KR20140024799A - Adhesive composition and adhesive - Google Patents
Adhesive composition and adhesiveDownload PDFInfo
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- KR20140024799A KR20140024799AKR1020130075177AKR20130075177AKR20140024799AKR 20140024799 AKR20140024799 AKR 20140024799AKR 1020130075177 AKR1020130075177 AKR 1020130075177AKR 20130075177 AKR20130075177 AKR 20130075177AKR 20140024799 AKR20140024799 AKR 20140024799A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—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
- C09J133/062—Copolymers with monomers not covered by C09J133/06
- C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
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- Adhesives Or Adhesive Processes (AREA)
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Abstract
Translated fromKoreanDescription
Translated fromKorean본 발명은 고온 환경 하에서도 접착력이나 유지력의 저하가 적은 점착제 조성물 및 점착제에 관한 것이다.The present invention relates to a pressure-sensitive adhesive composition and a pressure-sensitive adhesive with a small decrease in the adhesive force and the holding force even under a high temperature environment.
종래, 점착 테이프 또는 시트류는, 영구 접착의 용도가 주였지만, 요즘은 가(假)고정이나 재박리 등의 단중기(短中期) 접착을 목적으로 한 용도가 주목받고 있다.Background Art Conventionally, adhesive tapes or sheets have been mainly used for permanent adhesion, but nowadays, applications for the purpose of short-term adhesion such as temporary fixing and re-peeling have been attracting attention.
이와 같은 단중기 접착을 목적으로 한 접착 테이프 또는 시트류는, 최근, 광학 부재의 첩합(貼合)이나 부재 보호를 위한 가접착 등의 공정에서 사용되는 것이 증가하고 있다. 따라서, 이러한 경우에는, 내열성이 요구되어진다.BACKGROUND ART In recent years, adhesive tapes or sheets for the purpose of short-term adhesion have been increasingly used in processes such as bonding of optical members and provisional bonding for protecting members. Therefore, in such a case, heat resistance is required.
일반적으로, 내열성이 요구되는 용도에서는, 열적으로 안정한 실리콘계 접착 테이프 또는 시트류가 사용되는 경우가 많다. 당해 실리콘계 접착 테이프 또는 시트류는, 단순히 열에 의해 열화(劣化)가 생기지 않는다는 것뿐만 아니라, 150℃를 초과하는 고온의 영역이어도, 비교적 안정한 점착 특성을 유지할 수 있는 메리트를 갖고 있다. 그러나, 하드디스크 드라이브를 비롯한 전자 관련 용도에서는, 실리콘계 화합물은 오염 등의 문제로부터 사용하기 어려운 경우가 있다. 또한, 실리콘계 화합물은 가격이 높다는 디메리트도 갖고 있다.Generally, thermally stable silicone adhesive tapes or sheets are often used in applications requiring heat resistance. The silicone adhesive tape or sheet not only does not deteriorate due to heat, but also has a merit that can maintain relatively stable adhesive properties even in a high temperature region exceeding 150 ° C. However, in electronic-related applications including hard disk drives, silicon-based compounds may be difficult to use due to problems such as contamination. In addition, silicone compounds also have a dimer of high price.
이와 같은 배경으로부터, 최근에는 오염의 걱정이 없으며, 또한 저렴한 아크릴계 점착제가 주목받고 있다.From such a background, there is no worry of contamination in recent years, and inexpensive acrylic adhesives have attracted attention.
상기 내열성을 갖는 아크릴계 점착제로서는, 예를 들면 테르펜계 (메타)아크릴레이트 화합물을 사용하여 얻어진 아크릴 수지를 함유하는 점착제 조성물이 알려져 있다(예를 들면 특허문헌 1을 참조). 상기의 방법에 의해 내열성은 개선되고는 있지만, 시장은 아크릴계 점착제에 있어서 내열성의 향상을 더 요구하고 있다.As an acrylic adhesive which has the said heat resistance, the adhesive composition containing the acrylic resin obtained using the terpene-type (meth) acrylate compound, for example is known (for example, refer patent document 1). Although heat resistance is improved by the said method, the market requires further improvement of heat resistance in an acrylic adhesive.
본 발명이 해결하고자 하는 과제는, 고온 환경 하에서도 접착력이나 유지력의 저하가 적은 점착제 조성물을 제공하는 것이다.The problem to be solved by the present invention is to provide a pressure-sensitive adhesive composition which is less deteriorated in adhesive force and holding force even under a high temperature environment.
본 발명자들은, 상기 과제를 해결하기 위해 예의 연구를 진행시키는 가운데, (메타)아크릴 단량체의 종류에 착목하여, 연구를 진행시켰다.MEANS TO SOLVE THE PROBLEM In order to solve the said subject, the present inventors advanced the research, focusing on the kind of (meth) acryl monomer.
그 결과, (메타)아크릴산 및 에스테르기를 2∼6개의 범위에서 갖는 (메타)아크릴 단량체를 함유하는 카르복시기를 갖는 (메타)아크릴 단량체를, 그 밖의 특정의 (메타)아크릴 단량체와 중합하여 얻어지는 아크릴 수지를 사용하고, 용매 및 가교제를 더 조합시킴으로써 상기 과제를 해결하는 것을 알아내어, 본 발명을 완성하기에 이르렀다.As a result, the acrylic resin obtained by superposing | polymerizing the (meth) acryl monomer which has a carboxy group containing the (meth) acrylic monomer which has a (meth) acrylic acid and ester group in 2-6 ranges with another specific (meth) acryl monomer. It was found that the above problems were solved by further using a solvent and a crosslinking agent, thereby completing the present invention.
즉, 본 발명은 (메타)아크릴산알킬에스테르(a-1), 카르복시기를 갖는 (메타)아크릴 단량체(a-2) 및 수산기를 갖는 (메타)아크릴 단량체(a-3)를 중합하여 얻어진 아크릴 수지(A), 용매(B) 및 가교제(C)를 함유하는 점착제 조성물에 있어서, 상기 (메타)아크릴 단량체(a-2)가, (메타)아크릴산 및 에스테르기를 2∼6개의 범위에서 갖는 (메타)아크릴 단량체를 함유하는 것을 특징으로 하는 점착제 조성물 및 점착제를 제공하는 것이다.That is, this invention is an acrylic resin obtained by superposing | polymerizing the (meth) acrylic-acid alkylester (a-1), the (meth) acryl monomer (a-2) which has a carboxyl group, and the (meth) acryl monomer (a-3) which has a hydroxyl group. In the adhesive composition containing (A), a solvent (B), and a crosslinking agent (C), the said (meth) acryl monomer (a-2) has a (meth) acrylic acid and ester group in the range of 2-6 (meth) An acrylic monomer is contained, and it is providing the adhesive composition and adhesive.
본 발명의 점착제 조성물을 사용하여 얻어지는 점착제는, 고온 환경 하에서도 접착력이나 유지력의 저하가 적은(이하, 「내열성」이라고 약기함) 것이다.The adhesive obtained using the adhesive composition of this invention is a thing with little fall of adhesive force and holding force even in high temperature environment (it abbreviates as "heat resistance" hereafter).
본 발명의 점착제 조성물을 사용하여 얻어지는 점착제는, 광학 부재에 사용되는 점착제로서 호적(好適)하게 사용할 수 있다. 특히, 터치 패널, 액정 디스플레이, 플라스마 디스플레이, LED, 유기 EL, PC, 휴대 전화 등의 제조에 호적하게 사용할 수 있다.The adhesive obtained using the adhesive composition of this invention can be used suitably as an adhesive used for an optical member. In particular, it can use suitably for manufacture of a touchscreen, a liquid crystal display, a plasma display, LED, organic electroluminescent, a PC, a mobile telephone.
본 발명의 점착제 조성물은, (메타)아크릴산알킬에스테르(a-1), (메타)아크릴산 및 에스테르기를 2∼6개의 범위에서 갖는 (메타)아크릴 단량체를 함유하는 카르복시기를 갖는 (메타)아크릴 단량체(a-2) 및 수산기를 갖는 (메타)아크릴 단량체(a-3)를 중합하여 얻어진 아크릴 수지(A), 용매(B) 및 가교제(C)를 함유하는 것이다. 한편, 본 발명에 있어서, 「(메타)아크릴」이란, 아크릴 및／또는 메타크릴을 나타내고, 「(메타)아크릴레이트」란, 아크릴레이트 및／또는 메타크릴레이트를 나타내며, 「(메타)아크릴로일」이란, 아크릴로일 및／또는 메타크릴로일을 나타낸다.The pressure-sensitive adhesive composition of the present invention is a (meth) acryl monomer having a (meth) acrylic acid alkyl ester (a-1), a (meth) acrylic acid and a (meth) acryl monomer having a (meth) acryl monomer having an ester group in the range of 2 to 6 ( It contains an acrylic resin (A), a solvent (B), and a crosslinking agent (C) obtained by superposing | polymerizing the (meth) acryl monomer (a-3) which has a-2) and a hydroxyl group. In addition, in this invention, "(meth) acryl" shows an acryl and / or methacryl, and "(meth) acrylate" shows an acrylate and / or methacrylate, and it is a "(meth) acryl "" Refers to acryloyl and / or methacryloyl.
상기 (메타)아크릴산알킬에스테르(a-1)의 알킬기의 탄소 원자수로서는, 통상 1∼20의 범위, 바람직하게는 1∼12의 범위, 보다 바람직하게는 1∼8의 범위, 더 바람직하게는 4∼8의 범위이다.As carbon number of the alkyl group of the said (meth) acrylic-acid alkylester (a-1), it is the range of 1-20 normally, Preferably it is the range of 1-12, More preferably, it is the range of 1-8, More preferably It is the range of 4-8.
상기 (메타)아크릴산알킬에스테르(a-1)로서는, 예를 들면 메틸(메타)아크릴레이트, 에틸(메타)아크릴레이트, n-부틸(메타)아크릴레이트, iso-부틸(메타)아크릴레이트, tert-부틸(메타)아크릴레이트, n-프로필(메타)아크릴레이트, n-헥실(메타)아크릴레이트, 2-에틸헥실(메타)아크릴레이트, n-옥틸(메타)아크릴레이트, 이소데실(메타)아크릴레이트, 라우릴(메타)아크릴레이트, 세틸(메타)아크릴레이트, 스테아릴(메타)아크릴레이트, 시클로헥실(메타)아크릴레이트, 이소보르닐(메타)아크릴레이트 등을 사용할 수 있다. 이들 화합물은 단독으로 사용해도 2종 이상을 병용(倂用)해도 된다. 이들 중에서도, 중합성, 점착 물성, 작업성 등을 보다 한층 향상시킬 수 있고, 또한 원료를 입수하기 쉬운 점에서, n-부틸(메타)아크릴레이트, 2-에틸헥실(메타)아크릴레이트를 사용하는 것이 바람직하다.As said (meth) acrylic-acid alkylester (a-1), for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, tert -Butyl (meth) acrylate, n-propyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isodecyl (meth) Acrylate, lauryl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, etc. can be used. These compounds may be used singly or in combination of two or more kinds. Among them, n-butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate are used because polymerizability, adhesive properties, workability and the like can be further improved and raw materials are easily obtained. It is preferable.
상기 (메타)아크릴산알킬에스테르(a-1)의 사용량으로서는, (메타)아크릴산알킬에스테르(a-1), 카르복시기를 갖는 (메타)아크릴 단량체(a-2) 및 수산기를 갖는 (메타)아크릴 단량체(a-3)의 합계 100질량부에 대하여, 80∼95질량부의 범위가 바람직하고, 85∼90질량부의 범위가 더 바람직하다.As the usage-amount of the said (meth) acrylic-acid alkylester (a-1), the (meth) acrylic-acid alkylester (a-1), the (meth) acryl monomer (a-2) which has a carboxyl group, and the (meth) acryl monomer which has a hydroxyl group The range of 80-95 mass parts is preferable with respect to a total of 100 mass parts of (a-3), and the range of 85-90 mass parts is more preferable.
상기 에스테르기를 2∼6개의 범위에서 갖는 (메타)아크릴 단량체로서는, 예를 들면 카르복시에틸(메타)아크릴레이트, 카르복시펜틸(메타)아크릴레이트, (메타)아크릴아미드N-글리콜산, (아크릴로일아미노)히드록시아세트산, 이타콘산, 무수 이타콘산, 말레산, 무수 말레산, 푸마르산, 크로톤산, 하기 일반식(1)으로 표시되는 (메타)아크릴 단량체, 하기 일반식(2)으로 표시되는 (메타)아크릴 단량체 등을 사용할 수 있다. 이들 단량체는 단독으로 사용해도 2종 이상을 병용해도 된다. 이들 중에서도, 후술하는 가교제(C)를 사용했을 때의 가교간 거리나 가교성의 효과로부터 내열성이 보다 한층 향상하는 점에서, 에스테르기를 2∼4개의 범위에서 갖는 (메타)아크릴 단량체를 사용하는 것이 바람직하고, 하기 일반식(1)으로 표시되는 (메타)아크릴 단량체 및 하기 일반식(2)으로 표시되는 (메타)아크릴 단량체로 이루어지는 군에서 선택되는 1종 이상의 (메타)아크릴 단량체를 사용하는 것이 더 바람직하다. 한편, 상기 에스테르기를 셀 때에는, (메타)아크릴로일기 유래의 에스테르기도 포함시킨다.As a (meth) acryl monomer which has the said ester group in 2-6 ranges, For example, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, (meth) acrylamide N-glycolic acid, (acryloyl) Amino) hydroxyacetic acid, itaconic acid, itaconic anhydride, maleic anhydride, maleic anhydride, fumaric acid, crotonic acid, (meth) acrylic monomer represented by the following general formula (1), represented by the following general formula (2) Meta) acryl monomers and the like can be used. These monomers may be used independently or may use 2 or more types together. Among these, it is preferable to use the (meth) acryl monomer which has an ester group in the range of 2-4 from the point which heat resistance further improves from the distance between crosslinks and crosslinking effect at the time of using the crosslinking agent (C) mentioned later. It is further preferable to use at least one (meth) acryl monomer selected from the group consisting of a (meth) acryl monomer represented by the following general formula (1) and a (meth) acryl monomer represented by the following general formula (2). desirable. In addition, when counting the said ester group, the ester group derived from a (meth) acryloyl group is also included.
(식(1) 중, n은 반복 단위수의 평균으로 1∼3의 범위를 나타내고, R1은 수소 원자 또는 메틸기를 나타냄)(In formula (1), n represents the range of 1-3 as an average of the number of repeating units, R <1> represents a hydrogen atom or a methyl group.)
(식(2) 중, n은 반복 단위수의 평균으로 1∼2의 범위를 나타내고, R2은 수소 원자 또는 메틸기를 나타냄)(In formula (2), n represents a range of 1 to 2 as an average of the number of repeating units, and R2 represents a hydrogen atom or a methyl group.)
상기 카르복시기를 갖는 (메타)아크릴 단량체(a-2) 중에서의, 상기 (메타)아크릴산과, 상기 에스테르기를 2∼6개의 범위에서 갖는 (메타)아크릴 단량체의 질량 비율로서는, 점착 물성이나 후술하는 가교제(C)를 사용했을 때의 가교간 거리나 가교성의 효과로부터 내열성이 보다 한층 향상하는 점에서, 95／5∼50／50의 범위가 바람직하고, 94／6∼70／30의 범위가 보다 바람직하며, 93／7∼80／20의 범위가 더 바람직하고, 92／8∼85／15의 범위가 특히 바람직하다.As mass ratio of the said (meth) acrylic acid and the (meth) acryl monomer which has the said ester group in 2-6 ranges in the (meth) acryl monomer (a-2) which has the said carboxyl group, it is adhesive physical property and a crosslinking agent mentioned later From the point which improves heat resistance further from the distance between bridge | crosslinks and crosslinking effect at the time of using (C), the range of 95 / 5-50 / 50 is preferable, and the range of 94 / 6-70 / 30 is more preferable. The range of 93/7 to 80/20 is more preferable, and the range of 92/8 to 85/15 is particularly preferable.
상기 카르복시기를 갖는 (메타)아크릴 단량체(a-2)의 사용량으로서는, 내열성이 보다 향상하는 점에서, (메타)아크릴산알킬에스테르(a-1), 카르복시기를 갖는 (메타)아크릴 단량체(a-2) 및 수산기를 갖는 (메타)아크릴 단량체(a-3)의 합계 100질량부에 대하여, 3∼18질량부의 범위가 바람직하고, 5∼15질량부의 범위가 더 바람직하며, 8∼12질량부의 범위가 특히 바람직하다.As the usage-amount of the (meth) acryl monomer (a-2) which has the said carboxyl group, since heat resistance improves more, (meth) acrylic-acid alkylester (a-1) and the (meth) acryl monomer (a-2) which has a carboxyl group The range of 3-18 mass parts is preferable with respect to a total of 100 mass parts of the (meth) acryl monomer (a-3) which has a) and a hydroxyl group, The range of 5-15 mass parts is more preferable, The range of 8-12 mass parts Is particularly preferred.
상기 수산기를 갖는 (메타)아크릴 단량체(a-3)로서는, 예를 들면 2-히드록시에틸(메타)아크릴레이트, 2-히드록시프로필(메타)아크릴레이트, 3-히드록시프로필(메타)아크릴레이트, 2-히드록시부틸(메타)아크릴레이트, 4-히드록시부틸(메타)아크릴레이트, 2-히드록시헥실(메타)아크릴레이트, 6-히드록시헥실(메타)아크릴레이트, 8-히드록시옥틸(메타)아크릴레이트, 10-히드록시데실(메타)아크릴레이트, 12-히드록시라우릴(메타)아크릴레이트 등의 히드록시알킬(메타)아크릴레이트나, 폴리옥시에틸렌(메타)아크릴레이트, 폴리옥시프로필렌(메타)아크릴레이트, 글리세롤(메타)아크릴레이트 등을 사용할 수 있다. 이들 단량체는 단독으로 사용해도 2종 이상을 병용해도 된다. 이들 중에서도, 가교 반응성을 보다 한층 향상시킬 수 있는 점에서, 2-히드록시에틸(메타)아크릴레이트, 3-히드록시프로필(메타)아크릴레이트, 4-히드록시부틸(메타)아크릴레이트를 사용하는 것이 바람직하다.As a (meth) acryl monomer (a-3) which has the said hydroxyl group, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acryl Latex, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxyhexyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxy Hydroxyalkyl (meth) acrylates such as octyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, polyoxyethylene (meth) acrylate, Polyoxypropylene (meth) acrylate, glycerol (meth) acrylate, etc. can be used. These monomers may be used independently or may use 2 or more types together. Among these, since the crosslinking reactivity can be improved further, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate are used. It is preferable.
상기 수산기를 갖는 (메타)아크릴 단량체(a-3)의 사용량으로서는, (메타)아크릴산알킬에스테르(a-1), 카르복시기를 갖는 (메타)아크릴 단량체(a-2) 및 수산기를 갖는 (메타)아크릴 단량체(a-3)의 합계 100질량부에 대하여, 0.001∼2질량부의 범위가 바람직하고, 0.01∼1질량부의 범위가 더 바람직하다.As a usage-amount of the (meth) acryl monomer (a-3) which has the said hydroxyl group, (meth) acrylic-acid alkylester (a-1), the (meth) acryl monomer (a-2) which has a carboxyl group, and (meth) which has a hydroxyl group The range of 0.001-2 mass parts is preferable with respect to a total of 100 mass parts of an acryl monomer (a-3), and the range of 0.01-1 mass part is more preferable.
상기 아크릴 수지(A)의 제조 방법으로서는, 예를 들면 아크릴 단량체가 갖는 중합성 이중 결합에 기인한 라디칼 중합법을 사용할 수 있다. 구체적으로는, 상기 성분(a-1)∼(a-3), 필요에 따라 그 밖의 비닐 단량체, 중합 개시제 및 후술하는 용매(B)를, 바람직하게는 40∼90℃의 온도 하에서 혼합, 교반하여, 라디칼 중합을 진행시키는 방법을 사용할 수 있다.As a manufacturing method of the said acrylic resin (A), the radical polymerization method resulting from the polymerizable double bond which an acrylic monomer has can be used, for example. Specifically, the above components (a-1) to (a-3), other vinyl monomers, a polymerization initiator, and a solvent (B) to be described later are preferably mixed and stirred at a temperature of 40 to 90 ° C. To advance the radical polymerization.
상기 그 밖의 비닐 단량체로서는, 예를 들면 스티렌설폰산, 알릴설폰산, 2-(메타)아크릴아미드-2-메틸프로판설폰산, (메타)아크릴아미드프로판설폰산, 설포프로필(메타)아크릴레이트, (메타)아크릴로일옥시나프탈렌설폰산, 비닐설폰산나트륨 등의 설폰산기를 갖는 (메타)아크릴 단량체; 2-히드록시에틸아크릴로일포스페이트기 및 인산기를 갖는 (메타)아크릴 단량체; 아크릴로니트릴, 메타크릴로니트릴 등의 시아노기를 갖는 단량체; 글리시딜(메타)아크릴레이트, 메틸글리시딜(메타)아크릴레이트, 알릴글리시딜에테르 등의 글리시딜기를 갖는 (메타)아크릴 단량체; 아세트산비닐, 프로피온산비닐, 라우르산비닐, 스티렌, 클로로스티렌, 클로로메틸스티렌, α-메틸스티렌, 그 밖의 치환 스티렌, 메틸비닐에테르, 에틸비닐에테르, 이소부틸비닐에테르 등의 비닐 단량체 등을 사용할 수 있다.Examples of the other vinyl monomers include styrene sulfonic acid, allyl sulfonic acid, 2- (meth) acrylamide-2-methylpropanesulfonic acid, (meth) acrylamide propanesulfonic acid, sulfopropyl (meth) acrylate, (Meth) acryl monomer which has sulfonic-acid groups, such as (meth) acryloyloxy naphthalene sulfonic acid and sodium vinyl sulfonate; (Meth) acrylic monomers having a 2-hydroxyethylacryloyl phosphate group and a phosphoric acid group; Monomers having cyano groups such as acrylonitrile and methacrylonitrile; (Meth) acryl monomers having glycidyl groups such as glycidyl (meth) acrylate, methylglycidyl (meth) acrylate and allyl glycidyl ether; Vinyl monomers such as vinyl acetate, vinyl propionate, vinyl laurate, styrene, chlorostyrene, chloromethylstyrene, α-methylstyrene, other substituted styrene, methyl vinyl ether, ethyl vinyl ether, and isobutyl vinyl ether have.
상기 중합 개시제로서는, 예를 들면 과산화수소, 과황산칼륨, 과황산나트륨, 과황산암모늄 등의 과산화물; 벤조일퍼옥사이드, t-부틸퍼옥시-2-에틸헥사노에이트, 쿠멘하이드로퍼옥사이드 등의 유기 과산화물; 2,2'-아조비스-(2-아미노디프로판)2염산염, 2,2'-아조비스-(N,N'-디메틸렌이소부틸아미딘)2염산염, 2,2'-아조비스{2-메틸-N-[1,1-비스(히드록시메틸)-2-히드록시에틸]프로피온아미드}, 아조비스이소부티로니트릴, 2,2'-아조비스(2-메틸부티로니트릴) 등의 아조 화합물 등을 사용할 수 있다.As said polymerization initiator, For example, peroxides, such as hydrogen peroxide, potassium persulfate, sodium persulfate, ammonium persulfate; Organic peroxides such as benzoyl peroxide, t-butylperoxy-2-ethylhexanoate and cumene hydroperoxide; 2,2'-azobis- (2-aminodipropane) dihydrochloride, 2,2'-azobis- (N, N'-dimethyleneisobutylamidine) dihydrochloride, 2,2'-azobis { 2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide}, azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile) Azo compounds, such as these, can be used.
상기 중합 개시제의 사용량으로서는, 양호한 반응성을 부여할 수 있는 점에서, 아크릴 수지(A)의 투입 원료 100질량부에 대하여, 0.01∼5질량부의 범위인 것이 바람직하다.As a usage-amount of the said polymerization initiator, since it can provide favorable reactivity, it is preferable that it is the range of 0.01-5 mass parts with respect to 100 mass parts of input raw materials of an acrylic resin (A).
상기 용매(B)로서는, 유기 용매를 사용하는 것이 바람직하고, 예를 들면 아세트산에틸, 아세트산메틸, 아세트산부틸 등의 에스테르계 용매; 아세톤, 메틸에틸케톤, 메틸이소부틸케톤 등의 케톤계 용매; 헵탄, 헥산, 시클로헥산, 메틸시클로헥산 등의 지방족 탄화수소계 용매; 톨루엔, o-자일렌, m-자일렌, p-자일렌 등의 방향족 탄화수소계 용매; 메탄올, 에탄올, 이소프로필알코올, 이소부탄올, sec-부탄올, tert-부탄올 등의 알코올계 용매 등을 사용할 수 있다. 이들 용매는 단독으로 사용해도 2종 이상을 병용해도 된다.As said solvent (B), it is preferable to use an organic solvent, For example, Ester solvent, such as ethyl acetate, methyl acetate, butyl acetate; Ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; Aliphatic hydrocarbon solvents such as heptane, hexane, cyclohexane and methylcyclohexane; Aromatic hydrocarbon solvents such as toluene, o-xylene, m-xylene and p-xylene; Alcohol solvents, such as methanol, ethanol, isopropyl alcohol, isobutanol, sec-butanol, and tert-butanol, etc. can be used. These solvent may be used independently or may use 2 or more types together.
상기 용매(B)의 사용량은, 본 발명의 점착제 조성물 중의 30∼80질량％의 범위인 것이 바람직하다.It is preferable that the usage-amount of the said solvent (B) is 30 to 80 mass% in the adhesive composition of this invention.
이상의 방법에 의해 얻어지는 아크릴 수지(A)의 중량 평균 분자량으로서는, 점착 물성이나 내열성 등을 보다 한층 향상시킬 수 있는 점에서, 20만∼200만의 범위인 것이 바람직하고, 30만∼150만의 범위가 보다 바람직하며, 40∼100만의 범위가 더 바람직하다. 한편, 상기 아크릴 수지(A)의 중량 평균 분자량은, 겔·퍼미에이션·크로마토그래피(GPC)법에 의해, 하기의 조건으로 측정하여 얻어진 값을 나타낸다.As a weight average molecular weight of the acrylic resin (A) obtained by the above method, from the point which can improve adhesive physical property, heat resistance, etc. further, it is preferable that it is the range of 200,000-2 million, and the range of 300,000-1,500,000 is more Preferably, the range of 40 to 1 million is more preferable. In addition, the weight average molecular weight of the said acrylic resin (A) shows the value obtained by measuring on condition of the following by the gel permeation chromatography (GPC) method.
측정 장치: 고속 GPC 장치(도소 가부시키가이샤제 「HLC-8220GPC」)Measuring device: High speed GPC device (“HLC-8220GPC” manufactured by Tosoh Corporation)
칼럼: 도소 가부시키가이샤제의 하기의 칼럼을 직렬로 접속하여 사용했다.Column: The following columns, manufactured by Tosoh Corporation, were connected in series.
「TS㎏el G5000」(7.8㎜I.D.×30㎝)×1개`` TSkgel G5000 '' (7.8mmI.D. * 30cm) * 1
「TS㎏el G4000」(7.8㎜I.D.×30㎝)×1개`` TS kgel G4000 '' (7.8mmI.D. * 30cm) * 1
「TS㎏el G3000」(7.8㎜I.D.×30㎝)×1개`` TS kgel G3000 '' (7.8mmI.D. * 30cm) * 1
「TS㎏el G2000」(7.8㎜I.D.×30㎝)×1개`` TS kgel G2000 '' (7.8mmI.D. * 30cm) * 1
검출기: RI(시차 굴절계)Detector: RI (Differential Refractometer)
칼럼 온도: 40℃Column temperature: 40 DEG C
용리액: 테트라히드로퓨란(THF)Eluent: tetrahydrofuran (THF)
유속: 1.0mL／분Flow rate: 1.0mL / min
주입량: 100μL(시료 농도 0.4질량％의 테트라히드로퓨란 용액)Injection amount: 100 microliters (tetrahydrofuran solution of 0.4 mass% of sample concentration)
표준 시료: 하기의 표준 폴리스티렌을 사용하여 검량선을 작성했다.Standard sample: The calibration curve was created using the following standard polystyrene.
(표준 폴리스티렌)(Standard polystyrene)
도소 가부시키가이샤제 「TS㎏el 표준 폴리스티렌 A-500」"TS kgel standard polystyrene A-500" made by Toso Corporation
도소 가부시키가이샤제 「TS㎏el 표준 폴리스티렌 A-1000」"TS kgel standard polystyrene A-1000" made by Toso Corporation
도소 가부시키가이샤제 「TS㎏el 표준 폴리스티렌 A-2500」"TS kgel standard polystyrene A-2500" made by Toso Corporation
도소 가부시키가이샤제 「TS㎏el 표준 폴리스티렌 A-5000」"TS kgel standard polystyrene A-5000" made by Toso Corporation
도소 가부시키가이샤제 「TS㎏el 표준 폴리스티렌 F-1」"TS kgel standard polystyrene F-1" made by Toso Corporation
도소 가부시키가이샤제 「TS㎏el 표준 폴리스티렌 F-2」"TS kgel standard polystyrene F-2" made by Toso Corporation
도소 가부시키가이샤제 「TS㎏el 표준 폴리스티렌 F-4」"TS kgel standard polystyrene F-4" made by Toso Corporation
도소 가부시키가이샤제 「TS㎏el 표준 폴리스티렌 F-10」"TS kgel standard polystyrene F-10" made by Toso Corporation
도소 가부시키가이샤제 「TS㎏el 표준 폴리스티렌 F-20」"TS kgel standard polystyrene F-20" made by Toso Corporation
도소 가부시키가이샤제 「TS㎏el 표준 폴리스티렌 F-40」"TS kgel standard polystyrene F-40" made by Toso Corporation
도소 가부시키가이샤제 「TS㎏el 표준 폴리스티렌 F-80」"TS kgel standard polystyrene F-80" made by Toso Corporation
도소 가부시키가이샤제 「TS㎏el 표준 폴리스티렌 F-128」"TS kgel standard polystyrene F-128" made by Toso Corporation
도소 가부시키가이샤제 「TS㎏el 표준 폴리스티렌 F-288」"TS kgel standard polystyrene F-288" made by Toso Corporation
도소 가부시키가이샤제 「TS㎏el 표준 폴리스티렌 F-550」"TS kgel standard polystyrene F-550" made by Toso Corporation
상기 가교제(C)로서는, 예를 들면 에폭시 화합물, 폴리이소시아네이트 화합물, 멜라민 화합물, 금속 킬레이트 등을 사용할 수 있다. 이들 중에서도, 에폭시 화합물을 사용하는 것이 점착 물성이나 내열성 등을 보다 한층 향상시킬 수 있는 점에서 바람직하다.As said crosslinking agent (C), an epoxy compound, a polyisocyanate compound, a melamine compound, a metal chelate, etc. can be used, for example. Among these, using an epoxy compound is preferable at the point which can improve adhesive physical property, heat resistance, etc. further.
상기 에폭시 화합물로서는, 예를 들면 비스페놀A·에피클로로히드린형의 에폭시 수지나, 에틸렌글리콜디글리시딜에테르, 폴리에틸렌글리콜디글리시딜에테르, 글리세린디글리시딜에테르, 글리세린트리글리시딜에테르, 1,6-헥산디올디글리시딜에테르, 트리메틸올프로판트리글리시딜에테르, 소르비톨폴리글리시딜에테르, 폴리글리세롤폴리글리시딜에테르, 펜타에리트리톨폴리글리시딜에리트리톨, 디글리세롤폴리글리시딜에테르, 1,3-비스(N,N-디글리시딜아미노메틸)시클로헥산, N,N,N',N'-테트라글리시딜-m-자일렌디아민 등을 사용할 수 있다. 이들 화합물은 단독으로 사용해도 2종 이상을 병용해도 된다.As said epoxy compound, the bisphenol A epichlorohydrin type epoxy resin, ethylene glycol diglycidyl ether, polyethyleneglycol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylol propane triglycidyl ether, sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl erythritol, diglycerol polyglycidyl Dimethyl ether, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ', N'-tetraglycidyl-m-xylenediamine, and the like can be used. These compounds may be used independently or may use 2 or more types together.
상기 가교제(C)의 사용량으로서는, 점착 물성이나 내열성을 보다 한층 향상시킬 수 있는 점에서, 상기 아크릴 수지(A) 100질량부에 대하여, 0.01∼20질량부의 범위인 것이 바람직하고, 0.1∼5질량부의 범위가 보다 바람직하며, 0.1∼3질량부의 범위가 특히 바람직하다.As the usage-amount of the said crosslinking agent (C), since adhesive property and heat resistance can be improved further, it is preferable that it is the range of 0.01-20 mass parts with respect to 100 mass parts of said acrylic resin (A), and is 0.1-5 mass The range of parts is more preferable, and the range of 0.1-3 mass parts is especially preferable.
본 발명의 점착제 조성물은, 상기 아크릴 수지(A), 상기 용매(B) 및 상기 가교제(C)를 함유하지만, 필요에 따라 그 밖의 첨가제를 함유해도 된다.Although the adhesive composition of this invention contains the said acrylic resin (A), the said solvent (B), and the said crosslinking agent (C), you may contain another additive as needed.
상기 그 밖의 첨가제로서는, 예를 들면 방청제, 틱소 부여제, 증감제, 중합 금지제, 레벨링제, 점착 부여제, 왁스, 열 안정제, 대전 방지제, 난연제, 정포제, 소포제, 방부제, 브로킹 방지제, 실란 커플링제 등을 사용할 수 있다.As said other additive, For example, a rust inhibitor, a thixotropic agent, a sensitizer, a polymerization inhibitor, a leveling agent, a tackifier, a wax, a heat stabilizer, an antistatic agent, a flame retardant, a foam stabilizer, an antifoamer, a preservative, an anti-broking agent, Silane coupling agents and the like can be used.
본 발명의 점착제의 제조 방법으로서는, 예를 들면 상기 방법으로 제조한 아크릴 수지(A), 용매(B) 및 가교제(C)를 혼합, 교반함으로써 제조할 수 있다. 상기 가교제(C)를 배합하면, 즉시 가교 반응이 진행되기 때문에, 혼합 후에는 신속히 도공 등을 행하는 것이 바람직하다.As a manufacturing method of the adhesive of this invention, it can manufacture by mixing and stirring the acrylic resin (A), the solvent (B), and the crosslinking agent (C) which were manufactured by the said method, for example. When the said crosslinking agent (C) is mix | blended, since a crosslinking reaction advances immediately, it is preferable to carry out coating etc. immediately after mixing.
[실시예][Example]
이하, 본 발명을 실시예에 의해, 구체적으로 설명한다.Hereinafter, the present invention will be described in detail with reference to Examples.
[합성예 1][Synthesis Example 1]
<아크릴 수지(A-1)의 합성><Synthesis of Acrylic Resin (A-1)>
교반기, 환류 냉각기, 질소 도입관, 온도계를 구비한 반응 용기에, n-부틸아크릴레이트 1070질량부, 아크릴산 117질량부, 4-히드록시부틸아크릴레이트 1질량부, 에스테르기를 갖는 아크릴 단량체(1)(상기 일반식(1)에서, n이 2, R2이 수소 원자인 아크릴 단량체) 12질량부, 아세트산에틸 2,200질량부를 투입하여, 교반 하, 질소를 취입(吹入)하면서 70℃까지 승온했다. 1시간 후에, 미리 아세트산에틸로 용해한 아조비스이소부티로니트릴 용액(고형분 5질량％) 20질량부를 첨가했다. 그 후, 교반 하 70℃에서 8시간 홀드한 후, 내용물을 냉각하고 200메쉬 금망(金網)으로 여과하여, 불휘발분 30질량％, 점도 10,000mPa·s, 중량 평균 분자량 60만의 아크릴 수지(A-1)를 얻었다.Acrylic monomer (1) having 1070 parts by mass of n-butyl acrylate, 117 parts by mass of acrylic acid, 1 part by mass of 4-hydroxybutyl acrylate, and an ester group in a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, and a thermometer. (In the said General formula (1), 12 mass parts and 2,200 mass parts of ethyl acetates were injected | thrown-in and acrylic acid whose n is 2 and R <2> is a hydrogen atom, and it heated up to 70 degreeC, blowing in nitrogen, stirring. . After 1 hour, 20 parts by mass of an azobisisobutyronitrile solution (5% by mass solid content) dissolved in ethyl acetate in advance was added. Thereafter, the mixture was held at 70 ° C for 8 hours under stirring, and then the contents were cooled and filtered through a 200-mesh gold mesh to obtain 30 mass% of nonvolatile content, a viscosity of 10,000 mPa · s, and a weight average molecular weight of 600,000 acrylic resin (A- 1) was obtained.
[합성예 2][Synthesis Example 2]
<아크릴 수지(A-2)의 합성><Synthesis of Acrylic Resin (A-2)>
합성예 1에 있어서, 에스테르기를 갖는 아크릴 단량체(1) 대신에, 에스테르기를 갖는 아크릴 단량체(2)(상기 일반식(2)에서, n이 1.4, R1이 수소 원자인 아크릴 단량체)를 사용한 것 이외는, 합성예 1과 같이 하여, 불휘발분 30질량％, 점도 10,000mPa·s, 중량 평균 분자량 66만의 아크릴 수지(A-2)를 얻었다.In the synthesis example 1, instead of the acryl monomer (1) which has an ester group, the acryl monomer (2) which has an ester group (in the said General formula (2), n is 1.4 and R <1> is an acrylic monomer whose R <1> is a hydrogen atom) was used. A acrylic resin (A-2) having a nonvolatile content of 30% by mass, a viscosity of 10,000 mPa · s and a weight average molecular weight of 660,000 was obtained except in the same manner as in Synthesis example 1.
[합성예 3][Synthesis Example 3]
<아크릴 수지(A-3)의 합성><Synthesis of Acrylic Resin (A-3)>
합성예 1에 있어서, n-부틸아크릴레이트의 사용량을 1,080질량부, 아크릴산의 사용량을 71질량부, 에스테르기를 갖는 아크릴 단량체(1)의 사용량을 120질량부로 변경한 것 이외는, 합성예 1과 같이 하여, 불휘발분 30질량％, 점도 10,000mPa·s, 중량 평균 분자량 120만의 아크릴 수지(A-3)를 얻었다.In Synthesis Example 1, except that the amount of the n-butyl acrylate used was 1,080 parts by mass, the amount of the acrylic acid used was 71 parts by mass and the amount of the acrylic monomer (1) having an ester group was changed to 120 parts by mass. Thus, 30 mass% of non volatile matters, the viscosity 10,000 mPa * s, and the acrylic resin (A-3) of the weight average molecular weight 1.2 million were obtained.
[합성예 4][Synthesis Example 4]
<아크릴 수지(A-4)의 합성><Synthesis of Acrylic Resin (A-4)>
교반기, 환류 냉각기, 질소 도입관, 온도계를 구비한 반응 용기에, n-부틸아크릴레이트 1,080질량부, 아크릴산 120질량부, 4-히드록시부틸아크릴레이트 1질량부, 아세트산에틸 2,200질량부를 투입하여, 교반 하, 질소를 취입하면서 아세트산에틸의 비점(沸点)까지 승온했다. 1시간 후에, 미리 아세트산에틸로 용해한 아조비스이소부티로니트릴 용액(고형분 5질량％) 20질량부를 첨가했다. 그 후, 교반 하 아세트산에틸의 비점에서 8시간 홀드한 후, 내용물을 냉각하고 200메쉬 금망으로 여과하여, 불휘발분 30질량％, 점도 10,000mPa·s, 중량 평균 분자량 71만의 아크릴 수지(A-4)를 얻었다.Into a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, and a thermometer, 1,080 parts by mass of n-butyl acrylate, 120 parts by mass of acrylic acid, 1 part by mass of 4-hydroxybutyl acrylate, and 2,200 parts by mass of ethyl acetate were added. The temperature was raised to the boiling point of ethyl acetate while blowing nitrogen while stirring. After 1 hour, 20 parts by mass of an azobisisobutyronitrile solution (solid content 5% by mass) dissolved in ethyl acetate was added. Thereafter, the mixture was held for 8 hours at a boiling point of ethyl acetate under stirring, and then the contents were cooled and filtered through a 200 mesh gold mesh to obtain 30% by mass of nonvolatile matter, a viscosity of 10,000 mPa · s, and a weight average molecular weight of 710,000 (A-4). )
[실시예 1]Example 1
합성예 1에서 얻어진 아크릴 수지(A-1) 100질량부에 대하여, 가교제로서 1,3-비스(N,N-디글리시딜아미노메틸)시클로헥산(「TETRAD-C」미쯔비시가스가가쿠 가부시키가이샤제) 0.5질량부를 첨가하여, 균일해지도록 교반 혼합함으로써 점착제 조성물을 얻었다.1,3-bis (N, N-diglycidylaminomethyl) cyclohexane ("TETRAD-C" Mitsubishi Gas Chemical Co., Ltd.) as a crosslinking agent based on 100 parts by mass of the acrylic resin (A-1) obtained in Synthesis Example 1 0.5 mass part) was added, and the adhesive composition was obtained by stirring and mixing so that it may become uniform.
[실시예 2∼3, 비교예 1][Examples 2-3 and Comparative Example 1]
실시예 1에 있어서, 사용하는 아크릴 수지의 종류를 표 1에 나타내는 바와 같이 변경한 것 이외는, 실시예 1과 같이 하여 점착제 조성물을 얻었다.In Example 1, the adhesive composition was obtained like Example 1 except having changed the kind of acrylic resin to be used as shown in Table 1.
[점착 필름의 제작 방법][Production Method of Adhesive Film]
표면에 이형(離型) 처리된 두께 25㎛의 폴리에틸렌테레프탈레이트 필름(이형 PET25)의 표면에, 건조 후에 있어서의 막두께가 25㎛가 되도록 실시예 및 비교예에서 얻어진 점착제 조성물을 도포하고, 100℃에서 2분간 건조했다. 그 후, 점착제 조성물 도공면 위에 두께 25㎛의 폴리에틸렌테레프탈레이트 필름을 첩합했다. 그 후, 40℃에서 3일간 양생하여, 점착 필름을 얻었다.The adhesive composition obtained in the Example and the comparative example was apply | coated to the surface of the polyethylene terephthalate film (release PET25) of thickness 25 micrometers which carried out the mold release process on the surface so that the film thickness after drying might be 25 micrometers, and 100 It dried at 2 degreeC. Then, the 25-micrometer-thick polyethylene terephthalate film was bonded together on the adhesive composition coating surface. Then, curing was carried out at 40 ° C. for 3 days to obtain an adhesive film.
[접착력의 측정 방법][Measuring method of adhesive force]
상술한 방법으로 얻어진 점착 필름을 종, 횡 25㎜ 폭으로 재단한 것을 시험편으로 했다. 이를 경면(鏡面) 마무리한 스테인리스판에 대하여, 접착 면적이 25㎜×25㎜가 되도록 2㎏ 롤을 2왕복시켜 첩부(貼付)했다. 첩부 1시간 후에 23℃와 100℃의 분위기 하에서 각각 180도 박리 강도를 측정하여, 23℃ 접착력 및 100℃ 접착력으로 했다.What cut | disconnected the adhesion film obtained by the method mentioned above by the length and width of 25 mm was made into the test piece. The 2 kg roll was reciprocated 2 times and adhere | attached so that the adhesion area might become 25 mm x 25 mm with respect to the stainless steel plate which mirrored this. After 1 hour of sticking, 180 degree peeling strength was measured in 23 degreeC and 100 degreeC atmospheres, respectively, and it was set as 23 degreeC adhesive force and 100 degreeC adhesive force.
[유지력의 측정 방법][Measurement of Holding Force]
상술한 방법으로 얻어진 점착 필름을 종, 횡 25㎜ 폭으로 재단한 것을 시험편으로 했다. 이를 경면 마무리한 스테인리스판에 대하여, 접착 면적이 25㎜×25㎜가 되도록 2㎏ 롤을 2왕복시켜 첩부했다. 이 스테인리스판에 첩부한 시험편에 대하여, 1㎏의 하중을 스테인리스판에 대하여 0°의 방향(전단(剪斷) 방향)에 가하고, 분위기 온도 70∼160℃까지 0.6℃／분의 속도로 승온을 행하여, 시험편이 피착체로부터 어긋나 떨어졌을 때의 온도를 측정하여, 유지력(℃)으로 했다.What cut | disconnected the adhesion film obtained by the method mentioned above by the length and width of 25 mm was made into the test piece. The 2 kg roll was reciprocated 2 times and affixed on the mirror-finished stainless steel plate so that an adhesive area might be set to 25 mm x 25 mm. With respect to the test piece affixed to this stainless steel plate, 1 kg of load was applied to the direction (shear direction) of 0 degree with respect to a stainless steel plate, and temperature rising at the speed of 0.6 degree-C / min to atmospheric temperature 70-160 degreeC It carried out, measured the temperature at which the test piece shifted | deviated from the to-be-adhered body, and set it as the holding force (degreeC).
[표 1][Table 1]
※1. 표 1 중에서의 아크릴 수지(A)를 구성하는 각 아크릴 단량체의 단위는 질량％이다.※One. The unit of each acrylic monomer which comprises the acrylic resin (A) in Table 1 is mass%.
※2. 「23℃ 접착력／100℃ 접착력」의 비는, 유효 숫자 2자리 이하를 사사오입한 값을 나타낸다.※2. The ratio of "23 degreeC adhesive force / 100 degreeC adhesive force" shows the value which rounded off two significant figures.
본 발명의 점착제 조성물을 사용하여 얻어진 점착제는, 고온 환경 하에서도 접착력의 저하가 적어, 고온에서도 유지력을 가짐을 알 수 있었다.It was found that the pressure-sensitive adhesive obtained by using the pressure-sensitive adhesive composition of the present invention has a low drop in adhesive force even under a high temperature environment, and has a holding force even at a high temperature.
한편, 비교예 1은, 에스테르기를 2∼6개의 범위에서 갖는 (메타)아크릴 단량체를 사용하지 않은 태양이지만, 고온에서의 접착력의 저하가 현저함을 알 수 있었다.On the other hand, the comparative example 1 is an aspect which does not use the (meth) acryl monomer which has an ester group in the range of 2-6, It turned out that the fall of the adhesive force at high temperature is remarkable.
Claims (5)
Translated fromKorean상기 에스테르기를 2∼6개의 범위에서 갖는 (메타)아크릴 단량체가, 하기 일반식(1)으로 표시되는 (메타)아크릴 단량체 및 하기 일반식(2)으로 표시되는 (메타)아크릴 단량체로 이루어지는 군에서 선택되는 1종 이상인 점착제 조성물.
(식(1) 중, n은 반복 단위수의 평균으로 1∼3의 범위를 나타내고, R1은 수소 원자 또는 메틸기를 나타냄)
(식(2) 중, n은 반복 단위수의 평균으로 1∼2의 범위를 나타내고, R2은 수소 원자 또는 메틸기를 나타냄)The method of claim 1,
In the group which the (meth) acryl monomer which has the said ester group in 2-6 ranges consists of the (meth) acryl monomer represented by following General formula (1), and the (meth) acryl monomer represented by following General formula (2) One or more selected adhesive compositions.
(In formula (1), n represents the range of 1-3 as an average of the number of repeating units, R <1> represents a hydrogen atom or a methyl group.)
(In formula (2), n represents a range of 1 to 2 as an average of the number of repeating units, and R2 represents a hydrogen atom or a methyl group.)
카르복시기를 갖는 (메타)아크릴 단량체(a-2)의 사용량이, (메타)아크릴산알킬에스테르(a-1), 카르복시기를 갖는 (메타)아크릴 단량체(a-2) 및 수산기를 갖는 (메타)아크릴 단량체(a-3)의 합계 100질량부에 대하여, 3∼18질량부의 범위인 점착제 조성물.The method of claim 1,
The usage-amount of the (meth) acryl monomer (a-2) which has a carboxyl group has the (meth) acrylic-acid alkylester (a-1), the (meth) acryl monomer (a-2) which has a carboxyl group, and the (meth) acryl which has a hydroxyl group The adhesive composition which is a range of 3-18 mass parts with respect to a total of 100 mass parts of a monomer (a-3).
상기 (메타)아크릴산과, 상기 에스테르기를 2∼6개의 범위에서 갖는 (메타)아크릴 단량체와의 질량 비율이, 95／5∼50／50의 범위인 점착제 조성물.The method of claim 1,
The adhesive composition whose mass ratio of the said (meth) acrylic acid and the (meth) acryl monomer which has the said ester group in 2-6 ranges is 95/5-50/50.
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| JP2012182306AJP6032472B2 (en) | 2012-08-21 | 2012-08-21 | Adhesive composition and adhesive |
| JPJP-P-2012-182306 | 2012-08-21 |
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| JP (1) | JP6032472B2 (en) |
| KR (1) | KR20140024799A (en) |
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| WO2015156259A1 (en)* | 2014-04-07 | 2015-10-15 | 日本ゼオン株式会社 | Production method for pressure-sensitive adhesive laminated sheet and pressure-sensitive adhesive laminated sheet |
| CN104610897B (en)* | 2015-02-12 | 2016-08-24 | 矽照光电（厦门）有限公司 | A kind of preparation method of the acrylic acid modified epoxy resin for LED encapsulation |
| JP7147559B2 (en) | 2017-03-17 | 2022-10-05 | 三菱ケミカル株式会社 | Adhesive composition, adhesive, adhesive tape, and airtight and waterproof adhesive tape |
| JP7275650B2 (en)* | 2018-03-02 | 2023-05-18 | 三菱ケミカル株式会社 | Adhesive composition for difficult-to-adhere adherends, adhesive for difficult-to-adhere adherends, and adhesive tape for difficult-to-adhere adherends |
| AU2020240898A1 (en) | 2019-03-19 | 2021-10-07 | Mitsubishi Chemical Corporation | Adhesive composition, adhesive, and adhesive tape |
| CN112210325B (en)* | 2019-07-10 | 2023-11-17 | 日东电工（上海松江）有限公司 | Adhesive composition |
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| JP2627719B2 (en)* | 1993-12-07 | 1997-07-09 | 三洋化成工業株式会社 | Pressure sensitive adhesive composition |
| CA2273289A1 (en)* | 1996-11-29 | 1998-06-04 | Takao Yoshikawa | Thermally conductive pressure-sensitive adhesive and adhesive sheet containing the same |
| JP3202627B2 (en)* | 1996-12-27 | 2001-08-27 | 株式会社日本触媒 | Method for producing (meth) acrylic polymer |
| JP3909955B2 (en)* | 1998-06-03 | 2007-04-25 | 日東電工株式会社 | Thermally conductive pressure-sensitive adhesive sheets |
| JP2003238910A (en)* | 2002-01-31 | 2003-08-27 | Three M Innovative Properties Co | Heating releasable thermoset adhesive film |
| JP2007000338A (en)* | 2005-06-23 | 2007-01-11 | Nichiban Co Ltd | Medical adhesive composition |
| JP4140736B2 (en)* | 2006-03-15 | 2008-08-27 | 日東電工株式会社 | Adhesive optical film, laminated optical film, and image display device |
| JP2008127431A (en)* | 2006-11-17 | 2008-06-05 | Toray Fine Chemicals Co Ltd | Pressure-sensitive adhesive composition |
| JP5038224B2 (en)* | 2007-05-08 | 2012-10-03 | 日東電工株式会社 | Adhesive optical film and image display device |
| JP5539630B2 (en)* | 2008-08-04 | 2014-07-02 | 日東電工株式会社 | Double-sided pressure-sensitive adhesive sheet, foam fixing method and laminate |
| WO2012050049A1 (en)* | 2010-10-12 | 2012-04-19 | 日本合成化学工業株式会社 | Adhesive composition for optical components, adhesive for optical components, optical component with adhesive layer, and image display device |
- 2012
- 2012-08-21JPJP2012182306Apatent/JP6032472B2/ennot_activeExpired - Fee Related
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- 2013-06-28KRKR1020130075177Apatent/KR20140024799A/ennot_activeWithdrawn
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| JP6032472B2 (en) | 2016-11-30 |
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