KR101925073B1 - New multi-functional isocyanate crosslinker and composition for adhesive comprising the same - Google Patents

New multi-functional isocyanate crosslinker and composition for adhesive comprising the same Download PDF

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KR101925073B1
KR101925073B1 KR1020120156074A KR20120156074A KR101925073B1 KR 101925073 B1 KR101925073 B1 KR 101925073B1 KR 1020120156074 A KR1020120156074 A KR 1020120156074A KR 20120156074 A KR20120156074 A KR 20120156074A KR 101925073 B1 KR101925073 B1 KR 101925073B1
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crosslinking agent
group
isocyanate
examples
agent
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KR1020120156074A
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KR20140086048A (en
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최한영
권혜림
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동우 화인켐 주식회사
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Priority to PCT/KR2013/011784 priority patent/WO2014104645A1/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or 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 of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
    • C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
    • C08G18/6225—Polymers of esters of acrylic or methacrylic acid
    • C08G18/6229—Polymers of hydroxy groups containing esters of acrylic or methacrylic acid with aliphatic polyalcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
    • C08G18/625—Polymers of alpha-beta ethylenically unsaturated carboxylic acids; hydrolyzed polymers of esters of these acids
    • C08G18/6254—Polymers of alpha-beta ethylenically unsaturated carboxylic acids and of esters of these acids containing hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or 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 of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of 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
    • 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
    • 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
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes

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  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

본 발명은 신규의 다관능성 이소시아네이트계 가교제 및 이를 함유한 점착제 조성물에 관한 것으로서, 보다 상세하게는 이소시아네이트계 가교제와, 2개 이상의 친핵성 작용기를 갖고 상기 친핵성 작용기간의 화학결합이 5개 이하인 연결제가 일정비로 중합된 다관능성 이소시아네이트계 가교제와, 상기 다관능성 이소시아네이트계 가교제를 함유함으로써 가혹 조건(고온 또는 고온 다습)에서의 점착 내구성이 우수한 점착제 조성물에 관한 것이다.The present invention relates to a novel multifunctional isocyanate crosslinking agent and a pressure-sensitive adhesive composition containing the same, and more particularly, to a novel multifunctional isocyanate-based crosslinking agent and an adhesive composition containing the isocyanate crosslinking agent and a linking agent having two or more nucleophilic functional groups, The present invention relates to a pressure-sensitive adhesive composition which is excellent in adhesion durability under severe conditions (high temperature or high temperature and high humidity) by containing a polyfunctional isocyanate-based crosslinking agent polymerized at a predetermined ratio and the polyfunctional isocyanate-based crosslinking agent.

Description

신규의 다관능성 이소시아네이트계 가교제 및 이를 함유한 점착제 조성물 {NEW MULTI-FUNCTIONAL ISOCYANATE CROSSLINKER AND COMPOSITION FOR ADHESIVE COMPRISING THE SAME}TECHNICAL FIELD [0001] The present invention relates to a novel multifunctional isocyanate-based cross-linking agent and a pressure-sensitive adhesive composition containing the same. BACKGROUND ART < RTI ID = 0.0 >

본 발명은 신규의 다관능성 이소시아네이트계 가교제 및 상기 가교제를 함유하여 내구성을 향상시킨 점착제 조성물에 관한 것이다.
The present invention relates to a novel multifunctional isocyanate crosslinking agent and a pressure-sensitive adhesive composition containing the crosslinking agent and having improved durability.

일반적으로 액정표시장치(Liquid crystal display device, LCD)는 액정을 포함하고 있는 액정셀과 편광판이 구비되며, 상기 액정표시장치의 표시 품위를 향상시키기 위하여 여러 가지 광학필름(위상차판, 시야각 확대필름, 휘도 향상필름 등)이 사용된다. In general, a liquid crystal display device (LCD) includes a liquid crystal cell including a liquid crystal and a polarizing plate. In order to improve the display quality of the liquid crystal display device, various optical films (retardation plate, A brightness enhancement film or the like) is used.

액정표시장치는 퍼스널 컴퓨터나 텔레비전, 카 내비게이션 등의 표시장치로서 광범위하게 사용되고 있다. 그에 따라 고온 고습과 같은 가혹한 환경하에서의 사용에 있어서도 내구성이 우수한, 즉, 장기간의 사용에 있어서도 벗겨짐이나 기포발생 등이 발생하지 않는 점착제가 요구되고 있다.BACKGROUND ART Liquid crystal display devices are widely used as display devices for personal computers, televisions, car navigation systems, and the like. Accordingly, there is a demand for a pressure-sensitive adhesive which is excellent in durability even in use under severe environments such as high temperature and high humidity, that is, does not cause peeling or bubble generation even in long-term use.

이에 카르복실기와 수산기를 갖는 아크릴계 공중합체에 이소시아네이트 화합물을 가교제로 사용한 점착제 조성물이 제시되어 있다(일본특허공개 제2004-224873호). 상기 방법으로 제조된 점착제 조성물은 대형 액정표시장치에 적용하는 경우 만족할 정도의 내구성을 나타내지 못하는 단점이 있다.A pressure-sensitive adhesive composition using an isocyanate compound as a crosslinking agent in an acrylic copolymer having a carboxyl group and a hydroxyl group has been proposed (JP-A-2004-224873). The pressure-sensitive adhesive composition prepared by the above method has a disadvantage in that it can not show satisfactory durability when applied to a large-sized liquid crystal display device.

통상 이소시아네이트계 가교제는 관능기의 수가 증가할수록 점착제 조성물의 내구성이 향상되는 경향을 보이나, 현재 4관능기 이상의 이소시아네이트계 가교제는 그 합성이 어려워 실제 이의 사용은 제한되고 있는 실정이다.
In general, the isocyanate-based crosslinking agent tends to improve the durability of the pressure-sensitive adhesive composition as the number of functional groups increases. However, at present, isocyanate-based crosslinking agents having four or more functional groups are difficult to synthesize.

본 발명은 종래 알려진 3관능 이소시아네이트계 가교제의 분자간 반응을 이용한 다관능성을 갖는 이소시아네이트계 가교제를 제공하는 데 그 목적이 있다.An object of the present invention is to provide an isocyanate-based crosslinking agent having a multifunctionality by using intermolecular reaction of a known trifunctional isocyanate-based crosslinking agent.

또한, 본 발명은 상기 다관능성을 갖는 이소시아네이트계 가교제를 함유하여, 가혹 조건(고온 또는 고온 다습)에서의 점착 내구성을 월등히 향상시킬 수 있는 점착제 조성물을 제공하는데 그 목적이 있다.
It is another object of the present invention to provide a pressure-sensitive adhesive composition containing the above-mentioned polyfunctional isocyanate-based crosslinking agent and capable of significantly improving adhesion durability under severe conditions (high temperature or high temperature and high humidity).

상기 목적을 달성하기 위하여, 본 발명은 이소시아네이트계 가교제와 2개 이상의 친핵성 작용기를 갖고 상기 작용기간의 화학결합이 5개 이하인 연결제가 중합되고; 상기 이소시아네이트계 가교제는 2,4-톨루엔 디이소시아네이트 삼량체, 2,4-톨루엔 디이소시아네이트-트리메틸올프로판 어덕트, 이소포론 디이소시아네이트 삼량체 및 이소포론 디이소시아네이트-트리메틸올프로판 어덕트로 이루어진 군에서 선택된 1종 이상이며; 상기 이소시아네이트계 가교제의 NCO기 1몰에 대하여, 연결제의 친핵성 작용기가 0.1 내지 0.7몰비가 중합된 것인 다관능성 이소시아네이트계 가교제를 제공한다.In order to achieve the above object, the present invention relates to a process for producing a crosslinking agent, which comprises polymerizing a crosslinking agent having an isocyanate crosslinking agent and two or more nucleophilic functional groups and having a chemical bond of 5 or less in the above- The isocyanate-based crosslinking agent is selected from the group consisting of 2,4-toluene diisocyanate trimer, 2,4-toluene diisocyanate-trimethylol propane adduct, isophorone diisocyanate trimer and isophorone diisocyanate-trimethylolpropane adduct At least one selected; Wherein the nucleophilic functional group of the linking agent is polymerized in an amount of 0.1 to 0.7 mol based on 1 mol of the NCO group of the isocyanate crosslinking agent.

바람직하기로, 상기 연결제의 친핵성 작용기간의 화학결합이 3 내지 5일 수 있다. Preferably, the chemical bond of the nucleophilic functional period of the linking agent can be from 3 to 5.

상기 연결제의 친핵성 작용기는 히드록시기, 아미노기, 티올기, 아마이드기, 아민기 및 카르복시산기로 이루어진 군에서 선택된 1종 이상일 수 있다.The nucleophilic functional group of the linking agent may be at least one selected from the group consisting of a hydroxyl group, an amino group, a thiol group, an amide group, an amine group and a carboxylic acid group.

상기 연결제는

Figure 112012108920838-pat00001
,
Figure 112012108920838-pat00002
,
Figure 112012108920838-pat00003
,
Figure 112012108920838-pat00004
,
Figure 112012108920838-pat00005
,
Figure 112012108920838-pat00006
,
Figure 112012108920838-pat00007
,
Figure 112012108920838-pat00008
,
Figure 112012108920838-pat00009
,
Figure 112012108920838-pat00010
,
Figure 112012108920838-pat00011
,
Figure 112012108920838-pat00012
,
Figure 112012108920838-pat00013
,
Figure 112012108920838-pat00014
,
Figure 112012108920838-pat00015
,
Figure 112012108920838-pat00016
,
Figure 112012108920838-pat00017
,
Figure 112012108920838-pat00018
,
Figure 112012108920838-pat00019
,
Figure 112012108920838-pat00020
,
Figure 112012108920838-pat00021
,
Figure 112012108920838-pat00022
,
Figure 112012108920838-pat00023
,
Figure 112012108920838-pat00024
,
Figure 112012108920838-pat00025
,
Figure 112012108920838-pat00026
,
Figure 112012108920838-pat00027
,
Figure 112012108920838-pat00028
,
Figure 112012108920838-pat00029
,
Figure 112012108920838-pat00030
,
Figure 112012108920838-pat00031
,
Figure 112012108920838-pat00032
,
Figure 112012108920838-pat00033
,
Figure 112012108920838-pat00034
,
Figure 112012108920838-pat00035
,
Figure 112012108920838-pat00036
,
Figure 112012108920838-pat00037
,
Figure 112012108920838-pat00038
및
Figure 112012108920838-pat00039
로 이루어진 군에서 선택된 1종 이상일 수 있다.The connecting agent
Figure 112012108920838-pat00001
,
Figure 112012108920838-pat00002
,
Figure 112012108920838-pat00003
,
Figure 112012108920838-pat00004
,
Figure 112012108920838-pat00005
,
Figure 112012108920838-pat00006
,
Figure 112012108920838-pat00007
,
Figure 112012108920838-pat00008
,
Figure 112012108920838-pat00009
,
Figure 112012108920838-pat00010
,
Figure 112012108920838-pat00011
,
Figure 112012108920838-pat00012
,
Figure 112012108920838-pat00013
,
Figure 112012108920838-pat00014
,
Figure 112012108920838-pat00015
,
Figure 112012108920838-pat00016
,
Figure 112012108920838-pat00017
,
Figure 112012108920838-pat00018
,
Figure 112012108920838-pat00019
,
Figure 112012108920838-pat00020
,
Figure 112012108920838-pat00021
,
Figure 112012108920838-pat00022
,
Figure 112012108920838-pat00023
,
Figure 112012108920838-pat00024
,
Figure 112012108920838-pat00025
,
Figure 112012108920838-pat00026
,
Figure 112012108920838-pat00027
,
Figure 112012108920838-pat00028
,
Figure 112012108920838-pat00029
,
Figure 112012108920838-pat00030
,
Figure 112012108920838-pat00031
,
Figure 112012108920838-pat00032
,
Figure 112012108920838-pat00033
,
Figure 112012108920838-pat00034
,
Figure 112012108920838-pat00035
,
Figure 112012108920838-pat00036
,
Figure 112012108920838-pat00037
,
Figure 112012108920838-pat00038
And
Figure 112012108920838-pat00039
And the like.

또한, 본 발명은 아크릴계 공중합체 및 상기 다관능성 이소시아네이트계 가교제를 함유하는 점착제 조성물을 제공한다.The present invention also provides a pressure-sensitive adhesive composition containing an acrylic copolymer and the polyfunctional isocyanate-based crosslinking agent.

상기 다관능성 이소시아네이트계 가교제는 아크릴계 공중합체 100중량부에 대하여 0.1 내지 10중량부 함유할 수 있다.
The polyfunctional isocyanate crosslinking agent may be contained in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the acrylic copolymer.

본 발명의 다관능 이소시아네이트계 가교제는 종래 관능기가 3이하인 이소시아네이트계 가교제를 이용하여 상기 가교제 분자들 간의 결합을 유도하여 손쉽게 제조할 수 있는 이점이 있다.The polyfunctional isocyanate crosslinking agent of the present invention has an advantage that it can easily produce by inducing the bonding between the crosslinking agent molecules by using an isocyanate crosslinking agent having a conventional functional group of 3 or less.

또한, 본 발명의 점착제 조성물은 상기 다관능성 이소시아네이트계 가교제를 함유하여, 가혹 조건(고온 또는 고온 다습)에서의 점착 내구성이 우수한 이점이 있다.
Further, the pressure-sensitive adhesive composition of the present invention contains the above-mentioned polyfunctional isocyanate-based crosslinking agent and has an advantage of excellent adhesion durability under severe conditions (high temperature or high temperature and high humidity).

본 발명은 신규의 다관능성 이소시아네이트계 가교제 및 상기 가교제를 함유하여 내구성을 향상시킨 점착제 조성물에 관한 것이다.
The present invention relates to a novel multifunctional isocyanate crosslinking agent and a pressure-sensitive adhesive composition containing the crosslinking agent and having improved durability.

이한 본 발명을 상세히 설명하면 다음과 같다.Hereinafter, the present invention will be described in detail.

본 발명의 다관능성 이소시아네이트계 가교제는 이소시아네이트계 가교제와 2개 이상의 친핵성 작용기를 갖고 상기 작용기간의 화학결합이 5개 이하인 연결제가 중합된다. The multifunctional isocyanate crosslinking agent of the present invention is polymerized with an isocyanate crosslinking agent and a crosslinking agent having at least two nucleophilic functional groups and not more than five chemical bonds during the above-mentioned operation period.

본 발명은 종래 3관능기를 갖는 이소시아네이트계 가교제를 중합하되, 특정의 연결제를 사용하여 상기 가교제 분자들 간의 반응이 유도하여 4관능 이상의 다관능 이소시아네이트계 가교제를 합성한 것에 특징이 있다.The present invention is characterized in that an isocyanate crosslinking agent having a trifunctional group is polymerized, and a reaction between the crosslinking agent molecules is induced by using a specific linking agent to synthesize a tetrafunctional or higher polyfunctional isocyanate crosslinking agent.

상기 이소시아네이트계 가교제는 2,4-톨루엔 디이소시아네이트 삼량체(TDI), 2,4-톨루엔 디이소시아네이트(TDI)-트리메틸올프로판(TMP) 어덕트, 이소포론 디이소시아네이트(IPDI) 삼량체 및 이소포론 디이소시아네이트(IPDI)-트리메틸올프로판(TMP) 어덕트로 이루어진 군에서 선택된 1종 이상일 수 있다. 이중 친핵성 작용기를 가진 연결기와의 분자 내 반응은 억제하고 분자간 반응을 선택적으로 유도시의 반응 효율성을 고려하면 2,4-톨루엔 디이소시아네이트 삼량체와 이소포론 디이소시아네이트 삼량체가 바람직하다.The isocyanate crosslinking agent may be selected from the group consisting of 2,4-toluene diisocyanate trimer (TDI), 2,4-toluene diisocyanate (TDI) -trimethylol propane (TMP) adduct, isophorone diisocyanate (IPDI) (IPDI) -trimethylol propane (TMP) adducts. The 2,4-toluene diisocyanate trimer and the isophorone diisocyanate trimer are preferable in view of the reaction efficiency when the intramolecular reaction with the double nucleophilic functional group is inhibited and the intermolecular reaction is selectively induced.

상기 연결제는 이소시아네이트계 가교제의 분자간의 반응을 유도하기 위하여 2개 이상의 친핵성 작용기를 가지고, 친핵성 작용기간의 화학결합이 5개 이하 바람직하기로는 3 내지 5개인 것을 사용한다.The linking agent has two or more nucleophilic functional groups in order to induce the reaction between molecules of the isocyanate crosslinking agent and has 5 or less and preferably 3 to 5 chemical bonds in nucleophilic functional period.

상기 화학결합이 5개를 초과하는 경우에는 이소시아네이트계 가교제 분자간의 반응에 비해 분자내에서 반응이 먼저 발생될 수 있다.When the number of the chemical bonds is more than 5, the reaction may be generated first in the molecule as compared with the reaction between the isocyanate crosslinking agent molecules.

친핵성 작용기는 히드록시기, 아미노기, 티올기, 아마이드기, 아민기 및 카르복시산기로 이루어진 군에서 선택된 1종 이상일 수 있다. 구체적으로 상기 연결제는

Figure 112012108920838-pat00040
,
Figure 112012108920838-pat00041
,
Figure 112012108920838-pat00042
,
Figure 112012108920838-pat00043
,
Figure 112012108920838-pat00044
,
Figure 112012108920838-pat00045
,
Figure 112012108920838-pat00046
,
Figure 112012108920838-pat00047
,
Figure 112012108920838-pat00048
,
Figure 112012108920838-pat00049
,
Figure 112012108920838-pat00050
,
Figure 112012108920838-pat00051
,
Figure 112012108920838-pat00052
,
Figure 112012108920838-pat00053
,
Figure 112012108920838-pat00054
,
Figure 112012108920838-pat00055
,
Figure 112012108920838-pat00056
,
Figure 112012108920838-pat00057
,
Figure 112012108920838-pat00058
,
Figure 112012108920838-pat00059
,
Figure 112012108920838-pat00060
,
Figure 112012108920838-pat00061
,
Figure 112012108920838-pat00062
,
Figure 112012108920838-pat00063
,
Figure 112012108920838-pat00064
,
Figure 112012108920838-pat00065
,
Figure 112012108920838-pat00066
,
Figure 112012108920838-pat00067
,
Figure 112012108920838-pat00068
,
Figure 112012108920838-pat00069
,
Figure 112012108920838-pat00070
,
Figure 112012108920838-pat00071
,
Figure 112012108920838-pat00072
,
Figure 112012108920838-pat00073
,
Figure 112012108920838-pat00074
,
Figure 112012108920838-pat00075
,
Figure 112012108920838-pat00076
,
Figure 112012108920838-pat00077
및
Figure 112012108920838-pat00078
로 이루어진 군에서 선택된 1종 이상일 수 있다.The nucleophilic functional group may be at least one member selected from the group consisting of a hydroxyl group, an amino group, a thiol group, an amide group, an amine group and a carboxylic acid group. Specifically,
Figure 112012108920838-pat00040
,
Figure 112012108920838-pat00041
,
Figure 112012108920838-pat00042
,
Figure 112012108920838-pat00043
,
Figure 112012108920838-pat00044
,
Figure 112012108920838-pat00045
,
Figure 112012108920838-pat00046
,
Figure 112012108920838-pat00047
,
Figure 112012108920838-pat00048
,
Figure 112012108920838-pat00049
,
Figure 112012108920838-pat00050
,
Figure 112012108920838-pat00051
,
Figure 112012108920838-pat00052
,
Figure 112012108920838-pat00053
,
Figure 112012108920838-pat00054
,
Figure 112012108920838-pat00055
,
Figure 112012108920838-pat00056
,
Figure 112012108920838-pat00057
,
Figure 112012108920838-pat00058
,
Figure 112012108920838-pat00059
,
Figure 112012108920838-pat00060
,
Figure 112012108920838-pat00061
,
Figure 112012108920838-pat00062
,
Figure 112012108920838-pat00063
,
Figure 112012108920838-pat00064
,
Figure 112012108920838-pat00065
,
Figure 112012108920838-pat00066
,
Figure 112012108920838-pat00067
,
Figure 112012108920838-pat00068
,
Figure 112012108920838-pat00069
,
Figure 112012108920838-pat00070
,
Figure 112012108920838-pat00071
,
Figure 112012108920838-pat00072
,
Figure 112012108920838-pat00073
,
Figure 112012108920838-pat00074
,
Figure 112012108920838-pat00075
,
Figure 112012108920838-pat00076
,
Figure 112012108920838-pat00077
And
Figure 112012108920838-pat00078
And the like.

상기 연결제의 친핵성 작용기는 이소시아네이트계 가교제의 NCO기 1몰에 대하여, 0.1 내지 0.7몰비, 바람직하기로는 0.2 내지 0.5 몰비로 중합되는 것이 좋다. 친핵성 작용기가 0.1몰비 미만이면 내구성 향상 효과가 부족할 수 있고 0.7몰비를 초과하는 경우에는 가교반응이 저하되어 내구성 확보가 어려울 수 있다.
The nucleophilic functional group of the linking agent is preferably polymerized in an amount of 0.1 to 0.7 mol, preferably 0.2 to 0.5 mol, based on 1 mol of the NCO group of the isocyanate-based crosslinking agent. If the nucleophilic functional group is less than 0.1 molar ratio, the durability improving effect may be insufficient, and if it is more than 0.7 molar ratio, the crosslinking reaction may be lowered and it may be difficult to secure durability.

또한 본 발명은 상기 다관능성 이소시아네이트계 가교제를 함유하는 점착제 조성물에 특징이 있다. 상기 점착제 조성물은 아크릴계 공중합체 및 상기 다관능성 이소시아네이트계 가교제를 함유하는 것이 바람직하다.Further, the present invention is characterized by the pressure-sensitive adhesive composition containing the above-mentioned polyfunctional isocyanate-based crosslinking agent. The pressure-sensitive adhesive composition preferably contains an acrylic copolymer and the polyfunctional isocyanate-based crosslinking agent.

아크릴계 공중합체는 탄소수가 4 내지 12인 알킬 (메타)아크릴레이트 단량체 및 가교 가능한 관능기를 갖는 중합성 단량체를 함유하는 것이 바람직하다. 여기서, (메타)아크릴레이트는 아크릴레이트 및 메타크릴레이트를 의미한다. The acrylic copolymer preferably contains an alkyl (meth) acrylate monomer having 4 to 12 carbon atoms and a polymerizable monomer having a crosslinkable functional group. Here, (meth) acrylate means acrylate and methacrylate.

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.

가교 가능한 관능기를 갖는 중합성 단량체는 하기 가교제와의 화학 결합에 의해 응집력 또는 점착 강도를 부여하는 작용을 하는 것으로서, 히드록시기를 갖는 단량체, 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 polymerizable monomer having a crosslinkable functional group has the function of imparting cohesive strength or cohesive strength by chemical bonding with the following crosslinking agent, and includes a monomer having a hydroxyl group, a monomer having a carboxyl group, a monomer having an amide group and a monomer having a tertiary amine group And the like. These may be used alone or in combination of two or more.

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.

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 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.

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. 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.

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 for producing 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.

상기 다관능성 이소시아네이트계 가교제는 아크릴계 공중합체 100중량부에 대하여 0.1 내지 10중량부 함유될 수 있다.The polyfunctional isocyanate crosslinking agent may be contained in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the acrylic copolymer.

본 발명의 다관능성 이소시아네이트계 가교제는 4개 이상의 관능기를 가지므로 종래 3관능기를 갖는 이소시아네이트계 가교제에 비해 상대적으로 소량 사용될 수 있으며, 다관능성 이소시아네이트계 가교제 내에 함유된 NCO 당량수에 따라 그 함량이 적절히 조절될 수 있다.Since the polyfunctional isocyanate crosslinking agent of the present invention has at least four functional groups, it can be used in a relatively small amount as compared with an isocyanate crosslinking agent having a trifunctional group in the prior art, and the content thereof is appropriately adjusted according to the NCO equivalent number contained in the polyfunctional isocyanate crosslinking agent Lt; / RTI >

상기 0.1 내지 10중량부 범위는 본 발명이 목적으로 하는 물성 달성이 가능한 범위이며, 공정의 경제성, 내구성 등을 고려하면 0.1 내지 5중량부가 바람직하고, 보다 바람직하기로는 0.1 내지 3.0중량부 함유될 수 있다. The range of 0.1 to 10 parts by weight is a range in which the desired physical properties of the present invention can be attained and is preferably 0.1 to 5 parts by weight, more preferably 0.1 to 3.0 parts by weight, in view of economical efficiency and durability of the process. have.

상기 함유량이 0.1중량부 미만이면 부족한 가교도로 인해 응집력이 작게 되어 점착 내구성 및 절단성의 물성을 해칠 수 있으며, 10중량부를 초과할 경우에는 점착력이 지나치게 저하되어 내구성에 문제가 발생할 수 있다. If the content is less than 0.1 parts by weight, the cohesive force may be reduced due to insufficient crosslinking, which may deteriorate the durability of the adhesive durability and the cutability. If the content is more than 10 parts by weight, the adhesive strength may be too low to cause durability problems.

또한, 본 발명의 점착제 조성물은 실란커플링제를 추가로 함유할 수 있다.Further, the pressure-sensitive adhesive composition of the present invention may further contain 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, 레벨링제, 표면윤활제, 염료, 안료, 소포제, 충전제, 광안정제, 대전방지제 등의 첨가제를 더 함유할 수 있다. In addition to the above components, the pressure-sensitive adhesive composition may further contain 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 adhesion, cohesion, viscosity, elastic modulus, glass transition temperature, antistatic property, A pigment, a defoaming agent, a filler, a light stabilizer, an antistatic agent, and the like.

이러한 첨가제는 본 발명의 효과를 저해하지 않는 범위내에서 적절히 함량을 조절할 수 있다.Such an additive can appropriately control the content within a range that does not impair the effect of the present invention.

본 발명의 점착제 조성물은 특히 액정셀과의 접합을 위한 편광판용 점착제, 표면보호필름용 점착제로 사용할 수 있다. 또한, 보호필름, 반사시트, 구조용 점착시트, 사진용 점착시트, 차선표시용 점착시트, 광학용 점착제품, 전자부품용 점착제뿐만 아니라 일반 상업용 점착시트제품으로도 사용 가능하다.
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.

이하, 본 발명의 이해를 돕기 위하여 바람직한 실시예를 제시하나, 하기 실시예는 본 발명을 예시하는 것일 뿐 본 발명의 범주 및 기술사상 범위 내에서 다양한 변경 및 수정이 가능함은 당업자에게 있어서 명백한 것이며, 이러한 변형 및 수정이 첨부된 특허청구범위에 속하는 것도 당연한 것이다.
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.

제조예Manufacturing example : 아크릴계 공중합체 : Acrylic copolymer

질소가스가 환류되고 온도조절이 용이하도록 냉각장치를 설치한 1 L의 반응기에 n-부틸아크릴레이트(BA) 98중량부, 아크릴산(AA) 1중량부, 2-하이드록시에틸아크릴레이트 1중량부로 이루어진 단량체 혼합물을 투입한 후, 용제로 에틸아세테이트 100중량부를 투입하였다. 그 다음 산소를 제거하기 위하여 질소가스를 1시간 동안 퍼징한 후, 78℃로 유지하였다. 상기 혼합물을 균일하게 한 후, 반응개시제로 아조비스이소부티로니트릴(AIBN) 0.07중량부를 투입하고, 6시간 동안 반응시켜 중량평균분자량이 60만인 아크릴계 공중합체를 제조하였다.
98 parts by weight of n-butyl acrylate (BA), 1 part by weight of acrylic acid (AA), and 1 part by weight of 2-hydroxyethyl acrylate were added to a 1 L reactor equipped with a cooling device , And 100 parts by weight of ethyl acetate was added as a solvent. Nitrogen gas was then purged for 1 hour to remove oxygen and then maintained at 78 占 폚. After the mixture was homogenized, 0.07 part by weight of azobisisobutyronitrile (AIBN) as a reaction initiator was added and reacted for 6 hours to prepare an acrylic copolymer having a weight average molecular weight of 600,000.

실시예Example 1:  One: 다관능성Multifunctional 이소시아네이트계  Isocyanate system 가교제Cross-linking agent

실시예Example 1-1 1-1

질소가스가 환류되고 교반기가 설치된 1 L의 반응기에, 이소시아네이트계 가교제로 TDI 삼량체 522g(1.0mol, -NCO 3mol)을 넣고, 50℃로 반응기 온도를 조절하였다. 이후에 -OH/-NCO비가 0.33몰이 되도록 연결제로 에틸렌글리콜 31g(0.5mol, -OH 1.0mol)을 2시간 동안 드롭핑 펀넬(dropping funnel)을 이용하여 첨가하였다. 이후에 50℃에서 24시간 동안 교반하여 4관능의 이소시아네이트계 가교제를 합성하였다.In a 1 L reactor equipped with a reflux condenser and nitrogen gas, 522 g (1.0 mol, -NCO 3 mol) of TDI trimer was added as an isocyanate crosslinking agent and the temperature of the reactor was adjusted to 50 캜. 31 g (0.5 mol, -OH 1.0 mol) of ethylene glycol as a linking agent were then added for 2 hours using a dropping funnel such that the -OH / -NCO ratio was 0.33 mol. Thereafter, the mixture was stirred at 50 캜 for 24 hours to synthesize a tetrafunctional isocyanate crosslinking agent.

반응생성물을 NMR로 분석하여 첨가한 에틸렌글리콜의 피크가 모두 사라진 것을 확인하고, 반응이 완료되었음을 확인하였다. 또한 반응 혼합물의 점도 증가로 분자 내 반응보다 분자간의 반응이 진행하였음을 확인하였다. 이때, 반응 전후의 혼합물의 점도 변화량은 약 100% 정도였다.The reaction product was analyzed by NMR, and it was confirmed that all the peaks of the added ethylene glycol disappeared, and it was confirmed that the reaction was completed. It was also confirmed that the intermolecular reaction proceeded more intramolecularly due to the viscosity increase of the reaction mixture. At this time, the viscosity change amount of the mixture before and after the reaction was about 100%.

Figure 112012108920838-pat00079
Figure 112012108920838-pat00079

또한, GC/MS로 분석하여 상기 화학식의 분자량+1 (M+1)피크인 1107피크를 확인하였다.
Furthermore, analysis by GC / MS revealed a peak at 1107 having a molecular weight of +1 (M + 1) of the above formula.

실시예Example 1-2 내지 1-11 및  1-2 to 1-11 and 비교예Comparative Example 1-3 1-3

상기 실시예 1과 동일하게 실시하되, 하기 표 1과 같이 이소시아네이트계 가교제와 연결제의 종류 및 친핵성 작용기/-NCO의 몰비를 달리하여 다관능의 이소시아네이트계 가교제를 합성하였다.
The polyfunctional isocyanate crosslinking agent was synthesized as in Example 1 except that the isocyanate crosslinking agent, the coupling agent and the nucleophilic functional group / -NCO molar ratio were changed as shown in Table 1 below.

구분
division
이소시아네이트계
가교제 (몰)Isocyanate system
Cross-linking agent (mol) 연결제
(몰)Connector
(mole) 친핵성 작용기/-NCO (몰비)Nucleophilic functional group / -NCO (molar ratio) A-1A-1 A-2A-2 A-3A-3 A-4A-4 B-1B-1 B-2B-2 B-3B-3 B-4B-4 B-5B-5 B-6B-6 실시예1-1Example 1-1 1.01.0 -- -- -- 0.50.5 -- -- -- -- -- 0.330.33 실시예1-2Examples 1-2 -- 1.01.0 -- -- 0.50.5 -- -- -- -- -- 0.330.33 실시예1-3Example 1-3 -- -- 1.01.0 -- 0.50.5 -- -- -- -- -- 0.330.33 실시예1-4Examples 1-4 -- -- -- 1.01.0 0.50.5 -- -- -- -- -- 0.330.33 실시예1-5Examples 1-5 1.01.0 -- -- -- -- 0.50.5 -- -- -- -- 0.330.33 실시예1-6Examples 1-6 1.01.0 -- -- -- -- -- 0.50.5 -- -- -- 0.330.33 실시예1-7Examples 1-7 1.01.0 -- -- -- -- -- -- 0.50.5 -- -- 0.330.33 실시예1-8Examples 1-8 1.01.0 -- -- -- -- -- -- -- 0.50.5 -- 0.330.33 실시예1-9Examples 1-9 1.01.0 -- -- -- 0.150.15 -- -- -- -- -- 0.10.1 실시예1-10Example 1-10 1.01.0 -- -- -- 0.750.75 -- -- -- -- -- 0.50.5 실시예1-11Example 1-11 1.01.0 -- -- -- 1.051.05 -- -- -- -- -- 0.70.7 비교예1Comparative Example 1 1.01.0 -- -- -- -- -- -- -- -- 0.50.5 0.330.33 비교예2Comparative Example 2 1.01.0 -- -- -- 0.0750.075 -- -- -- -- -- 0.050.05 비교예3Comparative Example 3 1.01.0 -- -- -- 1.21.2 -- -- -- -- -- 0.80.8 A-1:TDI 삼량체 (2,4-톨루엔 디이소시아네이트 삼량체)
A-2: TDI-TMP어덕트 (2,4-톨루엔 디이소시아네이트-트리메틸올프로판 어덕트)
A-3: IPDI 삼량체 (이소포론 디이소시아네이트 삼량체)
A-4: IPDI-TMP 어덕트 (이소포론 디이소시아네이트-트리메틸올프로판 어덕트)
B-1: 에틸렌글리콜(화학결합=3)
B-2: 피페라진(화학결합=3)
B-3: 프탈산(화학결합=5)
B-4:

Figure 112012108920838-pat00080
(화학결합=4)
B-5:
Figure 112012108920838-pat00081
아미노 알콜계(화학결합=3)
B-6: 1,6-헥산디올(화학결합=7)A-1: TDI trimer (2,4-toluene diisocyanate trimer)
A-2: TDI-TMP adduct (2,4-toluene diisocyanate-trimethylolpropane adduct)
A-3: IPDI trimer (isophorone diisocyanate trimer)
A-4: IPDI-TMP Adduct (isophorone diisocyanate-trimethylolpropane adduct)
B-1: Ethylene glycol (chemical bond = 3)
B-2: Piperazine (chemical bond = 3)
B-3: Phthalic acid (chemical bond = 5)
B-4:
Figure 112012108920838-pat00080
(Chemical bond = 4)
B-5:
Figure 112012108920838-pat00081
Amino alcohol system (chemical bond = 3)
B-6: 1,6-hexanediol (chemical bond = 7)

실시예Example 2: 점착제 조성물  2: Pressure sensitive adhesive composition

상기 제조예의 아크릴계 공중합체, 실시예 1의 가교제 및 실란커플링제(KBM-403, 신에츠사제)를 하기 표 2의 조성으로 혼합한 후 14중량%의 농도로 희석하여 점착제 조성물을 제조하였다. 이때, 가교제의 함량은 각각의 가교제 내에 거의 동일한 NCO당량이 유지되도록 조절하였다.The acrylic copolymer of Example 1, the crosslinking agent of Example 1 and the silane coupling agent (KBM-403, manufactured by Shinetsu Co., Ltd.) were mixed in the composition shown in Table 2 and diluted to a concentration of 14% by weight to prepare a pressure-sensitive adhesive composition. At this time, the content of the crosslinking agent was adjusted so that almost the same NCO equivalent was retained in each crosslinking agent.

구분
(중량부)division
(Parts by weight) 아크릴계 공중합체
(제조예)Acrylic copolymer
(Production example) 가교제Cross-linking agent 실란커플링제Silane coupling agent 실시예2-1Example 2-1 100100 실시예1-1 (0.75)Example 1-1 (0.75) 0.50.5 실시예2-2Example 2-2 100100 실시예1-2 (0.75)Example 1-2 (0.75) 0.50.5 실시예2-3Example 2-3 100100 실시예1-3 (0.75)Examples 1-3 (0.75) 0.50.5 실시예2-4Examples 2-4 100100 실시예1-4 (0.75)Examples 1-4 (0.75) 0.50.5 실시예2-5Example 2-5 100100 실시예1-5 (0.75)Examples 1-5 (0.75) 0.50.5 실시예2-6Examples 2-6 100100 실시예1-6 (0.75)Examples 1-6 (0.75) 0.50.5 실시예2-7Examples 2-7 100100 실시예1-7 (0.75)Examples 1-7 (0.75) 0.50.5 실시예2-8Examples 2-8 100100 실시예1-8 (0.75)Examples 1-8 (0.75) 0.50.5 실시예2-9Examples 2-9 100100 실시예1-9 (0.56)Examples 1-9 (0.56) 0.50.5 실시예2-10Examples 2-10 100100 실시예1-10 (1.0)Examples 1-10 (1.0) 0.50.5 실시예2-11Examples 2-11 100100 실시예1-11 (1.7)Example 1-11 (1.7) 0.50.5 실시예2-12 Examples 2-12 100100 실시예1-1 (0.2)Example 1-1 (0.2) 0.50.5 실시예2-13Examples 2-13 100100 실시예1-1 (0.5)Example 1-1 (0.5) 0.50.5 실시예2-14Examples 2-14 100100 실시예1-1 (1.5)Example 1-1 (1.5) 0.50.5 실시예2-15Examples 2-15 100100 실시예1-1 (2.0)Example 1-1 (2.0) 0.50.5 비교예4Comparative Example 4 100100 비교예1(0.75)Comparative Example 1 (0.75) 0.50.5 비교예5Comparative Example 5 100100 비교예2 (0.53)Comparative Example 2 (0.53) 0.50.5 비교예6Comparative Example 6 100100 비교예3 (2.5)Comparative Example 3 (2.5) 0.50.5 비교예7Comparative Example 7 100100 TDI 삼량체 (0.5)TDI trimer (0.5) 0.50.5 비교예8Comparative Example 8 100100 TDI -TMP어덕트(0.5)The TDI-TMP actuator (0.5) 0.50.5 비교예9Comparative Example 9 100100 IPDI 삼량체(0.5)IPDI trimer (0.5) 0.50.5 비교예10Comparative Example 10 100100 IPDI-TMP 어덕트(0.5)The IPDI-TMP adapter (0.5) 0.50.5

상기에서 제조된 점착제 조성물을 실리콘 이형제가 코팅된 이형필름 상에 두께가 25㎛가 되도록 도포하고 100℃에서 1분 동안 건조시켜 점착층을 형성하였다. 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. 제조된 편광판을 23℃, 60%RH의 조건 하에서 양생 기간 동안 보관하였다.
The pressure-sensitive adhesive layer prepared above was laminated on an iodine-based polarizing plate having a thickness of 185 탆 by pressure-sensitive adhesive processing to produce a polarizer with a pressure-sensitive adhesive. The prepared polarizing plate was stored for a curing period under the conditions of 23 캜 and 60% RH.

시험예Test Example

상기 실시예 및 비교예에서 제조된 점착제 조성물, 점착제 부착 편광판의 물성을 하기의 방법으로 측정하고, 그 결과를 하기 표 3에 나타내었다.
The properties of the pressure-sensitive adhesive composition and the polarizer with a pressure-sensitive adhesive prepared in the above Examples and Comparative Examples were measured by the following methods, and the results are shown in Table 3 below.

내열/Heat resistance / 내습열성Humidity Durability

점착제 부착 편광판을 90㎜×170㎜로 절단하고 이형필름을 박리한 후, 유리기판(110㎜×190㎜×0.7㎜)의 양면으로 각 편광판의 흡수축이 직교가 되도록 부착하였다. 이때 가해진 압력은 5kg/cm2으로 기포나 이물이 생기지 않도록 크린룸 작업을 수행하여 시편을 제조하였다. The polarizing plate with a pressure-sensitive adhesive was cut into a size of 90 mm x 170 mm and the release film was peeled off. The polarizing plate was attached to both sides of a glass substrate (110 mm x 190 mm x 0.7 mm) such that the absorption axes of the respective polarizing plates were orthogonal. At this time, the applied pressure was 5 kg / cm 2 , and a clean room operation was performed so that bubbles or foreign matter would not be generated.

상기 시편은 60℃(내열)/60℃, 90RH%(내습열)에서 각각 300시간 동안 방치한 후에 기포나 박리의 발생 여부를 관찰하였다. 시편의 상태를 평가하기 직전에 상온에서 24시간 방치한 후 실시하였다. The specimens were allowed to stand at 60 ° C. (heat resistance) / 60 ° C. and 90 RH% (wet heat resistance) for 300 hours, respectively, and then bubbles or peeling were observed. The specimens were allowed to stand at room temperature for 24 hours immediately before evaluating the state of the specimens.

<평가기준><Evaluation Criteria>

기포나 박리가 육안으로 확인안됨: ⓞBubbles or peeling can not be confirmed with the naked eye: ⓞ

미세기포나 매우 적은 영역에 한하여 박리가 확인됨: ○Peeling was confirmed only for micro bubbles or very small areas: ○

기포나 박리가 육안으로 확인됨: ×
Bubbles or peeling were visually confirmed: ×

구분division 내열성Heat resistance 내습열성Humidity Durability 실시예2-1Example 2-1 ◎◎ ◎◎ 실시예2-2Example 2-2 ○○ ○○ 실시예2-3Example 2-3 ◎◎ ◎◎ 실시예2-4Examples 2-4 ○○ ○○ 실시예2-5Example 2-5 ◎◎ ○○ 실시예2-6Examples 2-6 ◎◎ ◎◎ 실시예2-7Examples 2-7 ○○ ○○ 실시예2-8Examples 2-8 ◎◎ ○○ 실시예2-9Examples 2-9 ○○ ○○ 실시예2-10Examples 2-10 ◎◎ ◎◎ 실시예2-11Examples 2-11 ○○ ○○ 실시예2-12Examples 2-12 ○○ ◎◎ 실시예2-13 Examples 2-13 ◎◎ ◎◎ 실시예2-14Examples 2-14 ○○ ○○ 실시예2-15Examples 2-15 ○○ ○○ 비교예4Comparative Example 4 ×× ○○ 비교예5Comparative Example 5 ×× ×× 비교예6Comparative Example 6 ×× ×× 비교예7Comparative Example 7 ×× ○○ 비교예8Comparative Example 8 ×× ×× 비교예9Comparative Example 9 ×× ○○ 비교예10Comparative Example 10 ×× ××

상기 표 2와 같이, 본 발명에 따른 신규의 다관능성 이소시아네이트계 가교제를 함유한 실시예 2-1 내지 2-15의 점착제 조성물은 비교예 4 내지 10에 비해 내열 및 내습열 등의 내구성이 우수하다는 것을 확인할 수 있었다.
As shown in Table 2, the pressure-sensitive adhesive compositions of Examples 2-1 to 2-15 containing the novel multifunctional isocyanate-based crosslinking agent according to the present invention had excellent durability against heat and moisture and heat, as compared with Comparative Examples 4 to 10 .

Claims (6)

이소시아네이트계 가교제와, 2개 이상의 친핵성 작용기를 갖고 상기 친핵성 작용기간의 화학결합이 5개 이하인 연결제가 중합되고;
상기 이소시아네이트계 가교제는 2,4-톨루엔 디이소시아네이트 삼량체, 2,4-톨루엔 디이소시아네이트-트리메틸올프로판 어덕트, 이소포론 디이소시아네이트 삼량체 및 이소포론 디이소시아네이트-트리메틸올프로판 어덕트로 이루어진 군에서 선택된 1종 이상이며;
상기 이소시아네이트계 가교제의 NCO기 1몰에 대하여, 연결제의 친핵성 작용기가 0.1 내지 0.7몰비가 중합된 것인 다관능성 이소시아네이트계 가교제.
An isocyanate crosslinking agent and a linking agent having two or more nucleophilic functional groups and not more than five chemical bonds in the nucleophilic functional period are polymerized;
The isocyanate crosslinking agent may be selected from the group consisting of 2,4-toluene diisocyanate trimer, 2,4-toluene diisocyanate-trimethylol propane adduct, isophorone diisocyanate trimer and isophorone diisocyanate-trimethylolpropane adduct At least one selected;
Wherein the nucleophilic functional group of the linking agent is polymerized in an amount of 0.1 to 0.7 mol based on 1 mol of the NCO group of the isocyanate crosslinking agent.
청구항 1에 있어서, 상기 연결제의 친핵성 작용기간의 화학결합은 3 내지 5인 것인 다관능성 이소시아네이트계 가교제.
The multifunctional isocyanate based crosslinking agent according to claim 1, wherein the chemical bond of the nucleating action period of the linking agent is 3 to 5.
청구항 1에 있어서, 상기 연결제의 친핵성 작용기는 히드록시기, 아미노기, 티올기, 아마이드기, 아민기 및 카르복시산기로 이루어진 군에서 선택된 1종 이상인 것인 다관능성 이소시아네이트계 가교제.
The multifunctional isocyanate crosslinking agent according to claim 1, wherein the nucleophilic functional group of the linking agent is at least one member selected from the group consisting of a hydroxyl group, an amino group, a thiol group, an amide group, an amine group and a carboxylic acid group.
청구항 3에 있어서, 상기 연결제는
Figure 112012108920838-pat00082
,
Figure 112012108920838-pat00083
,
Figure 112012108920838-pat00084
,
Figure 112012108920838-pat00085
,
Figure 112012108920838-pat00086
,
Figure 112012108920838-pat00087
,
Figure 112012108920838-pat00088
,
Figure 112012108920838-pat00089
,
Figure 112012108920838-pat00090
,
Figure 112012108920838-pat00091
,
Figure 112012108920838-pat00092
,
Figure 112012108920838-pat00093
,
Figure 112012108920838-pat00094
,
Figure 112012108920838-pat00095
,
Figure 112012108920838-pat00096
,
Figure 112012108920838-pat00097
,
Figure 112012108920838-pat00098
,
Figure 112012108920838-pat00099
,
Figure 112012108920838-pat00100
,
Figure 112012108920838-pat00101
,
Figure 112012108920838-pat00102
,
Figure 112012108920838-pat00103
,
Figure 112012108920838-pat00104
,
Figure 112012108920838-pat00105
,
Figure 112012108920838-pat00106
,
Figure 112012108920838-pat00107
,
Figure 112012108920838-pat00108
,
Figure 112012108920838-pat00109
,
Figure 112012108920838-pat00110
,
Figure 112012108920838-pat00111
,
Figure 112012108920838-pat00112
,
Figure 112012108920838-pat00113
,
Figure 112012108920838-pat00114
,
Figure 112012108920838-pat00115
,
Figure 112012108920838-pat00116
,
Figure 112012108920838-pat00117
,
Figure 112012108920838-pat00118
,
Figure 112012108920838-pat00119
및
Figure 112012108920838-pat00120
로 이루어진 군에서 선택된 1종 이상인 것인 다관능성 이소시아네이트계 가교제.
4. The connector according to claim 3,
Figure 112012108920838-pat00082
,
Figure 112012108920838-pat00083
,
Figure 112012108920838-pat00084
,
Figure 112012108920838-pat00085
,
Figure 112012108920838-pat00086
,
Figure 112012108920838-pat00087
,
Figure 112012108920838-pat00088
,
Figure 112012108920838-pat00089
,
Figure 112012108920838-pat00090
,
Figure 112012108920838-pat00091
,
Figure 112012108920838-pat00092
,
Figure 112012108920838-pat00093
,
Figure 112012108920838-pat00094
,
Figure 112012108920838-pat00095
,
Figure 112012108920838-pat00096
,
Figure 112012108920838-pat00097
,
Figure 112012108920838-pat00098
,
Figure 112012108920838-pat00099
,
Figure 112012108920838-pat00100
,
Figure 112012108920838-pat00101
,
Figure 112012108920838-pat00102
,
Figure 112012108920838-pat00103
,
Figure 112012108920838-pat00104
,
Figure 112012108920838-pat00105
,
Figure 112012108920838-pat00106
,
Figure 112012108920838-pat00107
,
Figure 112012108920838-pat00108
,
Figure 112012108920838-pat00109
,
Figure 112012108920838-pat00110
,
Figure 112012108920838-pat00111
,
Figure 112012108920838-pat00112
,
Figure 112012108920838-pat00113
,
Figure 112012108920838-pat00114
,
Figure 112012108920838-pat00115
,
Figure 112012108920838-pat00116
,
Figure 112012108920838-pat00117
,
Figure 112012108920838-pat00118
,
Figure 112012108920838-pat00119
And
Figure 112012108920838-pat00120
Wherein the polyfunctional isocyanate-based crosslinking agent is at least one selected from the group consisting of a polyfunctional isocyanate-based crosslinking agent.
아크릴계 공중합체 및 상기 청구항 1 내지 4중 어느 한 항의 다관능성 이소시아네이트계 가교제를 함유하는 점착제 조성물.
Acrylic copolymer and the polyfunctional isocyanate-based crosslinking agent of any one of claims 1 to 4.
청구항 5에 있어서, 상기 다관능성 이소시아네이트계 가교제는 아크릴계 공중합체 100중량부에 대하여 0.1 내지 10중량부 함유하는 점착제 조성물.
The pressure-sensitive adhesive composition according to claim 5, wherein the polyfunctional isocyanate-based crosslinking agent is contained in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the acrylic copolymer.
KR1020120156074A 2012-12-28 2012-12-28 New multi-functional isocyanate crosslinker and composition for adhesive comprising the same KR101925073B1 (en)

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