KR980009412A - Acrylic emulsion pressure-sensitive adhesive composition - Google Patents

Acrylic emulsion pressure-sensitive adhesive composition Download PDF

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Publication number
KR980009412A
KR980009412A KR1019960028390A KR19960028390A KR980009412A KR 980009412 A KR980009412 A KR 980009412A KR 1019960028390 A KR1019960028390 A KR 1019960028390A KR 19960028390 A KR19960028390 A KR 19960028390A KR 980009412 A KR980009412 A KR 980009412A
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South Korea
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monomer
sensitive adhesive
acrylic emulsion
emulsion pressure
acrylate
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KR1019960028390A
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Korean (ko)
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KR0165527B1 (en
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오상택
유종선
윤정식
김구니
김욱
최상근
장기영
신수범
전득주
김영묵
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박상욱
한국신발피혁연구소
이창호
명광화학공업 주식회사
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00Adhesives 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
    • C09J133/04Homopolymers or copolymers of esters
    • C09J133/06Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/08Homopolymers or copolymers of acrylic acid esters
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08Macromolecular additives

Abstract

본 발명은 내열특성 및 점착성이 우수하고 고교형분자에 의하여 건조시간의 단축이 가능한 아크릴계 에멀젼 점착제에 관한 것이다.The present invention relates to an acrylic emulsion pressure-sensitive adhesive excellent in heat resistance characteristics and adhesiveness and capable of shortening the drying time by high molecular weight molecules.

본 발명의 아크릴계 에멀젼 점착제는 단량체의 조성을 변화시켜 유리전이온도와 극성을 적절히 변화시키고 가교 가능한 작용기를 갖는 단량체를 사용하고 점착성 부여수지나 액상고무 또는 일반 고체고무를 적절하게 사용하므로서 고도의 점착력과 응집력 및 내열성 등을 발휘하므로서 고도의 점착력과 응집력 및 내열성이 요구되는 분야에 사용될 수 있는 아크릴계 에멀젼 점착제를 제공한다.The acrylic emulsion pressure-sensitive adhesive of the present invention can be produced by changing the composition of a monomer to appropriately change the glass transition temperature and polarity, using a monomer having a crosslinkable functional group, and appropriately using a tacky resin, a liquid rubber or a general solid rubber, And heat resistance, thereby providing an acrylic emulsion pressure-sensitive adhesive which can be used in fields requiring high adhesive force, cohesive force and heat resistance.

Description

아크릴계 에멀젼 점착제 조성물Acrylic emulsion pressure-sensitive adhesive composition

본 발명은 아크릴계 에멀젼 점착제에 대한 것으로서 더욱 상세하게는 내열 특성 및 점착성이 우수하고 고고형분화에 의하여 건조시간의 단축이 가능한 아크릴계 에멀젼 점착제에 관한 것이다.The present invention relates to an acrylic emulsion pressure-sensitive adhesive, and more particularly, to an acrylic emulsion pressure-sensitive adhesive excellent in heat resistance characteristics and adhesiveness and capable of shortening a drying time by high-pressure type differentiation.

지금까지 수분산성 점착제는 점착력이나 내열성 등 성능면에서 유기용제형 점착제에 비하여 저하되므로 점착성이나 내열성이 크게 요구되지 않는 분야에 한정되어 사용되어 왔으나 점착제 산업의 무공해와, 작업청정화에 대한 요구의 증대에 따라 수분산성 점착제에 대한 요구도 증대되고 있는 실정이다.So far, water-dispersible pressure-sensitive adhesives have been used only in fields where adhesiveness and heat resistance are not required so much as they are deteriorated in view of performance such as adhesion and heat resistance, compared with organic solvent-type pressure-sensitive adhesives. However, the demand for cleanliness and cleanliness of the pressure- Accordingly, there is a growing demand for water-dispersible pressure-sensitive adhesives.

따라서 수분산성 점착제는 지금까지 용제형 점착제가 사용되고 있던 고성능, 고기능 점착제 분야로 응용범위를 확장하고 있으나 아직까지 수분산성 점착제가 갖는 내수성, 초기 점착성이 떨어지는 문제, 약한 점착력 등의 문제로 인해 사용량이 한정되고 있으며, 특히 수분산성 아크릴계 에멀젼 점착제를 자동화와 같이 높은 점착력을 요구하면서도 고도의 응집력과 내열성 등 요구물성이 까다로운 분야에 응용하기 위해서는 해결하여야 할 문제가 많은 것으로 알려져 있다.Therefore, the water-dispersible pressure-sensitive adhesive has been applied to the field of high-performance and high-performance pressure-sensitive adhesive, which has been used up to now, but the water-soluble pressure-sensitive adhesive has a problem of low water resistance, poor initial adhesion, In particular, it is known that there are many problems to be solved in order to apply the water-dispersible acrylic emulsion pressure-sensitive adhesive in a field requiring high cohesion and heat resistance while demanding a high adhesive force like automation.

본 출원인은 상기와 같은 사항을 고려하여 고도의 점착력과 응집력 및 내열성이 요구되는 분야에 사용될 수 있는 아크릴계 에멀젼 점착제를 개발하기 위하여 예의 연구 검토한 결과 건조시간이 짧고 낮은 유리전이 온도를 가지면서도 고도의 응집력과 내열성을 발휘하는 아크릴계 에멀젼 점착제를 개발하는 본 발명을 완성하였다.Taking account of the above considerations, the present applicant has conducted intensive research to develop an acrylic emulsion pressure-sensitive adhesive which can be used in fields requiring high adhesion, cohesion and heat resistance. As a result, The present invention has been completed to develop an acrylic emulsion pressure-sensitive adhesive exhibiting cohesive strength and heat resistance.

본 발명의 아크릴계 에멀젼 점착제는 단량체의 조성을 변화시켜 유리전이 온도와 극성을 적절히 변화시키고 점착성 부여수지나 액상고무 또는 일반 고체고무를 적절하게 사용하고 가교 가능한 작용기를 갖는 단량체를 적정량 사용하므로서 고도의 점착력과 응집력 및 내열성 등을 발휘할 수 있다.The acrylic emulsion pressure-sensitive adhesive of the present invention can be produced by changing the composition of a monomer to appropriately change the glass transition temperature and polarity, and appropriately use a monomer having a cross-linkable functional group by appropriately using a tackifier resin, a liquid rubber or a general solid rubber, Cohesion and heat resistance can be exhibited.

이하 본 발명에 대하여 상세히 설명한다.Hereinafter, the present invention will be described in detail.

본 발명에 사용될 수 있는 단량체로서는 불포화 카르본산 알킬 에스테르 단량체로서 메틸아크릴레이트, 메틸메타크리레이트, 에틸아크릴레이트, 에틸메타크릴레이트, 부틸아크릴레이트, 그리시딜메타크릴레이트, 디메틸푸말레이트, 디에틸푸말레이트, 디메틸말레이트, 디메틸이타코네이트, 모노메틸푸말레이트, 모노에틸푸말레이트, 2-에틸헥실아크릴레이트 등이 있다.Examples of the monomers that can be used in the present invention include unsaturated carboxylic acid alkyl ester monomers such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, glycidyl methacrylate, dimethyl fumarate, Dimethyl maleate, dimethyl itaconate, monomethyl fumarate, monoethyl fumarate, 2-ethylhexyl acrylate, and the like.

또한, 알케닐 방향족 단량체로서 스티렌, 알파-메틸스티렌, 비닐톨루엔, 디비닐벤젠 등이 사용될 수 있으며 아크릴로니트릴, 메타크릴로니트릴, 알파-클로로아크릴로니트릴, 알파-에틸아크릴로니트릴 등의 시안화 비닐 단량체가 사용될 수 있다.As the alkenyl aromatic monomer, styrene, alpha-methylstyrene, vinyltoluene, divinylbenzene and the like can be used, and cyanuric acid such as acrylonitrile, methacrylonitrile, alpha-chloroacrylonitrile and alpha-ethyl acrylonitrile Vinyl monomers may be used.

본 발명에서는 분자쇄 중에 카르복실기의 도입을 위하여 전체 단량체 사용량의 1-10% 범위 내에서 에틸렌계 불포화 카르본산 단량체를 사용할 수 있으며 에틸렌계 불포화 카르본산 단량체로서는 아크릴산, 메타크릴산, 크로톤산, 말레인산, 푸말산, 이타콘산 등을 들 수 있다.In the present invention, an ethylenically unsaturated carboxylic acid monomer may be used in an amount of 1-10% of the total amount of monomers used for introduction of a carboxyl group into the molecular chain. Examples of the ethylenically unsaturated carboxylic acid monomer include acrylic acid, methacrylic acid, crotonic acid, Fumaric acid, itaconic acid, and the like.

기타 히드록시 알킬기를 함유하는 단량체로서 2-히드록시에틸아크리레이트, 2-히드록시메틸메타크릴레이트, 히드록시프로필아크릴레이트, 히드록시프로필메타크릴레잇, 히드록시부틸아크릴레이트, 히드록시부틸메타크릴레이트, 3-클로로-2-히드록시프로필메타크릴레이트, 디(에틸렌글리콜)말레이트, 디-(에틸렌글리콜)이타코네이트, 2-히드록시에틸말레이트, 비스(2-히드록시에틸)말레이트, 2-히드록시에틸메틸푸말레씨트 등이 사용될 수 있으며 불포화 카르본산 아미드 단량체로서 아크릴아미드, 메타크릴아믿, N-메틸롤아크릴아미드, N-메틸올메타크릴아미드, N,N-디메틸아크릴아미드 등의 단량체를 사용할 수 있다.As the monomer containing other hydroxyalkyl groups, there may be mentioned 2-hydroxyethyl acrylate, 2-hydroxymethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate (Ethylene glycol) maleate, di- (ethylene glycol) itaconate, 2-hydroxyethyl maleate, bis (2-hydroxyethyl) Maleate, 2-hydroxyethyl methyl fumarate and the like can be used. As the unsaturated carboxylic acid amide monomer, acrylamide, methacrylamide, N-methylol acrylamide, N-methylol methacrylamide, N, Acrylamide and the like can be used.

또한 에폭시기를 함유하는 단량체로서 글리시딜아크릴레이트, 글리시딜메타크릴레이트, 메틸글리시딜아크릴레이트, 알릴글리시딜에테르 등을 사용할 수 있다.As the monomer containing an epoxy group, glycidyl acrylate, glycidyl methacrylate, methyl glycidyl acrylate, allyl glycidyl ether and the like can be used.

중합 반응은 통상의 유화중합 방법에 의하여 유화중합용 개시제로서는 특히 한정된 것은 아니고 일반적인 유화중합용 개시제는 모두 사용될 수 있다.The polymerization reaction is not particularly limited as an initiator for emulsion polymerization by a conventional emulsion polymerization method, and any conventional emulsion polymerization initiator may be used.

유화제 역시 한정되지는 않으며 음이온성 유화제, 비이온성 유화제, 양이온성유화제 및 이들을 병용하는 것도 가능하나 특히 음이온성 유화제와 비이온성 유화제를 병용하는 것이 좋다.The emulsifying agent is not limited, and anionic emulsifying agent, nonionic emulsifying agent, cationic emulsifying agent and a combination thereof can be used, but it is particularly preferable to use anionic emulsifying agent and nonionic emulsifying agent in combination.

이들 유화제는 단량체에 대하여 0.1-20 중량부, 더욱 바람직하기는 3-15중량부가 좋다.These emulsifiers are preferably used in an amount of 0.1 to 20 parts by weight, more preferably 3 to 15 parts by weight, based on the monomers.

본 발명에서는 점착력이나 응집력 등을 개선하기 위하여 액상고무, 고체고무, 라텍스 또는 점착성 부여 수지를 사용할 수 있다.In the present invention, a liquid rubber, a solid rubber, a latex, or a tackifier resin may be used to improve adhesion or cohesion.

본 발명에 의해 제조된 아크릴계 에멀젼 점착제 조성물은 점도가 500-50000 센티포이즈 범위의 라텍스형 점착제로서 철, 스텐레스, 알루미늄 등의 금속 표면에 폴리우레탄 스폰지, EVA 스폰지, 면 또는 가죽 등을 부착하는 점착제로 사용될 수 있을 뿐 아니라 내열성을 요하는 자동차용 점착제로도 사용될 수 있다.The acrylic emulsion pressure-sensitive adhesive composition produced by the present invention is a latex-type pressure-sensitive adhesive having a viscosity in the range of 500 to 50000 centipoise and is a pressure-sensitive adhesive for attaching a polyurethane sponge, EVA sponge, cotton or leather to metal surfaces such as iron, It can be used not only as a pressure sensitive adhesive for automobile but also as a pressure sensitive adhesive for automobile which requires heat resistance.

이하 본 발명을 실시예에 의거 더욱 상세히 설명하나 본 발명이 실시예에 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the Examples.

[실시예 1][Example 1]

교반기, 냉각기, 온도계, 적하깔때기, 질소주입장치가 장치된 6구 분리형 반응기에 표 1에 조성에 따라 먼저 단량체 유화액을 제조한다.A monomer emulsion is first prepared according to the composition shown in Table 1 in a six-necked separable reactor equipped with a stirrer, a condenser, a thermometer, a dropping funnel and a nitrogen injection device.

유화된 액을 4시간에 걸쳐 서서히 반응기에 적하하고 적하가 끝난 후 2시간 동안 숙성 시킨 다음 반응을 종결하여 아크릴계 점착제를 합성한다.The emulsified solution was slowly added dropwise to the reactor over 4 hours, aged for 2 hours after the dropwise addition, and the reaction was terminated to synthesize an acrylic pressure sensitive adhesive.

[실시예 2][Example 2]

상기 실시예 1에서 점착성 부여수지로서 방향족계 탄화수소 수지 대신에 터펜페놀계 수지를 사용하는 것 이외에는 실시예 1과 동일한 방법으로 아크릴계 에멀젼 점착제를 합성한다.An acrylic emulsion pressure-sensitive adhesive was synthesized in the same manner as in Example 1, except that a terpene phenolic resin was used instead of an aromatic hydrocarbon resin as the tackifier resin in Example 1.

[비교예 1][Comparative Example 1]

상기 실시예 1과 합성 방법은 동일하나 메틸메타크릴레이트 2, 부틸아크릴레이트 45, 2-에틸핵실아크릴레이트 52, 아크릴산 0.5, 글리시딜메타크릴레이트 0.5로서 단량체의 조성이 실시예와 다르며 점착성 부여 수지를 사용하지 않고 아크릴계 에멀젼 점착제를 합성한다.Although the same method as in Example 1 was used, the composition of the monomer was different from that of Example, and methyl methacrylate 2, butyl acrylate 45, 2-ethylhexyl acrylate 52, acrylic acid 0.5 and glycidyl methacrylate 0.5 were used. An acrylic emulsion pressure-sensitive adhesive is synthesized without using a resin.

[표 1] 실시예와 비교예에 대한 합성조건[Table 1] Synthetic conditions for Examples and Comparative Examples

(물성측정)(Measurement of physical properties)

(1) 점착력(1) Adhesion

1) 초기 점착력1) Initial adhesion

우레탄 포옴 시트와 스텐레스-304 시트를 손으로 압착하여 합체시킨 다음 1시간 후에 180° 박리강도를 측정.The urethane foam sheet and the Stainless-304 sheet were pressed together by hand and then measured 180 ° peel strength after 1 hour.

2) 말기 점착력2) End-tack

초기 점착력 측정법과 동일한 방법으로 시료를 제조한 후 24시간 후에 초기 점착력 측정법과 동일한 방법으로 180° 박리강도를 측정.The sample was prepared in the same manner as in the initial adhesion measurement, and after 24 hours, the 180 ° peel strength was measured in the same manner as in the initial adhesion measurement.

3) 시험편3) Specimen

① 재질: 우레탄 포옴 시트/스텐레스-304 시트① Material: Urethane foam sheet / Stainless-304 sheet

② 규격: 25㎜×150㎜② Specification: 25 mm × 150 mm

③ 박리속도: 50㎜/min(3) Peeling speed: 50 mm / min

(2) 전단 점착 강도(2) Shear Strength

우레탄 포옴 시트와 이디도장강판을 손으로 압착하여 합체시킨 후 1시간 뒤에 전단 점착강도를 측정하였으며 전단면의 면적은 25㎜×25㎜이다.The urethane foam sheet and the EDI coated steel sheet were pressed together by hand, and after 1 hour, the shear adhesive strength was measured. The cross section area was 25 mm × 25 mm.

(3) 내열성(3) Heat resistance

지름 42㎜의 스텐레스-304 파이프에 50×100㎟의 우레탄 포옴 시트를 감아서 실온에서 1시간 동안 방치시킨 후 100℃ 오븐에 투입, 1시간을 유지하여 떨어진 거리를 측정(좌·우 평균값).A 50 × 100 mm urethane foam sheet was wound on a stainless steel-304 pipe having a diameter of 42 mm and allowed to stand at room temperature for 1 hour, then put into an oven at 100 ° C. and maintained for 1 hour to measure a distance (left and right average value).

(4) 내열 크리프성(4) Heat-resistant creep property

50×150㎟의 우레탄 포옴 시트와 이디도장강판을 손으로 압착하여 24시간 실온에서 방치한 후 하중을 가하지 않은 상태로 100℃ 오븐에서 다시 1시간 동안 가열하고 105g의 하중을 걸어 1시간 동안에 우레탄 포옴시트와 이디도장강판이 박리된 거리를 측정.50 x 150 mm2 urethane foam sheet and epoxy coated steel sheet were pressed by hand and allowed to stand at room temperature for 24 hours, then heated in an oven at 100 캜 for 1 hour without applying a load, and a load of 105 g was applied to the urethane foam Measure the distance of peeling of sheet and edged steel plate.

[표 1] 실시예와 비교예에 대한 물성 비교[Table 1] Comparison of physical properties for Examples and Comparative Examples

이상과 같은 본 발명의 아크릴계 에멀젼 점착제는 단량체의 조성을 변화시켜 유리전이온도와 극성을 적절히 변화시키고 가교 가능한 작용기를 갖는 단량체를 사용하고 점착성 부여수지나 액상고무 또는 일반 고체고무를 적절하게 사용하므로서 고도의 점착력과 응집력 및 내열성 등을 발휘하므로서 고도의 점착력과 응집력 및 내열성이 요구되는 분야에 사용될 수 있는 유용한 것이다.The acrylic emulsion pressure-sensitive adhesive of the present invention as described above can be obtained by changing the composition of a monomer to appropriately change the glass transition temperature and polarity, using a monomer having a crosslinkable functional group, and appropriately using a tackifier resin, a liquid rubber or a general solid rubber, Cohesive force, heat resistance, and the like, which is useful for applications requiring high cohesion, cohesion and heat resistance.

Claims (3)

아크릴계 에멀젼 점착제에 있어서 점착성 단량체를 단독 혹은 혼합하여 50-90%, 응집성 단량체를 단독 혹은 혼합하여 5-40%, 가교를 위한 반응성 단량체로서 카르복실 그룹을 갖는 단량체를 1-10%, 에폭시 그룹을 갖는 단량체를 0.5-10%, 수산기와 아미드기를 갖는 단량체를 0.1-5% 사용하는 것을 특징으로 하는 아크릴계 에멀젼 점착제 조성물.In the acrylic emulsion pressure-sensitive adhesive, 50 to 90% of the viscous monomer is used alone or as a mixture thereof, 5-40% by weight of the cohesive monomer alone or as a mixture, 1-10% of the monomer having a carboxyl group as a reactive monomer for crosslinking, And 0.5 to 10% of a monomer having a hydroxyl group and 0.1 to 5% of a monomer having an amide group are used. 제1항에 있어서, 중합시에 액상고무, 고체고무, 라텍스, 점착성 부여수지를 단량체 100에 대하여 1-20부 사용하는 것을 특징으로 하는 아크릴계 에멀젼 점착제 조성물.The acrylic emulsion pressure-sensitive adhesive composition according to claim 1, wherein 1-20 parts of a liquid rubber, a solid rubber, a latex, and a tackifier resin are used for 100 monomers during polymerization. 제1항에 있어서, 점착성 단량체는 2-에틸헥실아크릴레이트나 부틸아크릴레이트 또는 에틸아크릴레이트 등이고, 응집성 단량체는 아크릴로니트릴이나 메틸메타크릴레이트 또는 스티렌 또는 비닐아세테이트 등이며, 반응성 단량체로서는 아크릴산이나 메타크릴산 또는 크로톤산 또는 이타콘산 또는 푸말산또는 말레인산 등이며, 에폭시 그룹을 갖는 단량체로서는 글리시딜아크릴레이트 또는 글리시딜메타크릴레이트 또는 메틸글리시딜아크릴레이트 또는 알릴글리시딜에테르 등이며, 수산기와 아미드기를 갖는 단량체는 N-메틸올 아크릴아미드 또는 N-부틸올아크릴아미드인 것을 특징으로 하는 아크릴계 에멀젼 점착제 조성물.[3] The method according to claim 1, wherein the viscous monomer is 2-ethylhexyl acrylate, butyl acrylate or ethyl acrylate, the cohesive monomer is acrylonitrile, methyl methacrylate, styrene or vinyl acetate, And the like. Examples of the monomer having an epoxy group include glycidyl acrylate or glycidyl methacrylate or methyl glycidyl acrylate or allyl glycidyl ether and the like, Wherein the monomer having a hydroxyl group and an amide group is N-methylol acrylamide or N-butylol acrylamide. ※ 참고사항 : 최초출원 내용에 의하여 공개하는 것임.※ Note: It is disclosed by the contents of the first application.
KR1019960028390A 1996-07-09 1996-07-09 Acryl-emulsion adhesvie composition KR0165527B1 (en)

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KR20210062810A (en) * 2019-11-22 2021-06-01 주식회사 라온티알엠 Adhesive composition with excellent heat-resistance and preparation method thereof

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