed.

<Evaluation Criteria>

Bubble and exfoliation 5 or more acknowledged: ×

Bubble and exfoliation 3 or 4 admitted: △

Less than 2 bubbles and peelings are admitted: ○

Bubbles and Peelings Unidentified: ◎

2. Reworkability

The pressure-sensitive adhesive polarizing plate was cut out to a width of 25 mm and a length of 100 mm, and the release film was peeled off. Then, the glass was laminated on Corning's # 1737 glass at a pressure of 0.25 MPa, and the autoclave was kept at 5 atmospheres and 50 ° C. for 20 minutes. Treatment to prepare an evaluation sample. After putting in a 50 ℃ oven was taken out after 5 hours and left at room temperature for 120 hours, it was peeled off at a rate of 1.3 cm / s. In addition, after being put into an oven at 60 ° C. and 90 RH% of moisture conditions, it was taken out after 4 hours and left at room temperature for 120 hours, followed by peeling at a speed of 1.3 cm / s.

<Evaluation Criteria>

-In both conditions, there is no adhesive left on the glass substrate and peeling off without tearing of the polarizing plate: ○

The adhesive remains on the panel under more than one condition or the polarizer is torn during the peeling process: ×

division Heat resistance Moisture and Heat Resistance Reworkability 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 ◎ ◎ ○ Example 24 ◎ ◎ ○ Example 25 ◎ ◎ ○ Example 26 ◎ ◎ ○ Example 27 △ ◎ ○ Comparative Example 1 × × × Comparative Example 2 × × ○ Comparative Example 3 × × × Comparative Example 4 × × ×

As shown in Table 2, the pressure-sensitive adhesive composition of Examples 1 to 27 using a specific acrylic copolymer in accordance with the present invention is superior in durability and rework resistance, such as heat and moisture resistance compared to Comparative Examples 1 to 4 I could confirm it.

Claims (9)

As an adhesive composition containing the acrylic copolymer containing the monomer which has an amide group, and the acrylic copolymer containing the monomer which has a carboxy group,
The acrylic copolymer containing the monomer having an amide group includes a (meth) acrylate monomer having an alkyl group having 1 to 12 carbon atoms and a monomer of Formula 1 or Formula 2 below:
[Formula 1]
Figure 112019064822736-pat00098

[Formula 2]
Figure 112019064822736-pat00099

(Formula 1 or 2, R 1 is hydrogen or methyl group, R 2 and R 3 are each independently C 1 -C 8 aliphatic hydrocarbon group, halogen-substituted C 1 -C 8 aliphatic hydrocarbon group or C 6 -C 8 aromatic hydrocarbon group).
The adhesive composition of Claim 1 containing 10-90 weight% of acrylic copolymers containing the monomer which has the said amide group, and 10-90 weight% of acrylic copolymers containing the monomer which has a carboxyl group.
delete The pressure-sensitive adhesive composition of claim 1, wherein R 1 is hydrogen or a methyl group, and R 2 and R 3 are each independently a C 1 -C 8 alkyl group, a halogen-substituted alkyl group, a benzyl group, or a phenyl group.
The pressure-sensitive adhesive composition of claim 1, wherein the monomer of Formula 1 or Formula 2 is at least one selected from the group consisting of Formulas 3 to 12:
[Formula 3]
Figure 112019064822736-pat00079

[Formula 4]
Figure 112019064822736-pat00080

[Formula 5]
Figure 112019064822736-pat00081

[Formula 6]
Figure 112019064822736-pat00082

[Formula 7]
Figure 112019064822736-pat00083

[Formula 8]
Figure 112019064822736-pat00084

[Formula 9]
Figure 112019064822736-pat00085

[Formula 10]
Figure 112019064822736-pat00086

[Formula 11]
Figure 112019064822736-pat00087

[Formula 12]
Figure 112019064822736-pat00088

 The pressure-sensitive adhesive composition of claim 1, wherein the monomer of Formula 1 or Formula 2 contains 0.1 to 10 parts by weight based on 100 parts by weight of the (meth) acrylate monomer having an alkyl group having 1 to 12 carbon atoms.
The pressure-sensitive adhesive composition of claim 1, wherein the acrylic copolymer containing a monomer having a carboxyl group contains a (meth) acrylate monomer having an alkyl group having 1 to 12 carbon atoms and at least one monomer selected from Formulas 13 to 21 below. :
[Formula 13]
Figure 112019064822736-pat00089

[Formula 14]
Figure 112019064822736-pat00090

[Formula 15]
Figure 112019064822736-pat00091

[Formula 16]
Figure 112019064822736-pat00092

[Formula 17]
Figure 112019064822736-pat00093

[Formula 18]
Figure 112019064822736-pat00094

[Formula 19]
Figure 112019064822736-pat00095

[Formula 20]
Figure 112019064822736-pat00096

[Formula 21]
Figure 112019064822736-pat00097

 The pressure-sensitive adhesive composition of claim 7, wherein the at least one monomer selected from Formulas 13 to 21 contains 0.1 to 10 parts by weight based on 100 parts by weight of the (meth) acrylate monomer having an alkyl group having 1 to 12 carbon atoms.
The pressure-sensitive adhesive composition of claim 1, wherein the pressure-sensitive adhesive composition further contains a crosslinking agent.
KR1020130102109A 2013-08-28 2013-08-28 Adhesive composition KR102051483B1 (en)

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JP2009197109A (en) * 2008-02-20 2009-09-03 Nippon Zeon Co Ltd Acrylic resin composition, thermally conductive pressure-sensitive adhesive sheet made of the acrylic resin composition, method of producing the thermally conductive pressure-sensitive adhesive sheet, and composite comprising substrate and the thermally conductive pressure-sensitive adhesive sheet
JP2012087258A (en) * 2010-10-22 2012-05-10 Toyo Ink Sc Holdings Co Ltd Resin composition for pressure sensitivity type adhesive, and pressure sensitivity type adhesive comprising using the same

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JP2009197109A (en) * 2008-02-20 2009-09-03 Nippon Zeon Co Ltd Acrylic resin composition, thermally conductive pressure-sensitive adhesive sheet made of the acrylic resin composition, method of producing the thermally conductive pressure-sensitive adhesive sheet, and composite comprising substrate and the thermally conductive pressure-sensitive adhesive sheet
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