KR100427407B1 - Removable pressure sensitive adhesive based on an acrylic emulsion - Google Patents
Removable pressure sensitive adhesive based on an acrylic emulsion Download PDFInfo
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- KR100427407B1 KR100427407B1 KR10-2001-0077861A KR20010077861A KR100427407B1 KR 100427407 B1 KR100427407 B1 KR 100427407B1 KR 20010077861 A KR20010077861 A KR 20010077861A KR 100427407 B1 KR100427407 B1 KR 100427407B1
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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
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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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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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
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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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/40—Adhesives in the form of films or foils characterised by release liners
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- Organic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Adhesive Tapes (AREA)
Abstract
본 발명은 재박리성이 우수한 아크릴 에멀젼 점착제에 관한 것으로서, 더욱 상세하게는 점착성 단량체 50 ∼ 95 중량%와 응집성 단량체 4 ∼ 42 중량%를 주성분으로 사용하고, 가교 가능한 작용기를 갖는 단량체로 카르복실기를 갖는 단량체 0.9 ∼ 5 중량%, 수산기와 아미드기를 함께 갖는 단량체 0.1 ∼ 3 중량% 내에서 병용하고, 음이온성 유화제와 비이온성 유화제를 혼합하여 전체 단량체 100 중량부에 대하여 전체 유화제의 함량 1.5 ∼ 4 중량부(고형분 기준)로 유화중합하여 제조된 재박리성이 우수한 아크릴 에멀젼 점착제에 관한 것이다.The present invention relates to an acrylic emulsion pressure-sensitive adhesive excellent in re-peelability, and more particularly, 50 to 95% by weight of the adhesive monomer and 4 to 42% by weight of the cohesive monomer as a main component, having a carboxyl group as a monomer having a crosslinkable functional group 0.9-5% by weight of monomer, 0.1-3% by weight of monomer having hydroxyl group and amide group together, mixed with anionic emulsifier and nonionic emulsifier, and total content of emulsifier 1.5-4 parts by weight based on 100 parts by weight of total monomer The present invention relates to an acrylic emulsion pressure sensitive adhesive having excellent re-peelability prepared by emulsion polymerization on a solid content basis.
Description
본 발명은 재박리성이 우수한 아크릴 에멀젼 점착제에 관한 것으로서, 더욱 상세하게는 점착성 단량체 50 ∼ 95 중량%와 응집성 단량체 4 ∼ 42 중량%를 주성분으로 사용하고, 가교 가능한 작용기를 갖는 단량체로 카르복실기를 갖는 단량체 0.9 ∼ 5 중량%, 수산기와 아미드기를 함께 갖는 단량체 0.1 ∼ 3 중량% 내에서 병용하고, 음이온성 유화제와 비이온성 유화제를 혼합하여 전체 단량체 100 중량부에 대하여 전체 유화제의 함량 1.5 ∼ 4 중량부(고형분 기준)로 유화중합하여 제조된 재박리성이 우수한 아크릴 에멀젼 점착제에 관한 것이다.The present invention relates to an acrylic emulsion pressure-sensitive adhesive excellent in re-peelability, and more particularly, 50 to 95% by weight of the adhesive monomer and 4 to 42% by weight of the cohesive monomer as a main component, having a carboxyl group as a monomer having a crosslinkable functional group 0.9-5% by weight of monomer, 0.1-3% by weight of monomer having hydroxyl group and amide group together, mixed with anionic emulsifier and nonionic emulsifier, and total content of emulsifier 1.5-4 parts by weight based on 100 parts by weight of total monomer The present invention relates to an acrylic emulsion pressure sensitive adhesive having excellent re-peelability prepared by emulsion polymerization on a solid content basis.
재박리성 점착제가 사용되는 분야로는 특수 라벨지나 테이프, 표면 보호용 점착 시트 및 마스킹용 점착 테이프 등이 있으며 박리 후 잔류물이 피착재에 존재하지 않는 특성을 필요로 한다.Re-peelable adhesives are used in special labels, tapes, adhesive sheets for surface protection, and adhesive tapes for masking, and require a property that residues do not exist on the adherend after peeling.
일반적으로 스텐레스판, 알루미늄판 등의 금속판 및 도장금속판, ABS판, 아크릴판, 유리판 등의 비금속 물체표면을 일시적으로 보호하기 위한 표면 보호재에재박리형 점착제가 가장 많이 사용되고 있으며 대체로 용제형 아크릴 또는 고무계 점착제가 사용되고 있다.In general, re-peelable adhesives are most commonly used for surface protection materials to temporarily protect non-metallic objects such as stainless plates and aluminum plates, and non-metallic objects such as painted metal plates, ABS plates, acrylic plates, and glass plates. An adhesive is used.
그러나, 고무계 점착제는 자외선에 의한 노화에 의하여 점착력이 감소하고 점착제가 피착재에 일부 잔류하는 문제점을 나타내며, 또한 아크릴계 점착제의 경우는 점착제층이 지지체에 대하여 젖음성이 서서히 증가되어 시간이 경과함에 따라 점착력이 증가하게 되는 등의 점착 특성의 경시 변화가 커 재박리성이 저하하는 문제가 있다. 여기에 더하여 환경친화형 점착제의 요구가 증대되고 있으나, 기존의 아크릴 에멀젼 점착제는 유화제 등의 영향으로 인해 만족할만한 재박리 특성을 나타내지 못하고 있다.However, the rubber-based adhesive shows a problem in that the adhesive strength decreases due to aging due to ultraviolet rays and the adhesive remains partially in the adherend, and in the case of the acrylic adhesive, the adhesive layer gradually increases the wettability with respect to the support, and thus the adhesive strength with time. There exists a problem that re-peelability falls large with time-dependent change of adhesive characteristics, such as this increasing. In addition to this, there is an increasing demand for environment-friendly pressure-sensitive adhesives, but the existing acrylic emulsion pressure-sensitive adhesives do not exhibit satisfactory re-peeling characteristics due to the influence of an emulsifier.
이에, 본 발명자들은 이러한 문제점을 해결하기 위하여 연구한 결과, 점착성 및 응집성 아크릴 단량체를 92 ∼ 99 중량%로 사용하여 점착제의 고유 물성을 갖게 하고 여기에 재박리성을 위해 카르복실기를 갖는 단량체와 수산기와 아미드기를 함께 갖는 단량체를 1 ∼ 8 중량% 범위내에서 병용한 접착제 조성물을 음이온성 유화제와 비이온성 유화제를 혼합하여 전체 단량체 조성물 100 중량부에 대하여 전체 유화제의 함량을 1.5 ∼ 4 중량부(고형분 기준)로 사용하여 유화중합하여 점착성과 점착력 및 응집력 등의 점착제 고유 물성을 유지하면서 재박리성이 우수한 아크릴 에멀젼 점착제를 개발함으로써 본 발명을 완성하게 되었다.Accordingly, the present inventors have studied to solve this problem, and as a result of using 92 to 99% by weight of the adhesive and cohesive acrylic monomer to give the inherent physical properties of the adhesive and the monomer and hydroxyl group having a carboxyl group for re-peelability The anionic emulsifier and the nonionic emulsifier were mixed in an adhesive composition using a monomer having an amide group within the range of 1 to 8% by weight, and the total emulsifier content was 1.5 to 4 parts by weight based on 100 parts by weight of the total monomer composition (based on solid content). The present invention was completed by developing an acrylic emulsion pressure-sensitive adhesive having excellent re-peelability while maintaining emulsion-specific properties such as adhesiveness, cohesion and cohesion by using emulsion polymerization.
따라서, 본 발명은 재박리성이 우수한 아크릴 에멀젼 점착제를 제공하는데그 목적이 있다.Therefore, an object of the present invention is to provide an acrylic emulsion pressure-sensitive adhesive excellent in re-peelability.
본 발명은 아크릴 에멀젼 점착제 조성물에 있어서, 점착성 단량체 50 ∼ 95 중량%, 응집성 단량체 4 ∼ 42 중량%, 가교 가능한 작용기를 갖는 단량체 1 ∼ 8 중량%로 이루어진 아크릴 에멀젼 점착제 조성물에 전체 단량체 조성물 100 중량부에 대하여유화제 1.5 ∼ 4 중량부(고형분 기준)를 유화중합하여 제조한 아크릴 에멀젼 점착제를 그 특징으로 한다.In the acrylic emulsion pressure-sensitive adhesive composition, 100 parts by weight of the total monomer composition in the acrylic emulsion pressure-sensitive adhesive composition consisting of 50 to 95% by weight of the adhesive monomer, 4 to 42% by weight of the cohesive monomer, and 1 to 8% by weight of the monomer having a crosslinkable functional group. It is characterized by an acrylic emulsion pressure-sensitive adhesive prepared by emulsion polymerization of 1.5 to 4 parts by weight (based on solids) of an emulsifier.
이와 같은 본 발명을 상세히 설명하면 다음과 같다.The present invention will be described in detail as follows.
본 발명에 사용된 아크릴 단량체는 유리전이 온도 -25 ℃ 이하의 점착성 단량체와 -25 ℃ 이상의 응집성 단량체를 혼합하여 사용한다. 점착성 단량체는 50 ∼ 95 중량부로 사용하는데, 50 중량부 미만일 경우 점착성이 저하되어 점착제로서의 물성을 나타내지 못하며, 95 중량부를 초과하면 점착제의 흐름성이 너무 커서 시간이 경과함에 따라 점착면적이 넓어지고 재박리성이 저하된다. 본 발명에 사용할 수 있는 점착성 단량체로는 유리전이온도가 -130 ∼ -25 ℃인 불포화카르본산에스테르로서, 예를 들어 프로필아크릴레이트, 부틸아크릴레이트, 2-에틸부틸아크릴레이트, 헥실아크릴레이트, 헵틸아크릴레이트, 옥틸아크릴레이트, n-펜틸아크릴레이트, 2-에틸헥실아크릴레이트 등이 있다.The acrylic monomer used in the present invention is used by mixing a cohesive monomer having a glass transition temperature of -25 ℃ or less and a cohesive monomer of -25 ℃ or more. The adhesive monomer is used in an amount of 50 to 95 parts by weight, but when it is less than 50 parts by weight, the adhesiveness is lowered and thus the physical properties of the adhesive are not exhibited. When the adhesive monomer is more than 95 parts by weight, the adhesive area becomes too large and the adhesive area becomes wider as time passes. Peelability falls. Examples of the viscous monomer that can be used in the present invention include unsaturated carboxylic acid esters having a glass transition temperature of -130 to -25 ° C. For example, propyl acrylate, butyl acrylate, 2-ethylbutyl acrylate, hexyl acrylate, heptyl Acrylate, octyl acrylate, n-pentyl acrylate, 2-ethylhexyl acrylate and the like.
또한, 응집성 단량체는 4 ∼ 42 중량부로 사용하는데, 4 중량부 미만일 경우 응집력이 낮아 크리프성이 감소하고 재박리성이 저하되며, 42 중량부 초과로 사용되면 Tg가 너무 높아 점착성이 저하되어 점착제로서의 물성을 나타내지 못한다. 본 발명에 사용할 수 있는 응집성 단량체로는 유리전이온도가 -25 ∼ 130 ℃인 불포화카르본산 에스테르로서, 예를 들어 메틸아크릴레이트, 메틸메타크릴레이트, 에틸아크릴레이트, 에틸메타크릴레이트, 프로필메타크릴레이트, 부틸메타크릴레이트, 이소부틸아크릴레이트, 이소부틸메타크릴레이트, 헥실메타크릴레이트, 펜틸메타크릴레이트, 옥틸메타크릴레이트 등이 있다.In addition, the cohesive monomer is used at 4 to 42 parts by weight, but less than 4 parts by weight, the cohesive force is low, so creep property is reduced and re-peelability is reduced. It does not exhibit physical properties. Cohesive monomers that can be used in the present invention are unsaturated carboxylic acid esters having a glass transition temperature of -25 to 130 ° C. For example, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, and propyl methacryl. And butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, hexyl methacrylate, pentyl methacrylate, octyl methacrylate and the like.
본 발명의 재박리성이 우수한 아크릴 에멀젼 점착제는 상기 점착성 및 응집성 아크릴 단량체를 주성분으로 하면서 재박리성을 부여하기 위하여 가교 가능한 작용기를 갖는 단량체를 1 ∼ 8 중량부로 유화중합한다.The acrylic emulsion pressure sensitive adhesive excellent in the re-peelability of this invention emulsifies-polymerizes 1-8 weight part of monomers which have a crosslinkable functional group in order to provide re-peelability with the said adhesive and cohesive acrylic monomer as a main component.
상기 가교 가능한 작용기를 갖는 단량체 1 ∼ 8 중량부는 카르복실기를 갖는 단량체 0.9 ∼ 5 중량부, 수산기 또는 아미드기를 갖는 단량체 0.1 ∼ 3 중량부 범위내에서 병용하여 사용하고, 카르복실기를 갖는 단량체가 0.9 중량부 미만일 경우 응집력이 낮아 재박리성이 저하되고, 5 중량부를 초과하면 기재에 대한 접착성이 증가되고 시간이 경과함에 따라 점착력이 증가되어 재박리성이 저하하게 된다. 본 발명에서 사용되는 카르복실기를 갖는 단량체로는 디 또는 모노 불포화카르본산 단량체를 사용하는데, 예를 들면 아크릴산, 메타크릴산, 크로톤산, 말레인산, 푸말산, 이타콘산 등을 사용할 수 있다. 또한, 수산기와 아미드기를 함께 갖는 단량체가 0.1 중량부 미만으로 사용될 경우 응집력이 낮아 요구되는 내열 크리프성과 재박리성을 얻을 수가 없고, 3 중량부 초과하면 지나친 가교로 인해 에멀젼의 안정성이 저하되고 점착성이 크게 저하되어 용도에 적합한 점착물성을 나타내지 못한다. 수산기와 아미드기를 함께 갖는 단량체로는 히드록시알킬(메타)아크릴아미드를 사용하는데, 예를 들면 N-메틸롤아크릴아미드, N-메틸롤메타크릴아미드, N-에틸롤아크릴아미드, N-부틸롤아크릴아미드 등을 사용할 수 있다. 수산기와 아미드기를 함께 갖는 단량체에 병용할 수 있는 가교성 단량체로 2-히드록시에틸아크릴레이트, 2-히드록시에틸메타크릴레이트, 2-히드록시메틸메타크릴레이트, 히드록시프로필아크릴레이트, 히드록시프로필메타크릴레이트, 히드록시부틸아크릴레이트, 히드록시부틸메타크릴레이트, 2-히드록시에틸말레이트 등을 사용할 수 있고, 아미드기를 갖는 단량체로 아크릴아미드, 메타크릴아미드, 부틸아크릴아미드, 디메틸아미노메타크릴레이트, 이소헥실아크릴아미드, N,N-디메틸아크릴아미드, 부틸메타크릴아미드 등을 사용할 수 있다. 또한, 상기 수산기와 아미드기를 함께 갖는 단량체 이외에 에폭시기를 갖는 단량체를 사용할 수 있는데, 예를 들어 글리시딜아크릴레이트, 글리시딜메타크릴레이트, 메틸글리시딜아크릴레이트, 알릴글리시딜에테르 등을 들 수 있다.1 to 8 parts by weight of the monomer having a crosslinkable functional group are used in combination within the range of 0.9 to 5 parts by weight of the monomer having a carboxyl group, and 0.1 to 3 parts by weight of the monomer having a hydroxyl group or an amide group, and the monomer having a carboxyl group is less than 0.9 parts by weight. In this case, the cohesion force is low, so the re-peelability is lowered. When it exceeds 5 parts by weight, the adhesion to the substrate is increased, and the adhesive force increases as time passes, thereby reducing the re-peelability. As the monomer having a carboxyl group used in the present invention, di or mono unsaturated carboxylic acid monomers are used, for example acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, and the like. In addition, when the monomer having both a hydroxyl group and an amide group is used in less than 0.1 parts by weight, the cohesive force is low and the required heat creep resistance and re-peelability cannot be obtained. If the content exceeds 3 parts by weight, the emulsion stability is deteriorated due to excessive crosslinking and adhesiveness It is greatly deteriorated and does not exhibit adhesive properties suitable for the application. Hydroxyalkyl (meth) acrylamide is used as a monomer which has a hydroxyl group and an amide group, For example, N-methylol acrylamide, N-methylol methacrylamide, N-ethylol acrylamide, N-butylol Acrylamide and the like can be used. As a crosslinkable monomer which can be used together with a monomer having a hydroxyl group and an amide group, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxymethyl methacrylate, hydroxypropyl acrylate, and hydroxy Propyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, 2-hydroxyethyl maleate and the like can be used.A monomer having an amide group may be acrylamide, methacrylamide, butylacrylamide, dimethylaminometha. Acrylate, isohexyl acrylamide, N, N-dimethyl acrylamide, butyl methacrylamide and the like can be used. In addition, monomers having an epoxy group may be used in addition to the monomer having both hydroxyl and amide groups. For example, glycidyl acrylate, glycidyl methacrylate, methylglycidyl acrylate, allyl glycidyl ether, and the like. Can be mentioned.
이상으로 구성된 단량체 조성물은 음이온성 유화제와 비이온성 유화제를 병용하여 일반적인 유화중합 공정으로 중합하는데, 이때 고형분 기준으로 음이온성 유화제 0.5 ∼ 1 중량부와 비이온성 유화제 0.5 ∼ 3 중량부를 병용하여 전체 유화제의 함량이 1.5 ∼ 4 중량부이 되도록 사용한다. 사용된 전체 유화제의 함량이 1.5 중량부 미만일 경우 에멀젼의 안정성이 저하되며 4 중량부 초과할 경우 유화제의 함량이 많아져 재박리성이 저하된다.The monomer composition composed of the above-mentioned anionic emulsifier and nonionic emulsifier are polymerized in a general emulsion polymerization process, and in this case, 0.5 to 1 parts by weight of anionic emulsifier and 0.5 to 3 parts by weight of nonionic emulsifier are used together on the basis of solids. The content is used to 1.5 to 4 parts by weight. If the total amount of the emulsifier used is less than 1.5 parts by weight, the stability of the emulsion is lowered. If it exceeds 4 parts by weight, the content of the emulsifier is increased, thereby reducing re-peelability.
본 발명에 사용되는 음이온성 유화제로는 특별히 한정되지는 않으나, 폴리옥시에틸렌 노닐페닐 에테르황산암모늄, 도데실벤젠술폰산소다, 라우릴황산나트륨 등을 사용할 수 있으며, 비이온성 유화제로는 HLB 값이 10 ∼ 19의 범위인 폴리옥시에틸렌 알킬페닐 에테르나 폴리옥시에틸렌 알킬 에테르, 폴리옥시에틸렌 소비탄 지방산 에스테르, 폴리옥시에틸렌 지방산 에스테르 등을 사용하는 것이 가능하다.The anionic emulsifier used in the present invention is not particularly limited, but polyoxyethylene nonylphenyl ether ammonium sulfate, sodium dodecylbenzenesulfonate, sodium lauryl sulfate and the like can be used. It is possible to use polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl ethers, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene fatty acid esters and the like in the range of 19.
본 발명에 사용된 개시제는 특별하게 한정되지 않으며, 일반적인 유화중합 개시제인 과황산암모늄, 과황산칼륨, 과황산나트륨, 술포키실산염, t-부틸히드로퍼옥사이드 등을 사용할 수 있다.The initiator used in the present invention is not particularly limited, and general emulsion polymerization initiators such as ammonium persulfate, potassium persulfate, sodium persulfate, sulfoxylate, t-butylhydroperoxide and the like can be used.
이와 같은 조성물로 유화중합에 의해 제조된 아크릴 에멀젼 점착제는 점도 1000 ∼ 20000 센티포이즈의 일반적인 점착물성이 우수하면서, 특히 내열 크리프성과 재박리성이 매우 우수하다.The acrylic emulsion pressure-sensitive adhesive prepared by emulsion polymerization with such a composition is excellent in general adhesiveness of viscosity 1000 to 20000 centipoise, and particularly excellent in heat creep resistance and re-peelability.
또한, 본 발명에 의해 제조된 아크릴 에멀젼 점착제에 이소시아네이트계 경화제를 혼합하면 물성향상의 효과를 얻을 수 있다.In addition, when the isocyanate-based curing agent is mixed with the acrylic emulsion pressure-sensitive adhesive prepared by the present invention, the effect of improving physical properties can be obtained.
이하, 본 발명을 실시예에 의거하여 상세히 설명하겠는바, 본 발명이 이에 한정되는 것은 아니다.Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited thereto.
제조예Production Example
혼합용기에 증류수 50 중량부를 넣고 음이온성 유화제와 비이온성 유화제를 혼합하여 넣은 후 600 rpm의 교반속도로 10분간 교반하고 여기에 단량체 조성물 100 중량부를 30분간 서서히 낙하 투입하여 단량체 유화액을 제조하였다. 이와다른 가열 장치가 있는 반응기에 환류 냉각기와 교반기, 온도계, 질소 주입 장치를 설치한 후 증류수 15 중량부와 음이온성 유화제 0.1 중량부를 넣고 80 ℃로 승온하여 70 rpm의 교반속도로 교반하였다. 이 반응기에 상기의 유화액 중 5%를 첨가하고 10분간 교반하고 여기에 증류수 5 중량부에 과황산암모늄 0.5 중량부를 녹인 용액의 5%를 첨가하여 중합을 개시하였다. 중합의 개시가 확인된 후 나머지 유화액과 개시제 용액을 3시간 동안 분할 투입하였다. 유화액의 투입이 종료된 후 85 ℃로 승온하고 증류수 1 중량부에 t-부틸히드로퍼옥사이드 0.1 중량부를 녹여 반응기에 투입하고 약 2시간 동안 숙성 중합하여 아크릴 에멀젼을 제조하였다.50 parts by weight of distilled water was added to the mixed container, anionic emulsifier and nonionic emulsifier were mixed and then stirred at a stirring speed of 600 rpm for 10 minutes, and 100 parts by weight of the monomer composition was slowly dropped into the mixture for 30 minutes to prepare a monomer emulsion. After installing a reflux condenser, a stirrer, a thermometer, and a nitrogen injector in a reactor having another heating device, 15 parts by weight of distilled water and 0.1 parts by weight of anionic emulsifier were added thereto, and the temperature was raised to 80 ° C., followed by stirring at a stirring speed of 70 rpm. 5% of the above emulsion was added to the reactor, stirred for 10 minutes, and 5% of a solution in which 0.5 parts by weight of ammonium persulfate was added to 5 parts by weight of distilled water was added to initiate polymerization. After the start of the polymerization was confirmed, the remaining emulsion and the initiator solution was added in 3 hours. After the addition of the emulsion was finished, the temperature was raised to 85 ℃, dissolved 0.1 part by weight of t- butyl hydroperoxide in 1 part by weight of distilled water was added to the reactor and aged for about 2 hours to prepare an acrylic emulsion.
실시예 1Example 1
부틸아크릴레이트 35 중량%, 2-에틸헥실아크릴레이트 35 중량%, 에틸아크릴레이트 10 중량%, 부틸메타크릴레이트 15 중량% 및 아크릴산 3 중량%와 N-메틸롤 아크릴아미드(50%) 4 중량%의 단량체 조성물과 전체 단량체 100 중량부에 대하여 음이온성 유화제 폴리옥시에틸렌 노닐페닐 에테르황산암모늄(30%) 2.7 중량부, 비이온성 유화제로 HLB값이 16인 폴리옥시에틸렌 노닐페닐 에테르 3 중량부를 상기 제조예와 같은 중합공정으로 재박리성이 우수한 아크릴 에멀젼 점착제를 제조하였다.35% by weight butyl acrylate, 35% by weight 2-ethylhexyl acrylate, 10% by weight ethyl acrylate, 15% by weight butyl methacrylate and 3% by weight acrylic acid and 4% by weight N-methylol acrylamide (50%) 2.7 parts by weight of anionic emulsifier polyoxyethylene nonylphenyl ether ammonium sulfate (30%), and 3 parts by weight of polyoxyethylene nonylphenyl ether having a HLB value of 16 as a nonionic emulsifier An acrylic emulsion pressure sensitive adhesive having excellent re-peelability was prepared by the polymerization process as in Example.
실시예 2Example 2
부틸아크릴레이트 50 중량%, 2-에틸헥실아크릴레이트 40 중량%, 메틸메타크릴레이트 5 중량% 및 아크릴산 3.5 중량%와 N-메틸롤아크릴아미드(50%) 1 중량%, 글리시딜메타크릴레이트 1 중량%의 단량체 조성물과 전체 단량체 100 중량부에 대하여 음이온성 유화제 폴리옥시에틸렌 노닐페닐 에테르황산암모늄(30%) 2.7 중량부, 비이온성 유화제로 HLB값이 16인 폴리옥시에틸렌 노닐페닐 에테르 3 중량부를 상기 제조예와 같은 중합공정으로 재박리성이 우수한 아크릴 에멀젼 점착제를 제조하였다.50% by weight of butyl acrylate, 40% by weight of 2-ethylhexyl acrylate, 5% by weight of methyl methacrylate and 3.5% by weight of acrylic acid and 1% by weight of N-methylolacrylamide (50%), glycidyl methacrylate 2.7 parts by weight of anionic emulsifier polyoxyethylene nonylphenyl ether ammonium sulfate (30%) based on 1% by weight of monomer composition and 100 parts by weight of total monomer, 3 weights of polyoxyethylene nonylphenyl ether having an HLB value of 16 as a nonionic emulsifier The part was prepared in the same polymerization process as in Preparation Example, to prepare an acrylic emulsion adhesive having excellent re-peelability.
실시예 3Example 3
부틸아크릴레이트 70 중량%, 2-에틸헥실아크릴레이트 10 중량%, 에틸아크릴레이트 10 중량%, 부틸메타크릴레이트 5 중량% 및 아크릴산 3 중량%와 N-메틸롤아크릴아미드(50%) 2 중량%, 2-히드록시에틸메타크릴레이트 1 중량%의 단량체 조성물과 전체 단량체 100 중량부에 대하여 음이온성 유화제 도데실벤젠술폰산소다(50%) 2 중량부, 비이온성 유화제로 HLB값이 16인 폴리옥시에틸렌 노닐페닐 에테르 2 중량부를 상기 제조예와 같은 중합공정으로 재박리성이 우수한 아크릴 에멀젼 점착제를 제조하였다.70% by weight butyl acrylate, 10% by weight 2-ethylhexyl acrylate, 10% by weight ethyl acrylate, 5% by weight butyl methacrylate and 3% by weight acrylic acid and 2% by weight N-methylol acrylamide (50%) , 2 parts by weight of anionic emulsifier dodecylbenzenesulfonate (50%) based on 1% by weight of 2-hydroxyethyl methacrylate monomer composition and 100 parts by weight of total monomer, polyoxy having an HLB value of 16 as a nonionic emulsifier 2 parts by weight of ethylene nonylphenyl ether was prepared in an acrylic emulsion pressure-sensitive adhesive having excellent re-peelability in the same polymerization process as in Preparation Example.
실시예 4Example 4
부틸아크릴레이트 20 중량%, 2-에틸헥실아크릴레이트 60 중량%, 에틸아크릴레이트 15 중량% 및 메타크릴산 2.5 중량%와 N-메틸롤아크릴아미드(50%) 1 중량%, 글리시딜메타크릴레이트 1 중량%, 2-히드록시에틸메타크릴레이트 1 중량%의 단량체조성물과 전체 단량체 100 중량부에 대하여 음이온성 유화제 도데실벤젠술폰산소다(50%) 2 중량부, 비이온성 유화제로 HLB값이 16인 폴리옥시에틸렌 노닐페닐 에테르 2 중량부를 상기 제조예와 같은 중합공정으로 재박리성이 우수한 아크릴 에멀젼 점착제를 제조하였다.20% by weight butyl acrylate, 60% by weight 2-ethylhexyl acrylate, 15% by weight ethyl acrylate and 2.5% by weight methacrylic acid and 1% by weight of N-methylolacrylamide (50%), glycidyl methacryl 2 parts by weight of anionic emulsifier dodecylbenzenesulfonic acid sodium sulfate (50%) relative to a monomer composition of 1% by weight, 1% by weight of 2-hydroxyethyl methacrylate and 100 parts by weight of the total monomers, and a HB value as a nonionic emulsifier. 2 parts by weight of polyoxyethylene nonylphenyl ether of 16 was prepared in an acrylic emulsion pressure-sensitive adhesive having excellent re-peelability in the same polymerization process as in Preparation Example.
비교예 1Comparative Example 1
부틸아크릴레이트 35 중량%, 2-에틸헥실아크릴레이트 35 중량%, 에틸아크릴레이트 10 중량%, 메틸메타크릴레이트 10 중량%, 부틸메타크릴레이트 10 중량%의 단량체 조성물과 전체 단량체 100 중량부에 대하여 음이온성 유화제 폴리옥시에틸렌 노닐페닐 에테르황산암모늄(30%) 2.7 중량부, 비이온성 유화제로 HLB값이 16인 폴리옥시에틸렌 노닐페닐 에테르 3 중량부를 상기 제조예와 같은 중합공정으로 아크릴 에멀젼 점착제를 제조하였다.Based on the monomer composition of 35% by weight of butyl acrylate, 35% by weight of 2-ethylhexyl acrylate, 10% by weight of ethyl acrylate, 10% by weight of methyl methacrylate, 10% by weight of butyl methacrylate and 100 parts by weight of the total monomers 2.7 parts by weight of anionic emulsifier polyoxyethylene nonylphenyl ether ammonium sulfate (30%), 3 parts by weight of polyoxyethylene nonylphenyl ether having an HLB value of 16 as a nonionic emulsifier to prepare an acrylic emulsion pressure-sensitive adhesive in the same polymerization process It was.
비교예 2Comparative Example 2
부틸아크릴레이트 30 중량%, 2-에틸헥실아크릴레이트 60 중량%, 부틸메타크릴레이트 4 중량% 및 아크릴산 1 중량%와 N-메틸롤아크릴아미드(50%) 10 중량%의 단량체 조성물과 전체 단량체 100 중량부에 대하여 음이온성 유화제 폴리옥시에틸렌 노닐페닐 에테르황산암모늄(30%) 2.7 중량부, 비이온성 유화제로 HLB값이 16인 폴리옥시에틸렌 노닐페닐 에테르 3 중량부를 상기 제조예와 같은 중합공정으로 아크릴 에멀젼 점착제를 제조하였다.Monomer composition of 30% by weight of butyl acrylate, 60% by weight of 2-ethylhexyl acrylate, 4% by weight of butyl methacrylate and 1% by weight of acrylic acid and 10% by weight of N-methylolacrylamide (50%) and total monomers 100 2.7 parts by weight of anionic emulsifier polyoxyethylene nonylphenyl ether ammonium sulfate (30%), and 3 parts by weight of polyoxyethylene nonylphenyl ether having a HLB value of 16 as a nonionic emulsifier in the same polymerization process An emulsion adhesive was prepared.
비교예 3Comparative Example 3
부틸아크릴레이트 40 중량%, 2-에틸헥실아크릴레이트 40 중량%, 메틸메타크릴레이트 10 중량% 및 메타크릴산 10 중량%의 단량체 조성물과 전체 단량체 100 중량부에 대하여 음이온성 유화제 도데실벤젠술폰산소다(50%) 2 중량부, 비이온성 유화제로 HLB값이 16인 폴리옥시에틸렌 노닐페닐 에테르 2 중량부를 상기 제조예와 같은 중합공정으로 아크릴 에멀젼 점착제를 제조하였다.40% by weight of butyl acrylate, 40% by weight of 2-ethylhexyl acrylate, 10% by weight of methyl methacrylate and 10% by weight of methacrylic acid monomer composition and 100 parts by weight of the total monomer monomer dodecylbenzenesulfonate (50%) 2 parts by weight, 2 parts by weight of polyoxyethylene nonylphenyl ether having an HLB value of 16 as a nonionic emulsifier was prepared in the same polymerization process as the acrylic emulsion pressure-sensitive adhesive.
비교예 4Comparative Example 4
부틸아크릴레이트 10 중량%, 2-에틸헥실아크릴레이트 50 중량%, 부틸메타크릴레이트 29 중량% 및 메타크릴산 1 중량%와 2-히드록시에틸메타크릴레이트 10 중량%의 단량체 조성물과 전체 단량체 100 중량부에 대하여 음이온성 유화제 도데실벤젠술폰산소다(50%) 2 중량부, 비이온성 유화제로 HLB값이 16인 폴리옥시에틸렌 노닐페닐 에테르 2 중량부를 상기 제조예와 같은 중합공정으로 아크릴 에멀젼 점착제를 제조하였다.Monomer composition of 10% by weight of butyl acrylate, 50% by weight of 2-ethylhexyl acrylate, 29% by weight of butyl methacrylate and 1% by weight of methacrylic acid and 10% by weight of 2-hydroxyethyl methacrylate and total monomers 100 2 parts by weight of anionic emulsifier dodecylbenzenesulfonic acid sodium (50%) and 2 parts by weight of polyoxyethylene nonylphenyl ether having an HLB value of 16 as a nonionic emulsifier were subjected to the polymerization process of the acrylic emulsion. Prepared.
비교예 5Comparative Example 5
부틸아크릴레이트 20 중량%, 2-에틸헥실아크릴레이트 50 중량%, 에틸아크릴레이트 20 중량%, 부틸메타크릴레이트 5 중량% 및 아크릴산 4 중량% 및 N-메틸롤아크릴아미드(50%) 2 중량%의 단량체 조성물과 전체 단량체 100 중량부에 대하여 음이온성 유화제 도데실벤젠술폰산소다(50%) 6 중량부, 비이온성 유화제로 HLB값이 16인 폴리옥시에틸렌 노닐페닐 에테르 4 중량부를 상기 제조예와 같은 중합공정으로 아크릴 에멀젼 점착제를 제조하였다.20% by weight butyl acrylate, 50% by weight 2-ethylhexyl acrylate, 20% by weight ethyl acrylate, 5% by weight butyl methacrylate and 4% by weight acrylic acid and 2% by weight N-methylol acrylamide (50%) 6 parts by weight of anionic emulsifier dodecylbenzenesulfonate (50%), and 4 parts by weight of polyoxyethylene nonylphenyl ether having a HLB value of 16 as a nonionic emulsifier based on 100 parts by weight of the monomer composition An acrylic emulsion pressure sensitive adhesive was prepared by a polymerization process.
상기 실시예 1 ∼ 4와 비교예 1 ∼ 5의 조성표를 다음 표 1에 나타내었다.The composition table of the said Examples 1-4 and Comparative Examples 1-5 is shown in following Table 1.
시험예Test Example
제조된 아크릴 에멀젼 점착제를 라벨지와 보호 테이프에 적용하여 물성을 평가하였으며, 그 결과를 다음 표 2와 표 3에 나타내었다.The prepared acrylic emulsion pressure-sensitive adhesive was applied to labels and protective tapes to evaluate physical properties, and the results are shown in Tables 2 and 3 below.
1) 라벨용 점착지 제작1) Making adhesive paper for label
제조된 아크릴 에멀젼을 이형지 위에 15 ㎛ 건조두께로 도포한 후 실온에서 약 30분간 방치하여 건조시키고, 다시 120 ℃에서 1분간 처리하여 완전 건조시켰다. 전사지를 합포한 후 55 ℃에서 24시간 숙성하여 라벨용 점착지를 제작하였다.The prepared acrylic emulsion was applied on a release paper with a dry thickness of 15 μm, left to dry at room temperature for about 30 minutes, and dried at 120 ° C. for 1 minute to be completely dried. After the transfer paper was combined, aged at 55 ° C. for 24 hours to prepare a label adhesive.
2) 보호 테이프 제작2) Protective tape making
제조된 아크릴 에멀젼을 보호 테이프용 폴리에틸렌 필름 위에 5 ㎛ 건조두께로 도포한 후 실온에서 약 30분간 방치하여 건조시키고, 다시 55 ℃에서 10분간 처리하고 완전 건조시켰다. 이형지를 합포한 후 55 ℃에서 24시간 숙성하여 보호 테이프를 제작하였다.The prepared acrylic emulsion was coated on a polyethylene film for protective tape with a dry thickness of 5 μm, left at room temperature for about 30 minutes, dried, treated at 55 ° C. for 10 minutes and completely dried. After releasing the release paper was aged for 24 hours at 55 ℃ to prepare a protective tape.
3) 점착성 평가3) adhesive evaluation
제조된 점착제 에멀젼의 점착성 측정은 ASTM D3121-73에 의한 방법을 기준으로 하였다. 이형지를 제거한 라벨지 및 보호 테이프를 유리판에 평평하게 부착하고 직경 7.1 ㎜(ball No.9)의 스테인레스 스틸구를 사용하여 경사각도 20°30′, 경사높이 65 mm의 위치에서 구가 굴러간 거리로서 점착성을 측정하였다.Tackiness measurement of the prepared pressure-sensitive adhesive was based on the method according to ASTM D3121-73. The distance between the rolled paper at a position of inclination angle of 20 ° 30 'and inclination height of 65 mm with the label paper and protective tape removed from the release paper flat on the glass plate and using a stainless steel ball with a diameter of 7.1 mm (ball No. 9). Tackiness was measured.
4) 점착력 평가4) Adhesion Evaluation
이형지를 제거한 라벨지 및 보호 테이프를 스테인레스판에 손으로 압착하여 합체하고 실온에서 1시간 방치한 후 다음과 같은 조건으로 180°박리강도를 측정하였다.The label paper and the protective tape from which the release paper was removed were combined by hand on a stainless steel plate, coalesced, and left at room temperature for 1 hour, and 180 ° peel strength was measured under the following conditions.
- 규격 : 20 mm ×150 mm-Size: 20 mm × 150 mm
- 박리속도 : 300 mm/min-Peeling speed: 300 mm / min
5) 경시 점착력 평가5) Evaluation of adhesiveness over time
이형지를 제거한 라벨지 및 보호 테이프를 스테인레스판에 손으로 압착하여 합체한 후 60 ℃ 오븐에서 24시간 방치한 다음 상온으로 냉각하고 상기 점착력 평가와 같은 조건으로 180°박리강도를 측정하였다.The label paper and the protective tape from which the release paper was removed were combined by hand on a stainless steel plate, and then allowed to stand for 24 hours in an oven at 60 ° C., then cooled to room temperature, and 180 ° peel strength was measured under the same conditions as in the evaluation of adhesion.
6) 크리프성 평가6) Creep Evaluation
이형지를 제거한 라벨지 및 보호 테이프를 스테인레스판과 일정면적(25 ㎜ ×25 ㎜)으로 합체하여 압착시켰다. 실온에서 1시간 방치 후 40 ℃ 및 70 ℃에서 1 kg의 하중을 걸어 1시간 동안 박리된 거리를 측정하여 상태 및 내열 크리프성을 평가하였다.The label paper and the protective tape from which the release paper was removed were coalesced into a stainless plate with a predetermined area (25 mm x 25 mm) and pressed. After standing at room temperature for 1 hour, a load of 1 kg was applied at 40 ° C. and 70 ° C., and the peeled distance was measured for 1 hour to evaluate condition and heat creep resistance.
7) 재박리성 평가7) Releasability Assessment
이형지를 제거한 라벨지 및 보호 테이프를 유리판에 부착하여 80 ℃에서 30분간 방치한 후 실온에서 120°로 박리하여 유리판면에 남겨지는 잔유물의 면적으로 다음 수학식 1과 같이 재박리성을 측정하였다.The label paper and the protective tape from which the release paper was removed were attached to a glass plate and left at 80 ° C. for 30 minutes, and then peeled to 120 ° at room temperature to measure the re-peelability as shown in Equation 1 below.
이상에서 설명한 바와 같이, 본 발명에 따른 아크릴 에멀젼 점착제는 점착성과 점착력 및 응집력 등의 점착제 고유의 물성을 유지하면서 재박리성이 우수하므로 재박리성을 요하는 라벨지나 보호용 테이프 등의 용도로 사용할 수 있다.As described above, the acrylic emulsion pressure sensitive adhesive according to the present invention is excellent in re-peelability while maintaining the inherent properties of the pressure-sensitive adhesive such as adhesiveness, cohesion and cohesion, so that it can be used for applications such as labels or protective tapes requiring re-peelability. have.
Claims (4)
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH01234485A (en) * | 1988-03-14 | 1989-09-19 | Japan Synthetic Rubber Co Ltd | Water-based pressure-sensitive adhesive |
| JPH10158617A (en) * | 1996-11-29 | 1998-06-16 | Nitto Denko Corp | Repeatedly peelable pressure-sensitive adhesive composition of water dispersion type and repeatedly peelable pressure-sensitive adhesive sheet and the like using the same |
| US5939479A (en) * | 1991-11-22 | 1999-08-17 | Avery Dennison Corporation | Removable and guillotinable emulsion pressure-sensitive adhesives |
| KR100385720B1 (en) * | 1999-04-30 | 2003-05-27 | 주식회사 엘지화학 | Acrylic pressure-sensitive adhesive composition for optical use having improved rework property and laminates coated therewith |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01234485A (en) * | 1988-03-14 | 1989-09-19 | Japan Synthetic Rubber Co Ltd | Water-based pressure-sensitive adhesive |
| US5939479A (en) * | 1991-11-22 | 1999-08-17 | Avery Dennison Corporation | Removable and guillotinable emulsion pressure-sensitive adhesives |
| JPH10158617A (en) * | 1996-11-29 | 1998-06-16 | Nitto Denko Corp | Repeatedly peelable pressure-sensitive adhesive composition of water dispersion type and repeatedly peelable pressure-sensitive adhesive sheet and the like using the same |
| KR100385720B1 (en) * | 1999-04-30 | 2003-05-27 | 주식회사 엘지화학 | Acrylic pressure-sensitive adhesive composition for optical use having improved rework property and laminates coated therewith |
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