KR20140140872A - Acrylic copolmer and adhesive composition containing threrof - Google Patents
Acrylic copolmer and adhesive composition containing threrof Download PDFInfo
- Publication number
- KR20140140872A KR20140140872A KR1020130061833A KR20130061833A KR20140140872A KR 20140140872 A KR20140140872 A KR 20140140872A KR 1020130061833 A KR1020130061833 A KR 1020130061833A KR 20130061833 A KR20130061833 A KR 20130061833A KR 20140140872 A KR20140140872 A KR 20140140872A
- Authority
- KR
- South Korea
- Prior art keywords
- group
- sensitive adhesive
- formula
- pressure
- weight
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
- C08F220/36—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate containing oxygen in addition to the carboxy oxygen, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/60—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing nitrogen in addition to the carbonamido nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/60—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing nitrogen in addition to the carbonamido nitrogen
- C08F220/603—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing nitrogen in addition to the carbonamido nitrogen and containing oxygen in addition to the carbonamido oxygen and nitrogen
-
- 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
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/10—Homopolymers or copolymers of methacrylic acid esters
-
- 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
- C09J139/00—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 a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Adhesives based on derivatives of such polymers
- C09J139/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
본 발명은 양생 기간이 단축되고, 내구성 및 리워크성이 우수한 점착제 조성물에 관한 것이다.
The present invention relates to a pressure-sensitive adhesive composition having a shortened curing period and excellent durability and reworkability.
액정표시장치(Liquid crystal display device, LCD)는 액정셀과 상기 액정셀의 양면에 점착제층을 매개로 접합된 편광판을 포함하는 액정패널을 구비한다.2. Description of the Related Art A liquid crystal display device (LCD) includes a liquid crystal cell and a liquid crystal panel including a polarizing plate bonded to both sides of the liquid crystal cell via an adhesive layer.
상기 점착제는 기재와의 밀착성, 빛샘방지성, 내열 및 내습열 등의 내구성뿐만 아니라 리워크성과 같은 물성을 동시에 만족시켜야 한다. 또한, 상기 물성과 함께 점착제는 양생 기간을 단축시켜 생산성도 향상시킬 것이 요구된다.The pressure-sensitive adhesive should simultaneously satisfy not only adhesiveness to a substrate, light resistance, heat resistance and durability but also physical properties such as reworkability. In addition, the pressure-sensitive adhesive along with the physical properties is required to shorten the curing period and improve the productivity.
이와 같이 종래 점착제로서 요구되는 물성을 유지하면서도 양생 기간을 단축시키기 위한 방법으로 한국공개특허 제2011-0056250호에는 히드록시기 함유 아크릴아미드 단량체를 가교성 단량체로 사용한 점착제 조성물이 제시되어 있다.As a conventional method for shortening the curing period while maintaining physical properties required as a pressure-sensitive adhesive, Korean Patent Laid-Open Publication No. 2011-0056250 discloses a pressure-sensitive adhesive composition using a hydroxy group-containing acrylamide monomer as a crosslinking monomer.
상기 점착제 조성물은 24시간 정도의 양생기간을 가지나, 최근 편광판의 생산성 향상을 위해 1일 출하를 목표로 공정이 진행되므로 24시간의 양생기간은 결코 단축이라 볼 수 없는 실정이다. 또한 양생기간이 24시간 이하인 경우에는 내구성 및 리워크성 등의 물성 확보가 불가능하여 편광판용 점착제로서 적용이 어렵다는 단점이 있다.
The pressure-sensitive adhesive composition has a curing period of about 24 hours. However, in order to improve the productivity of the polarizing plate, the curing process for 24 hours is never shortened because the process is carried out with the aim of shipment per day. In addition, when the curing period is less than 24 hours, it is impossible to secure physical properties such as durability and reworkability, which makes it difficult to apply as a pressure sensitive adhesive for a polarizing plate.
본 발명은 별도의 가교촉진제를 첨가하지 않고도 24 시간 이하로 양생 기간을 단축시킬 수 있고, 점착제로서 요구되는 물성도 만족시킬 수 있는 점착제 조성물을 제공하는 것을 목적으로 한다.
An object of the present invention is to provide a pressure-sensitive adhesive composition which can shorten a curing period to 24 hours or less without addition of a separate crosslinking accelerator, and can satisfy physical properties required as a pressure-sensitive adhesive.
상기 목적을 달성하기 위하여, 본 발명은 하기 화학식 1 또는 화학식 2의 화합물과 히드록시기를 함유하는 아크릴계 단량체를 함유하는 아크릴계 공중합체를 제공한다.In order to achieve the above object, the present invention provides an acrylic copolymer containing a compound of the following general formula (1) or (2) and an acrylic monomer containing a hydroxyl group.
(상기 식 중, R1은 수소 또는 메틸기이고, X는 O 또는 NH이고, R2는 탄소수 1-12의 직쇄 또는 분지쇄인 지방족 탄화수소기로, 상기 지방족 탄화수소기는 주쇄에 N 또는 O를 포함하거나 포함하지 않고, 곁사슬에 ?H를 포함하거나 포함하지 않으며, R3 및 R4는 각각 독립적으로 수소, 할로겐, -OR5, -N(R5)2, -SR5, -CN, -NO2 또는 탄소수 1~12의 지방족 탄화수소이고, R5는 탄소수 1-12의 지방족 탄화수소임) Wherein R 1 is hydrogen or a methyl group, X is O or NH, and R 2 is a straight or branched chain aliphatic hydrocarbon group having 1-12 carbon atoms, and the aliphatic hydrocarbon group includes N or O in the main chain And R 3 and R 4 are each independently selected from the group consisting of hydrogen, halogen, -OR 5 , -N (R 5 ) 2 , -SR 5 , -CN, -NO 2 or An aliphatic hydrocarbon having 1 to 12 carbon atoms and R 5 is an aliphatic hydrocarbon having 1 to 12 carbon atoms)
바람직하기로, 상기 상기 화학식 1 또는 2의 화합물은 R1 수소 또는 메틸기이고, X는 산소이고, R2는 주쇄에 에테르기, 에스테르기 또는 우레탄기를 포함하고 곁사슬에 -OH 또는 수소를 포함하는 탄소수 1-4의 지방족 탄화수소기이며, R3 및 R4는 각각 독립적으로 수소일 수 있다.Preferably, wherein the compound of formula 1 or 2, R 1 is hydrogen or methyl, X is oxygen, R 2 has carbon atoms containing an ether, ester or urethane in the main chain and the side chain containing the -OH or hydrogen And R < 3 > and R < 4 > may each independently be hydrogen.
상기 화학식 1 또는 화학식 2의 화합물은 하기 화학식 3 내지 5로 이루어진 군에서 선택된 1종 이상일 수 있다.The compound of Formula 1 or Formula 2 may be at least one compound selected from the group consisting of the following Formulas 3 to 5.
상기 아크릴계 공중합체는 탄소수 4-12의 알킬기를 갖는 (메타)아크릴레이트 단량체, 상기 화학식 1 또는 화학식 2의 화합물 및 히드록시기를 함유하는 단량체를 함유할 수 있다. The acrylic copolymer may contain a (meth) acrylate monomer having an alkyl group having 4 to 12 carbon atoms, a compound having the formula (1) or (2), and a monomer having a hydroxyl group.
상기 화학식 1 또는 화학식 2의 화합물은 탄소수 4-12의 알킬기를 갖는 (메타)아크릴레이트 단량체 100중량부에 대하여 0.1 내지 10중량부를 함유할 수 있다.The compound 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 4-12 carbon atoms.
또한, 본 발명은 상기 아크릴계 공중합체를 함유하는 점착제 조성물을 제공한다.The present invention also provides a pressure-sensitive adhesive composition containing the acrylic copolymer.
상기 점착제 조성물은 가교제를 추가로 함유할 수 있다.
The pressure-sensitive adhesive composition may further contain a crosslinking agent.
본 발명의 점착제 조성물은 별도의 가교촉진제를 첨가하지 않고도 24 시간 이하로 양생 기간을 단축시킬 수 있고, 점착제로서 요구되는 물성(저장안정성, 내구성 및 리워크성 등)도 만족시킬 수 있는 이점이 있다.
The pressure-sensitive adhesive composition of the present invention has an advantage that the curing period can be shortened to 24 hours or less without addition of a separate crosslinking accelerator, and satisfactory physical properties (storage stability, durability, and workability) required as a pressure-sensitive adhesive .
본 발명은 신규의 아크릴레이트계 화합물을 함유하는 아크릴계 공중합체를 사용하여 양생 기간이 단축되고, 내구성 및 리워크성이 우수한 점착제 조성물에 관한 것이다.
The present invention relates to a pressure-sensitive adhesive composition which is shortened in curing time by using an acrylic copolymer containing a novel acrylate-based compound and is excellent in durability and reworkability.
이하 본 발명을 상세히 설명하면 다음과 같다.Hereinafter, the present invention will be described in detail.
본 발명의 아크릴계 공중합체는 하기 화학식 1 또는 화학식 2의 화합물을 함유한다.The acrylic copolymer of the present invention contains a compound represented by the following general formula (1) or (2).
[화학식 1][Chemical Formula 1]
[화학식 2](2)
(상기 식 중, R1은 수소 또는 메틸기이고, X는 O 또는 NH이고, R2는 탄소수 1-12의 직쇄 또는 분지쇄인 지방족 탄화수소기로, 상기 지방족 탄화수소기는 주쇄에 N 또는 O를 포함하거나 포함하지 않고, 곁사슬에 ?H를 포함하거나 포함하지 않으며, R3 및 R4는 각각 독립적으로 수소, 할로겐, -OR5, -N(R5)2, -SR5, -CN, -NO2 또는 탄소수 1~12의 지방족 탄화수소이고, R5는 탄소수 1-12의 지방족 탄화수소임) Wherein R 1 is hydrogen or a methyl group, X is O or NH, and R 2 is a straight or branched chain aliphatic hydrocarbon group having 1-12 carbon atoms, and the aliphatic hydrocarbon group includes N or O in the main chain And R 3 and R 4 are each independently selected from the group consisting of hydrogen, halogen, -OR 5 , -N (R 5 ) 2 , -SR 5 , -CN, -NO 2 or An aliphatic hydrocarbon having 1 to 12 carbon atoms and R 5 is an aliphatic hydrocarbon having 1 to 12 carbon atoms)
바람직하기로는 상기 화학식 1 또는 2의 화합물은 R1 수소 또는 메틸기이고, X는 산소이고, R2는 주쇄에 에테르기, 에스테르기 또는 우레탄기를 포함하고 곁사슬에 -OH 또는 수소를 포함하는 탄소수 1-4의 지방족 탄화수소기이며, R3 및 R4는 각각 독립적으로 수소인 것이 좋다.Preferably the compounds of the formula (I) or (II) R 1 is hydrogen or methyl, X is oxygen, R 2 is a 1-carbon atoms containing an ether, ester or urethane in the main chain and the side chain containing the -OH or hydrogen Lt; 3 > and R < 4 > are each independently hydrogen.
보다 바람직하기로 상기 화학식 1 또는 화학식 2의 화합물은 하기 화학식 3 내지 5로 이루어진 군에서 선택된 1종 이상일 수 있다.More preferably, the compound of formula (1) or (2) may be at least one compound selected from the group consisting of the following formulas (3) to (5)
[화학식 3](3)
[화학식 4][Chemical Formula 4]
[화학식 5][Chemical Formula 5]
본 발명의 아크릴계 공중합체는 탄소수 4-12의 알킬기를 갖는 (메타)아크릴레이트 단량체 및 상기 화학식 1의 화합물을 함유하는 것이 바람직하다. 여기서 (메타)아크릴레이트는 아크릴레이트 및 메타크릴레이트를 의미한다.The acrylic copolymer of the present invention preferably contains a (meth) acrylate monomer having an alkyl group having 4 to 12 carbon atoms and a compound represented by the above formula (1). Here, (meth) acrylate means acrylate and methacrylate.
상기 화학식 1 또는 2의 화합물은 분자내에 염기성 촉매 역할을 수행하여, 아민을 함유한 아크릴계 공중합체로 가교제와 가교성 단량체와의 가교 반응성을 향상시켜서, 별도의 가교촉진제 등의 첨가 성분 없이도 양생기간이 단축된다. The compound of Formula 1 or 2 acts as a basic catalyst in the molecule to improve the crosslinking reactivity between the crosslinking agent and the crosslinkable monomer with an acrylic copolymer containing an amine so that the curing period is shortened without any additional components such as a crosslinking accelerator .
구체적으로 용액상태에서는 공중합체에 고정화되어 가교제와의 상호작용이어려우므로 조액안정성의 확보가 용이하며, 코팅 건조 후에는 가교성 단량체 및 가교제와의 반응을 촉진하여, 양생단축을 가능하게 한다.Specifically, it is immobilized on the copolymer in a solution state, and it is difficult to interact with the crosslinking agent, so stability of the liquid solution can be easily ensured. After the coating and drying, the reaction with the crosslinking monomer and the crosslinking agent is promoted to shorten curing.
또한, 상기 화학식 1 또는 2의 화합물은 가교의 형태에 영향을 주어, 점착제내의 응집력을 향상시키는데 기여하므로 내구성과 리워크성이 향상될 수 있다.
Further, the compound of the above formula (1) or (2) affects the form of crosslinking and contributes to enhance cohesion in the pressure-sensitive adhesive, so that durability and reworkability can be improved.
탄소수 4 내지 12의 알킬(메타)아크릴레이트 단량체로는 탄소수 4 내지 12의 지방족 알콜로부터 유도되는 (메타)아크릴레이트로서, 예를 들면 n-부틸(메타)아크릴레이트, 2-부틸(메타)아크릴레이트, t-부틸(메타)아크릴레이트, 펜틸(메타)아크릴레이트, 옥틸(메타)아크릴레이트, 2-에틸헥실(메타)아크릴레이트, 노닐(메타)아크릴레이트, 데실(메타)아크릴레이트, 라우릴(메타)아크릴레이트 등을 들 수 있으며, 이들은 단독 또는 2종 이상 혼합하여 사용할 수 있다. 이 중에서 n-부틸아크릴레이트, 2-에틸헥실아크릴레이트 또는 이들의 혼합물이 바람직하다. Examples of the alkyl (meth) acrylate monomer having 4 to 12 carbon atoms include (meth) acrylates derived from aliphatic alcohols having 4 to 12 carbon atoms such as n-butyl (meth) acrylate, Octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isopropyl (meth) acrylate, (Meth) acrylate, etc. These may be used alone or in combination of two or more. Of these, n-butyl acrylate, 2-ethylhexyl acrylate or a mixture thereof is preferable.
상기 화학식 1 또는 2의 화합물은 탄소수 4-12의 알킬기를 갖는 (메타)아크릴레이트 단량체 100중량부에 대하여 0.1 내지 10중량부, 바람직하기로는 0.1 내지 7중량부 함유할 수 있다. 함유량이 0.1중량부 미만이면 가교 반응 촉진 효과가 미미하여 양생 기간 단축 효과와 내구성 향상 효과를 기대하기 어려울 수 있다. 함량이 10중량부를 초과하는 경우에는 가교 반응이 지나치게 빨라져 조성물의 안정성에 문제가 발생할 수 있고 점착력이 박리력이 커져 리워크 작업 시 기재에 점착제가 잔류할 수 있다.The compound of formula (1) or (2) may contain 0.1 to 10 parts by weight, preferably 0.1 to 7 parts by weight, based on 100 parts by weight of the (meth) acrylate monomer having an alkyl group having 4-12 carbon atoms. If the content is less than 0.1 part by weight, the effect of accelerating the crosslinking reaction is insignificant and it may be difficult to expect a shortening effect of the curing period and an improvement in durability. When the content exceeds 10 parts by weight, the crosslinking reaction becomes excessively rapid, which may cause problems in the stability of the composition, and the peeling force of the adhesive force becomes large, so that the pressure-sensitive adhesive may remain on the substrate during reworking.
히드록시기를 갖는 단량체로는 2-히드록시에틸(메타)아크릴레이트, 2-히드록시프로필(메타)아크릴레이트, 2-히드록시부틸(메타)아크릴레이트, 4-히드록시부틸(메타)아크릴레이트, 6-히드록시헥실(메타)아크릴레이트, 2-히드록시에틸렌글리콜(메타)아크릴레이트, 2-히드록시프로필렌글리콜(메타)아크릴레이트, 알킬렌기의 탄소수가 2-4인 히드록시알킬렌글리콜(메타)아크릴레이트, 4-히드록시부틸비닐에테르, 5-히드록시펜틸비닐에테르, 6-히드록시헥실비닐에테르, 7-히드록시헵틸비닐에테르, 8-히드록시옥틸비닐에테르, 9-히드록시노닐비닐에테르 및 10-히드록시데실비닐에테르 등을 들 수 있으며, 이들 중에서 4-히드록시부틸비닐에테르가 바람직하다. 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. Of these, 4-hydroxybutyl vinyl ether is preferable.
상기 히드록시기를 갖는 단량체는 탄소수 4-12의 알킬기를 갖는 (메타)아크릴레이트 단량체 100중량부에 대하여 0.1 내지 5중량부, 바람직하기로는 1 내지 3중량부 함유할 수 있다. 함량이 0.1중량부 미만이면 응집력이 부족하여 내열조건에서 기포가 발생할 수 있고, 5중량부를 초과하는 경우에는 지나친 가교로 점착력이 저하되어 내열조건에서 박리불량이 발생할 수 있다.The monomer having a hydroxyl group may be contained in an amount of 0.1 to 5 parts by weight, preferably 1 to 3 parts by weight, based on 100 parts by weight of the (meth) acrylate monomer having an alkyl group having 4 to 12 carbon atoms. When the content is less than 0.1 parts by weight, cohesion is insufficient and bubbles may be generated under heat-resistant conditions. When the content is more than 5 parts by weight, the adhesive strength is reduced due to excessive crosslinking, and peeling failure may occur under heat-resistant conditions.
또한, 본 발명의 아크릴계 공중합체는 상기 화학식 1 또는 2의 화합물에 의한 가교관능기 이외에, 추가적으로 가교 가능한 관능기를 갖는 중합성 단량체를 추가로 함유할 수 있다. 상기 중합성 단량체는 하기 가교제와의 화학 결합에 의해 응집력 또는 점착 강도를 부여하는 작용을 하는 것으로서, 카르복시기를 갖는 단량체, 아미드기를 갖는 단량체 및 3차 아민기를 갖는 단량체 등을 들 수 있다. 이들은 단독 또는 2종 이상 혼합하여 사용할 수 있다. The acrylic copolymer of the present invention may further contain a polymerizable monomer having a crosslinkable functional group in addition to the crosslinkable functional group by the compound of the above formula (1) or (2). The polymerizable monomer has a function of imparting cohesive strength or adhesive strength by chemical bonding with the following crosslinking agent, and examples thereof include a monomer having a carboxyl group, a monomer having an amide group, and a monomer having a tertiary amine group. These may be used alone or in combination of two or more.
아미드기를 갖는 단량체로는 (메타)아크릴아미드, N-이소프로필아크릴아미드, N-3차부틸아크릴아미드, 3-히드록시프로필(메타)아크릴아미드, 4-히드록시부틸(메타)아크릴아미드, 6-히드록시헥실(메타)아크릴아미드, 8-히드록시옥틸(메타)아크릴아미드, 2-히드록시에틸헥실(메타)아크릴아미드 등을 들 수 있으며, 이들 중에서 (메타)아크릴아미드가 바람직하다. Examples of the monomer having an amide group include (meth) acrylamide, N-isopropyl acrylamide, N-tertiary butyl acrylamide, 3-hydroxypropyl (meth) acrylamide, 4-hydroxybutyl (Meth) acrylamide, 8-hydroxyoctyl (meth) acrylamide and 2-hydroxyethylhexyl (meth) acrylamide. Of these, (meth) acrylamide is preferable.
3차 아민기를 갖는 단량체로는 N,N-(디메틸아미노)에틸(메타)아크릴레이트, N,N-(디에틸아미노)에틸(메타)아크릴레이트, N,N-(디메틸아미노)프로필(메타)아크릴레이트 등을 들 수 있다. 카르복시기를 갖는 단량체로는 (메타)아크릴산, 크로톤산 등의 1가산; 말레인산, 이타콘산, 푸마르산 등의 2가산 및 이들의 모노알킬에스테르; 3-(메타)아크릴로일프로피온산; 알킬기의 탄소수가 2-3인 2-히드록시알킬(메타)아크릴레이트의 무수호박산 개환 부가체, 알킬렌기의 탄소수가 2-4인 히드록시알킬렌글리콜(메타)아크릴레이트의 무수 호박산 개환 부가체, 알킬기의 탄소수가 2-3인 2-히드록시알킬(메타)아크릴레이트의 카프로락톤 부가체에 무수 호박산을 개환 부가시킨 화합물 등을 들 수 있으며, 이들 중에서 (메타)아크릴산이 바람직하다. Examples of the monomer having a tertiary amine group include N, N- (dimethylamino) ethyl (meth) acrylate, N, N- (diethylamino) ethyl (meth) ) Acrylate, and the like. Examples of the monomer having a carboxyl group include monovalent acids such as (meth) acrylic acid and crotonic acid; Dicarboxylic acids such as maleic acid, itaconic acid, and fumaric acid, and monoalkyl esters thereof; 3- (meth) acryloylpropionic acid; A succinic anhydride ring-opening addition adduct of 2-hydroxyalkyl (meth) acrylate in which the alkyl group has 2 to 4 carbon atoms, anhydrous succinic ring opening adduct of a hydroxyalkylene glycol (meth) acrylate having 2 to 4 carbon atoms in the alkylene group , Compounds obtained by ring-opening addition of succinic anhydride to caprolactone adducts of 2-hydroxyalkyl (meth) acrylates whose alkyl groups have 2-3 carbon atoms, and among these, (meth) acrylic acid is preferable.
중합성 단량체는 아크릴계 공중합체의 제조에 사용되는 총 단량체 100중량부에 대하여 0.05 내지 10중량부로 포함되는 것이 바람직하고, 보다 바람직하게는 0.1 내지 8중량부인 것이 좋다. 함량이 0.05중량부 미만인 경우 점착제의 응집력이 작아지게 되어 내구성이 저하될 수 있으며, 10중량부 초과인 경우 높은 겔분율에 의해 점착력이 떨어지고 내구성에 문제를 야기할 수 있다. The polymerizable monomer 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 total monomers used in the production of the acrylic copolymer. 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.
또한, 상기 단량체들 이외에 다른 중합성 단량체가 점착력을 저하시키지 않는 범위, 예컨대 아크릴계 공중합체의 제조에 사용되는 총 단량체 100중량부에 대하여 10중량부 이하로 더 포함될 수 있다. In addition, other polymerizable monomers other than the above-mentioned monomers may be further added in an amount not lowering the adhesive force, for example, 10 parts by weight or less based on 100 parts by weight of the total monomers used in the production of the acrylic copolymer.
공중합체의 제조방법은 특별히 한정되지 않으며, 당 분야에서 통상적으로 사용되는 괴상중합, 용액중합, 유화중합 또는 현탁중합 등의 방법을 이용하여 제조할 수 있으며, 용액중합이 바람직하다. 또한, 중합 시 통상 사용되는 용매, 중합개시제, 분자량 제어를 위한 연쇄이동제 등을 사용할 수 있다. 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.
공중합체는 겔투과크로마토그래피(Gel permeation chromatography,GPC)에 의해 측정된 중량평균분자량(폴리스티렌 환산, Mw)이 5만 내지 200만, 바람직하게 40만 내지 200만인 것이 좋다. 상기 중량평균분자량이 5만 미만인 경우 공중합체 간의 응집력이 부족하여 점착 내구성에 문제를 야기할 수 있고, 200만 초과인 경우 도공 시 공정성을 확보하기 위하여 다량의 희석 용매를 필요로 할 수 있다.
The copolymer preferably has a weight average molecular weight (polystyrene conversion, Mw) of 50,000 to 2,000,000, preferably 400,000 to 2,000,000 as measured by gel permeation chromatography (GPC). If 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 diluting solvent may be required in order to ensure fairness in coating.
또한, 본 발명은 상기 아크릴계 공중합체를 함유한 점착제 조성물에 특징이 있다. 상기 점착제 조성물은 가교제를 추가로 함유할 수 있다. Further, the present invention is characterized by a pressure-sensitive adhesive composition containing the acrylic copolymer. The pressure-sensitive adhesive composition may further contain a crosslinking agent.
가교제는 공중합체를 적절히 가교함으로써 점착제의 응집력을 강화하기 위한 성분으로서, 그 종류는 특별히 한정되지 않는다. 예컨대, 이소시아네이트계 화합물, 에폭시계 화합물 등을 들 수 있으며, 이들은 단독 또는 2종 이상 혼합하여 사용할 수 있다.The crosslinking agent is a component for reinforcing the cohesive force of the pressure-sensitive adhesive by properly crosslinking the copolymer, and the kind thereof is not particularly limited. Examples thereof include isocyanate compounds and epoxy compounds, which may be used alone or in combination of two or more.
이소시아네이트계 화합물로는 톨릴렌디이소시아네이트, 자일렌디이소시아네이트, 2,4-디페닐메탄디이소시아네트, 4,4-디페닐메탄디이소시아네트, 헥사메틸렌디이소시아네이트, 이소포론디이소시아네이트, 테트라메틸자일렌디이소시아네이트, 나프탈렌디이소시아네이트 등의 디이소시아네이트 화합물; 트리메틸올프로판 등의 다가 알콜계 화합물 1몰에 디이소시아네이트 화합물 3몰을 반응시킨 부가체, 디이소시아네이트 화합물 3몰을 자기 축합시킨 이소시아누레이트체, 디이소시아네이트 화합물 3몰 중 2몰로부터 얻어지는 디이소시아네이트 우레아에 나머지 1몰의 디이소시아네이트가 축합된 뷰렛체, 트리페닐메탄트리이소시아네이트, 메틸렌비스트리이소시아네이트 등의 3개의 관능기를 함유하는 다관능 이소시아네이트 화합물 등을 들 수 있다.Examples of the isocyanate compound include tolylene diisocyanate, xylene diisocyanate, 2,4-diphenylmethane diisocyanate, 4,4-diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, tetramethyl xylene diisocyanate , Diisocyanate compounds such as naphthalene diisocyanate; An adduct obtained by reacting 3 moles of a diisocyanate compound with 1 mole of a polyhydric alcohol compound such as trimethylolpropane, an isocyanurate compound in which 3 moles of a diisocyanate compound is self-condensed, a diisocyanate obtained from 2 moles of 3 moles of a diisocyanate compound And multifunctional isocyanate compounds containing three functional groups such as burette, triphenylmethane triisocyanate and methylene bistriisocyanate in which the remaining one mole of diisocyanate is condensed in urea.
에폭시계 화합물로는 에틸렌글리콜디글리시딜에테르, 디에틸렌글리콜디글리시딜에테르, 폴리에틸렌글리콜디글리시딜에테르, 프로필렌글리콜디글리시딜에테르, 트리프로필렌글리콜디글리시딜에테르, 폴리프로필렌글리콜디글리시딜에테르, 네오펜틸글리콜디글리시딜에테르, 1,6-헥산디올디글리시딜에테르, 폴리테트라메틸렌글리콜디글리시딜에테르, 글리세롤디글리시딜에테르, 글리세롤트리글리시딜에테르, 디글리세롤폴리글리시딜에테르, 폴리글리세롤폴리글리시딜에테르, 레졸신디글리시딜에테르, 2,2-디브로모네오펜틸글리콜디글리시딜에테르, 트리메틸올프로판트리글리시딜에테르, 펜타에리트리톨폴리글리시딜에테르, 소르비톨폴리글리시딜에테르, 아디핀산디글리시딜에스테르, 프탈산디글리시딜에스테르, 트리스(글리시딜)이소시아누레이트, 트리스(글리시독시에틸)이소시아누레이트, 1,3-비스(N,N-글리시딜아미노메틸)시클로헥산, N,N,N',N'-테트라글리시딜-m-자일릴렌디아민 등을 들 수 있다.Examples of the epoxy compound include ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol Hexanediol diglycidyl ether, polytetramethylene glycol diglycidyl ether, glycerol diglycidyl ether, glycerol triglycidyl ether, glycerol diglycidyl ether, glycerol diglycidyl ether, Diglycerol polyglycidyl ether, polyglycerol polyglycidyl ether, resorcinol diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, trimethylol propane triglycidyl ether, pentaerythritol Polyglycidyl ether, sorbitol polyglycidyl ether, adipic acid diglycidyl ester, phthalic acid diglycidyl ester, tris (glycidyl) isocyanurate N, N ', N'-tetraglycidyl-m-glycidoxyethyl isocyanurate, 1,3-bis (N, N-glycidylaminomethyl) cyclohexane, Xylylenediamine, and the like.
또한, 이소시아네이트계 화합물, 에폭시계 화합물과 함께 멜라민계 화합물을 단독 또는 2종 이상 혼합하여 추가로 사용할 수 있다.In addition, an isocyanate compound, an epoxy compound, and a melamine compound may be used alone or in admixture of two or more.
멜리민계 화합물로는 헥사메틸올멜라민, 헥사메톡시메틸멜라민, 헥사부톡시메틸멜라민 등을 들 수 있다.Examples of the melamine-based compound include hexamethylol melamine, hexamethoxymethyl melamine, and hexabutoxymethyl melamine.
가교제는 고형분 함량을 기준으로 공중합체 100중량부에 대하여 0.1 내지 15중량부로 포함되는 것이 바람직하고, 보다 바람직하게는 0.1 내지 5중량부인 것이 좋다. 함량이 0.1중량부 미만인 경우 부족한 가교도로 인해 응집력이 작아지게 되어 들뜸과 같은 내구성 저하가 유발되고 절단성을 해칠 수 있으며, 15중량부 초과인 경우 과다 가교반응에 의해 잔류응력 완화에 문제가 발생할 수 있다.The crosslinking agent is preferably contained in an amount of 0.1 to 15 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the copolymer based on the solid content. When the content is less than 0.1 parts by weight, the cohesive force becomes small due to insufficient crosslinking, resulting in deterioration of durability such as peeling and deterioration of cutability. If the content is more than 15 parts by weight, excessive crosslinking reaction may cause a problem of relaxation of residual stress have.
또한, 본 발명의 점착제 조성물은 실란커플링제를 더 포함할 수 있다.In addition, the pressure-sensitive adhesive composition of the present invention may further comprise a silane coupling agent.
실란커플링제의 종류는 특별히 한정되지 않으며, 예컨대 비닐클로로실란, 비닐트리메톡시실란, 비닐트리에톡시실란, 2-(3,4-에폭시시클로헥실)에틸트리메톡시실란, 3-글리시독시프로필트리메톡시실란, 3-글리시독시프로필메틸디에톡시실란, 3-글리시독시프로필디에톡시실란, 3-글리시독시프로필트리에톡시실란, p-스티릴트리메톡시실란, 3-메타크릴옥시프로필트리에톡시실란, 3-메타크릴옥시프로필트리메톡시실란, 3-메타크릴옥시프로필메틸디메톡시실란, 3-메타크릴옥시프로필메틸디에톡시실란, 3-아크릴옥시프로필트리메톡시실란, N-2-(아미노에틸)-3-아미노프로필메틸디메톡시실란, N-2-(아미노에틸)-3-아미노프로필트리메톡시실란, N-2-(아미노에틸)-3-아미노프로필메틸트리에톡시실란, 3-아미노프로필트리메톡시실란, 3-아미노프로필트리에톡시실란, 3-트리에톡시실릴-N-(1,3-디메틸부틸리덴)프로필아민, N-페닐-3-아미노프로필트리메톡시실란, 3-클로로프로필트리메톡시실란, 3-머캅토프로필메틸디메톡시실란, 3-머캅토프로필트리메톡시실란, 비스(트리에톡시실릴프로필)테트라설파이드, 3-이소시아네이트프로필트리에톡시실란 등을 들 수 있다. 이들은 단독 또는 2종 이상 혼합하여 사용할 수 있다.The kind of the silane coupling agent is not particularly limited, and examples thereof include vinylchlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3- 3-glycidoxypropyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, Acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-acryloxypropyltrimethoxysilane , N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) Methyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethylbutylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3- Dimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis (triethoxysilylpropyl) tetrasulfide, 3-isocyanatepropyltriethoxysilane, and the like. These may be used alone or in combination of two or more.
실란커플링제는 고형분 함량을 기준으로 공중합체 100중량부에 대하여 0 내지 10중량부로 포함될 수 있으며, 바람직하게 0.005 내지 5중량부로 포함되는 것이 좋다. 함량이 10중량부 초과인 경우 내구성이 저하될 수 있다.The silane coupling agent may be contained in an amount of 0 to 10 parts by weight, preferably 0.005 to 5 parts by weight, based on 100 parts by weight of the copolymer based on the solid content. If the content exceeds 10 parts by weight, the durability may be lowered.
상기와 같은 성분 이외에, 점착제 조성물은 용도에 따라 요구되는 점착력, 응집력, 점성, 탄성률, 유리전이온도, 대전방지성 등을 조절하기 위하여, 점착성 부여 수지, 산화방지제, 부식방지제, 레벨링제, 표면윤활제, 염료, 안료, 소포제, 충전제, 광안정제, 대전방지제 등의 첨가제를 더 포함할 수 있다.In addition to the above-mentioned components, the pressure-sensitive adhesive composition may further contain additives such as a tackifier resin, an antioxidant, a corrosion inhibitor, a leveling agent, a surface lubricant, an antioxidant, , A dye, a pigment, a defoaming agent, a filler, a light stabilizer, an antistatic agent, and the like.
본 발명의 점착제 조성물은 액정셀과의 접합을 위한 편광판용 점착제뿐만 아니라 표면보호필름용 점착제로서도 모두 사용할 수 있다. 또한, 보호필름, 반사시트, 구조용 점착시트, 사진용 점착시트, 차선표시용 점착시트, 광학용 점착제품, 전자부품용 점착제뿐만 아니라 일반 상업용 점착시트제품, 의료용 패치로도 사용 가능하다.
The pressure-sensitive adhesive composition of the present invention can be used not only as a pressure-sensitive adhesive for a polarizing plate for bonding with a liquid crystal cell but also as a pressure-sensitive adhesive for a surface protective film. In addition, 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 or a medical patch.
실시예Example 1: 아크릴계 공중합체 제조 1: Production of acrylic copolymer
실시예Example 1-1 1-1
질소가스가 환류되고 온도조절이 용이하도록 냉각장치가 설치된 1L의 반응기에 n-부틸아크릴레이트(BA) 88중량부, 벤질메타크릴레이트(BzMA) 8중량부, 2중량부, 히드록시부틸아크릴레이트(HBA) 2중량부로 이루어진 단량체 혼합물을 투입한 후 용매로 에틸아세테이트(EA) 100중량부를 투입하였다. 그 후 산소를 제거하기 위하여 질소가스를 1 시간 동안 투입하여 치환시킨 후 온도를 80℃로 유지하였다. 단량체 혼합물을 균일하게 교반한 후 반응개시제로 아조비스이소부티로니트릴(AIBN) 0.07중량부를 투입하고 8시간 동안 반응시켜 중량평균분자량이 80만 이상인 아크릴계 공중합체(A-1)를 제조하였다.
88 parts by weight of n-butyl acrylate (BA), 8 parts by weight of benzyl methacrylate (BzMA), 1 part by weight of benzyl methacrylate (BzMA) were added to a 1 L reactor equipped with a cooling device, , 2 parts by weight of hydroxybutyl acrylate (HBA), and then 100 parts by weight of ethyl acetate (EA) was added as a solvent. After that, nitrogen gas was poured in for 1 hour to remove oxygen, and the temperature was maintained at 80 ° C. After homogeneously stirring the monomer mixture, 0.07 parts by weight of azobisisobutyronitrile (AIBN) as a reaction initiator was added and reacted for 8 hours to prepare an acrylic copolymer (A-1) having a weight average molecular weight of 80,000 or more.
실시예Example 1-2 내지 1-8 및 1-2 to 1-8 and 비교예Comparative Example 1-6 1-6
상기 제조예 1과 동일하게 실시하되, 하기 표 1의 조성으로 아크릴계 공중합체를 제조하였다.An acrylic copolymer was prepared in the same manner as in Preparation Example 1, except that the composition of the following Table 1 was used.
(중량부)division
(Parts by weight)
BzMA:벤질메타크릴레이트
HEA:히드록시에틸아크릴레이트
HBA:히드록시부틸아크릴레이트
HEAA:히드록시아크릴아마이드
AM: 아크릴아마이드
AA:아크릴산
화학식 3:
화학식 4:
화학식 5: BA: butyl acrylate
BzMA: Benzyl methacrylate
HEA: hydroxyethyl acrylate
HBA: hydroxybutyl acrylate
HEAA: Hydroxyacrylamide
AM: Acrylamide
AA: Acrylic acid
(3)
(4)
(5)
실시예Example 2-1 내지 2-11 및 2-1 to 2-11 and 비교예Comparative Example 7 내지 13 7 to 13
하기 표 2의 조성으로 혼합한 후 에틸아세테이트에 희석하여 점착제 조성물을 제조하였다. 상기에서 제조된 점착제 조성물을 실리콘 이형제가 코팅된 이형필름 상에 두께가 25㎛가 되도록 도포하고 100℃에서 1분 동안 건조시켜 점착층을 형성하였다. The ingredients were mixed in the composition shown in Table 2, and then diluted with ethyl acetate to prepare a pressure-sensitive adhesive composition. 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.
두께 185㎛의 요오드계 편광판에 상기 제조된 점착층을 점착 가공으로 적층하여 점착제 부착 편광판을 제조하였다. 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.
(중량부)division
(Parts by weight)
(100중량부)Acrylic copolymer
(100 parts by weight)
커플링제Silane
Coupling agent
촉진제Bridging
accelerant
A-2; 코로네이트-HXR (HDI의 이소아누레이트, 일본우레탄사)
A-3: D110N (HDI-TMP 어덕트, 미쯔이화학)
A-4: D140N (IPDI-TMP 어덕트, 미쯔이화학)
실란커플링제: 3-글리시독시프로필트리메톡시실란, KBM-403제품, 신에츠사
가교촉진제: DBTDLA, 디부틸틴디라우레이트A-1; Coronate-L (TDI TMP Adduct, Japan Urethane Co., Ltd.)
A-2; Coronate-HXR (isocyanurate of HDI, Urethane Company of Japan)
A-3: D110N (HDI-TMP adduct, Mitsui Chemicals)
A-4: D140N (IPDI-TMP adduct, Mitsui Chemicals)
Silane coupling agent: 3-glycidoxypropyltrimethoxysilane, KBM-403 product, Shin-Etsu Co., Ltd.
Crosslinking accelerator: DBTDLA, dibutyl tin dilaurate
시험예Test Example
상기 실시예 및 비교예에서 제조된 점착제 조성물, 점착시트 및 점착제 부착 편광판의 물성을 하기의 방법으로 측정하고, 그 결과를 하기 표 3에 나타내었다.
The properties of the pressure-sensitive adhesive composition, the pressure-sensitive adhesive sheet and the polarizer with a pressure-sensitive adhesive prepared in the above Examples and Comparative Examples were measured by the following methods, and the results are shown in Table 3 below.
1. 저장 안정성(점도 변화, %)1. Storage stability (viscosity change,%)
제조된 점착제 조성물의 초기 점도와 상온에서 24시간 동안 방치한 후의 점도를 점도측정계(Brookfield LVDV-Ⅱ+B형(spindle no.3, 30rpm))를 이용하여 측정하고, 점도의 변화율(△η)을 계산하였다. The initial viscosity of the pressure-sensitive adhesive composition thus prepared and the viscosity after standing at room temperature for 24 hours were measured using a viscosity meter (Brookfield LVDV-II + B type (spindle no. 3, 30 rpm)), Respectively.
<평가 기준><Evaluation Criteria>
○: △η < 10%?:?? ≪ 10%
△: 10% ≤ △η < 20%?: 10%??? <20%
×: 20% ≤ △η
×: 20% ≤Δη
2. 양생 기간2. Curing period
제조된 점착시트를 23℃, 65%RH에서 1 내지 10일 동안 양생하면서 1일 단위로 하기 방법으로 겔분율을 측정하고, 겔분율이 더 이상 증가하지 않는 일, 즉 양생 기간을 측정하였다.The adhesive sheet thus prepared was cured for 1 to 10 days at 23 DEG C and 65% RH, and the gel fraction was measured in the following manner for each day, and the curing period was measured, in which the gel fraction was no longer increased.
정칭(精秤)한 250메쉬의 철망(100㎜×100㎜)에 점착시트의 점착제층을 약 0.25g 첩부하고, 겔분이 새어나가지 않도록 감싼다. 정밀 천칭으로 중량을 정확하게 측정한 후 철망을 에틸아세테이트 용액에 3일간 침지한다. 침지된 철망을 꺼내어 소량의 에틸아세테이트 용액으로 세정하고, 120℃에서 24시간 건조한 후 중량을 측정한다. 측정된 중량을 이용하여 하기 수학식 1로 겔분율을 계산하였다. 계산된 겔분율의 값이 70 내지 80% 범위에 포함되고 경시적인 변화가 없는 시점을 기준으로 양생 기간을 결정하였다.Approximately 0.25 g of the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet is attached to a wire mesh (100 mm x 100 mm) of a 250 mesh precisely weighed, and the gel is wrapped so as not to leak. After accurately weighing the weight with a precision balance, the wire net is immersed in the ethyl acetate solution for 3 days. The immersed wire mesh is taken out, washed with a small amount of ethyl acetate solution, dried at 120 ° C for 24 hours and then weighed. Using the measured weight, the gel fraction was calculated by the following equation (1). The curing period was determined on the basis of the time when the calculated gel fraction was included in the range of 70 to 80% and there was no change with time.
[식 중, A는 철망의 중량(g), B는 점착제층을 첩부한 철망의 중량(B-A: 점착제 중량, g), C는 침지 후 건조한 철망의 중량(C-A: 겔화된 수지의 중량, g)임].
B is the weight of the wire netting attached to the pressure-sensitive adhesive layer (BA: weight of the pressure-sensitive adhesive, g); C is the weight of the wire netted after immersion (CA: weight of the gelled resin, g )being].
3. 내구성(내열, 3. Durability (heat resistance, 내습열Wet heat ))
제조된 점착제 부착 편광판을 90㎜×170㎜ 크기로 절단하고 이형필름을 박리한 후 유리 기판(110㎜×190㎜×0.7㎜)의 양면에 광학 흡수축이 직교하도록 부착하여 시편을 제작하였다. 이때, 가해진 압력은 5㎏/㎠이며 기포나 이물이 생기지 않도록 크린룸 작업을 하였다. 내열 특성은 80℃의 온도에서 1000시간 동안 방치한 후에 기포나 박리의 발생 여부를 관찰하였고, 내습열 특성은 60℃의 온도 및 90%RH의 조건 하에서 1000시간 방치한 후에 기포나 박리의 발생 여부를 관찰하였다. 이때, 시편의 상태를 평가하기 직전에 상온에서 24시간 방치한 후 관찰하였다.The prepared polarizer with a pressure-sensitive adhesive was cut into a size of 90 mm × 170 mm, and the release film was peeled off. Then, the optical absorption axis was perpendicularly attached to both sides of the glass substrate (110 mm × 190 mm × 0.7 mm). At this time, the applied pressure was 5 kg / cm < 2 >, and the clean room operation was performed so that bubbles or foreign matter would not occur. The heat resistance characteristics were evaluated by observing the occurrence of bubbles or peeling after being left at a temperature of 80 ° C. for 1000 hours. The moisture resistance characteristics were evaluated by observing the occurrence of bubbles or peeling after being left at a temperature of 60 ° C. and 90% RH for 1000 hours Respectively. At this time, the sample was allowed to stand at room temperature for 24 hours immediately before evaluating the state of the specimen.
<평가 기준><Evaluation Criteria>
ⓞ: 기포나 박리 없음.Ⓞ: No bubbles or peeling.
○: 기포나 박리 < 5개○: Bubbles or peeling <5
△: 5개 ≤ 기포나 박리 < 10개?: 5 pieces? Bubbles or peeling <10 pieces
×: 10개 ≤ 기포나 박리
X: 10 pieces < bubble &
4. 4. 리워크성Re-workability
제조된 점착제 부착 편광판을 25㎜×100㎜의 크기로 절단하고 이형필름을 박리한 후 유리 기판(#1737, 코닝사)에 0.25MPa의 압력으로 라미네이션하고, 50℃, 5기압의 조건으로 20분 동안 오토클레이브 처리하여 시편을 제작하였다. 내열 리워크성은 제작된 시편을 80℃의 오븐에서 10시간 동안 보관한 후 꺼내어 상온에서 120시간 동안 방치한 후 1.3㎝/초의 속도로 점착제층을 박리하고, 내습열 리워크성은 시편을 60℃, 90%RH의 오븐에서 12시간 동안 보관한 후 꺼내어 상온에서 120시간 동안 방치한 후 같은 속도로 점착제층을 박리하여 측정하고, 하기 기준에 의거하여 평가하였다.The prepared polarizing plate with a pressure-sensitive adhesive was cut into a size of 25 mm x 100 mm, the release film was peeled off, laminated to a glass substrate (# 1737, Corning) at a pressure of 0.25 MPa, The sample was autoclaved. The heat resistance of the specimens was measured at room temperature for 120 hours and then peeled off at a rate of 1.3 cm / sec. The heat resistance of the specimens was measured at 60 ℃, The sample was stored in an oven at 90% RH for 12 hours, taken out and allowed to stand at room temperature for 120 hours, peeled off at the same rate, and evaluated according to the following criteria.
<평가 기준><Evaluation Criteria>
○: 내열 및 내습열 리워크성 모두에서 유리 기판에 점착제의 남음이 없고 편광판의 찢어짐이 없이 깨끗이 박리됨.○: No adhesive residue is left on the glass substrate in both heat resistance and anti-wet heat resistance, and the polarizer is cleanly peeled without tearing.
△: 내열 및 내습열 리워크성 중 어느 하나 이상에서 유리 기판에 점착제가 소량 남아있고 편광판의 찢어짐이 없이 깨끗이 박리됨.?: A small amount of a pressure-sensitive adhesive remained on the glass substrate at any one or more of heat resistance and anti-wet heat resistance, and the polarizer was cleanly peeled without tearing.
×: 내열 및 내습열 리워크성 중 어느 하나 이상에서 유리 기판에 점착제가 많이 남아있거나 박리 과정에서 편광판이 찢어짐.
X: A large amount of adhesive is left on the glass substrate or the polarizer tears in the peeling process in at least one of heat resistance and anti-wet heat resistance.
상기 표 2와 같이, 본 발명에 따라 특정의 화합물과, 히드록시기를 함유하는 단량체를 함유하는 실시예 2-1 내지 2-11의 점착제 조성물은 비교예 7 내지 13에 비해 양생 기간이 짧고 저장안정성이 우수하며 내구성 및 리워크성이 우수하다는 것을 확인할 수 있었다.
As shown in Table 2, the pressure-sensitive adhesive compositions of Examples 2-1 to 2-11 containing a specific compound and a monomer containing a hydroxyl group according to the present invention had a shorter curing period and shorter storage stability than Comparative Examples 7 to 13 And excellent durability and reworkability were confirmed.
Claims (7)
[화학식 1]
[화학식 2]
(상기 식 중, R1은 수소 또는 메틸기이고, X는 O 또는 NH이고, R2는 탄소수 1-12의 직쇄 또는 분지쇄인 지방족 탄화수소기로, 상기 지방족 탄화수소기는 주쇄에 N 또는 O를 포함하거나 포함하지 않고, 곁사슬에 ?H를 포함하거나 포함하지 않으며, R3 및 R4는 각각 독립적으로 수소, 할로겐, -OR5, -N(R5)2, -SR5, -CN, -NO2 또는 탄소수 1~12의 지방족 탄화수소이고, R5는 탄소수 1-12의 지방족 탄화수소임).
An acrylic copolymer containing a compound represented by the following formula (1) or (2) and a monomer containing a hydroxyl group:
[Chemical Formula 1]
(2)
Wherein R 1 is hydrogen or a methyl group, X is O or NH, and R 2 is a straight or branched chain aliphatic hydrocarbon group having 1-12 carbon atoms, and the aliphatic hydrocarbon group includes N or O in the main chain And R 3 and R 4 are each independently selected from the group consisting of hydrogen, halogen, -OR 5 , -N (R 5 ) 2 , -SR 5 , -CN, -NO 2 or An aliphatic hydrocarbon having 1 to 12 carbon atoms and R 5 is an aliphatic hydrocarbon having 1 to 12 carbon atoms.
The compound according to claim 1, wherein the compound represented by Formula 1 or 2 is R 1 hydrogen or a methyl group, X is oxygen, and R 2 is a carbon number having an ether group, an ester group, or a urethane group in the main chain, And R < 3 > and R < 4 > are each independently hydrogen.
[화학식 3]
[화학식 4]
[화학식 5]
The acrylic copolymer according to claim 1, wherein the compound represented by Formula 1 or Formula 2 is at least one selected from the group consisting of the following Formulas 3 to 5:
(3)
[Chemical Formula 4]
[Chemical Formula 5]
The acrylic copolymer according to claim 1, wherein the acrylic copolymer contains a (meth) acrylate monomer having an alkyl group having 4 to 12 carbon atoms, a compound represented by the general formula (1) or (2), and a monomer containing a hydroxyl group.
[4] The acrylic copolymer according to claim 4, wherein the compound 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 4-12 carbon atoms.
A pressure-sensitive adhesive composition containing the acrylic copolymer according to any one of claims 1 to 5.
The pressure-sensitive adhesive composition according to claim 6, wherein the pressure-sensitive adhesive composition further comprises a crosslinking agent.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020130061833A KR20140140872A (en) | 2013-05-30 | 2013-05-30 | Acrylic copolmer and adhesive composition containing threrof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020130061833A KR20140140872A (en) | 2013-05-30 | 2013-05-30 | Acrylic copolmer and adhesive composition containing threrof |
Publications (1)
Publication Number | Publication Date |
---|---|
KR20140140872A true KR20140140872A (en) | 2014-12-10 |
Family
ID=52458528
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
KR1020130061833A KR20140140872A (en) | 2013-05-30 | 2013-05-30 | Acrylic copolmer and adhesive composition containing threrof |
Country Status (1)
Country | Link |
---|---|
KR (1) | KR20140140872A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2020089236A1 (en) * | 2018-11-02 | 2020-05-07 | Unilever Plc | Bioenergetic nicotinic acid glycerol esters, compositions and methods of using same |
-
2013
- 2013-05-30 KR KR1020130061833A patent/KR20140140872A/en not_active Application Discontinuation
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2020089236A1 (en) * | 2018-11-02 | 2020-05-07 | Unilever Plc | Bioenergetic nicotinic acid glycerol esters, compositions and methods of using same |
CN112955115A (en) * | 2018-11-02 | 2021-06-11 | 联合利华知识产权控股有限公司 | Bioenergy glyceryl nicotinates, compositions and methods of using the same |
CN112955115B (en) * | 2018-11-02 | 2023-06-30 | 联合利华知识产权控股有限公司 | Bioenergy glyceryl nicotinate, compositions and methods of using the same |
US11767314B2 (en) | 2018-11-02 | 2023-09-26 | Conopco, Inc. | Bioenergetic nicotinic acid glycerol esters, compositions and methods of using same |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
KR20110076839A (en) | Binder for adhesive composition, method for preparing thereof, adhesive composition comprising the same and optical member using the same | |
KR101991974B1 (en) | Adhesive composition | |
KR101314202B1 (en) | Adhesive composition | |
KR101938897B1 (en) | Acrylic copolmer, adhesive composition containing threrof and polarizing plate | |
KR101911997B1 (en) | Adhesive Composition and Polarizing Plate Comprising the Same | |
KR20140080998A (en) | Acrylic adhesive composition | |
KR101991971B1 (en) | Adhesive composition for acrylic film and polarizing plate containing threrof | |
KR101391297B1 (en) | Adhesive composition | |
KR20150111635A (en) | Adhesive Composition and Polarizing Plate Comprising the Same | |
KR20150025843A (en) | Adhesive composition | |
KR20120119691A (en) | Adhesive composition, polarizing plate and liquid crystal display device comprising the same | |
KR20140023856A (en) | Acrylic adhesive composition | |
KR20140140872A (en) | Acrylic copolmer and adhesive composition containing threrof | |
KR101852970B1 (en) | Copolymer and Pressure-sensitive adhesive composion comprising the same | |
KR20170022434A (en) | Adhesive Composition and Polarizing Plate Comprising the Same | |
KR101837057B1 (en) | Adhesive composition, polarizing plate and liquid crystal display device comprising the same | |
KR20140120080A (en) | Acrylic copolmer, adhesive composition containing threrof, and acrylate compounds | |
KR20150109239A (en) | Adhesive Composition and Polarizing Plate Comprising the Same | |
KR101798904B1 (en) | Copolymer and Pressure-sensitive adhesive composion | |
KR101881186B1 (en) | Adhesive composition | |
KR20120119387A (en) | Adhesive composition, polarizing plate and liquid crystal display device comprising the same | |
KR20140120490A (en) | Acrylic copolmer, adhesive composition containing threrof and polarizing plate | |
KR101919578B1 (en) | New heterocyclic amine and adhesive composition comprising the same | |
KR20140120063A (en) | Acrylic adhesive composition | |
KR20150001269A (en) | Acrylic copolmer and adhesive composition containing threrof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WITN | Application deemed withdrawn, e.g. because no request for examination was filed or no examination fee was paid |