KR102395361B1 - Composition of dismantlable two component type urethane adhesives and its dismantlement method - Google Patents
Composition of dismantlable two component type urethane adhesives and its dismantlement method Download PDFInfo
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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
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
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- 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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3225—Polyamines
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- 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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
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- 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
- C08G18/48—Polyethers
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
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- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
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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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Abstract
Description
본 발명은 기본적으로 사용 온도에서는 높은 모듈러스를 가지되, 해체 조건에서는 낮은 모듈러스 특성을 가질 수 있도록 하는, 해체성을 가지는 2액형 구조용 우레탄 접착제 조성물 및 이의 해체방법에 관한 것이다.The present invention basically relates to a two-component structural urethane adhesive composition having disintegrability, which has a high modulus at a working temperature but a low modulus at a dismantling condition, and a dismantling method thereof.
최근 들어 산업과 기술의 발전속도가 더욱 빨라지고 편리한 생활을 돕는 새로운 제품의 개발도 활발해짐에 따라 제품의 사용기간이 짧아지고 또한 폐기되는 제품의 양도 늘어나므로 이러한 영향으로 지구의 자원 고갈 및 환경오염이 심해지고 있다. 따라서 사용된 폐기물을 재사용하여 환경오염을 줄이고 자원의 재사용으로 지속적인 발전이 가능하게 하는 것이 요구되고 있다.Recently, as industries and technologies develop faster and new products that help people live more actively, the period of use of products is shortened and the amount of discarded products is also increasing. is losing Therefore, it is required to reuse the used waste to reduce environmental pollution and to enable sustainable development through the reuse of resources.
우리의 생활에 사용되는 제품들은 대부분 많은 구성 소재들로 접합되어 있으며, 접합의 방법중에서 접착제를 이용한 접착은 같은 재질이나 다른 재질의 소재를 결합하는 데 있어서 간편하고 경제적이어서 널리 사용되고 있다. 하지만 접착제로 결합된 부품은 해체하기가 어려워서 재료를 분별하여 회수 할 수 없는 문제가 있다.Most of the products used in our lives are joined by many constituent materials, and among the bonding methods, bonding using an adhesive is widely used because it is simple and economical to combine materials of the same or different materials. However, there is a problem in that it is difficult to dismantle the parts joined with adhesives, so it is not possible to separate the materials and recover them.
따라서 접착제로 결합되어있는 부품을 필요한 때에 쉽게 분리할 수 있다면 결합되어 있는 소재들을 재사용하기가 훨씬 쉬워질 것이며 환경오염도 줄일 수 있기 때문에 해체성 접착제에 대한 요구가 증대되고 있다Therefore, if the parts joined by adhesive can be easily separated when necessary, it will be much easier to reuse the joined materials, and since environmental pollution can be reduced, the demand for dismantling adhesives is increasing.
한편, 해체성 접착제에서 해체성이 의미하는 것은 특정 조건(가열, 화학적처리 등)을 가하였을 때 고화되어 접착되어 있던 접착제가 연화 또는 분해되어 피착재를 쉽게 분리할수 있게 하는 특성을 말하며 이를 이용하여 피착재의 재활용이 가능하도록 하는 것을 의미한다.On the other hand, in dismantling adhesives, dismantling means properties that allow the adhesive to be hardened and adhered to soften or decompose when a specific condition (heating, chemical treatment, etc.) is applied, so that the adherend can be easily separated. It means that the recycling of the adherend is possible.
관련 기술로써 특허문헌 1에서는 전체 조성물에 대하여 10 내지 60 중량%의 함량을 갖는 이소시아네이트 화합물로 이루어진 제1 성분; 및 사용 전에 상기 제1 성분과 접촉하지 않고, 전체 조성물에 대하여 각각 i) 폴리올 화합물 10 내지 40 중량%, ii) 유색안료 5 내지 30 중량%, iii) 글리시딜에스테르계 수지, 에폭시노볼락계 수지 또는 비스페놀 A형 노볼락계 수지로 이루어진 탄성수지 5 내지 40 중량%, iv) 0.01 내지 10 중량%의 충진제, 및 상온경화 촉진을 위한 제1 경화 촉진제로서 디부틸 틴 디라우레이트(DBTL) 및 고온경화 촉진을 위한 제2 경화 촉진제로서 아민계 화합물 포함하는 v) 경화 촉진제 5 내지 20 중량%로 이루어진 제2 성분을 포함하는, 이액형 폴리우레탄 접착제 조성물을 제안하였다.As a related art, in Patent Document 1, a first component consisting of an isocyanate compound having a content of 10 to 60% by weight based on the total composition; and without contact with the first component before use, i) 10 to 40% by weight of polyol compound, ii) 5 to 30% by weight of colored pigment, iii) glycidyl ester-based resin, epoxy novolac-based resin, respectively, based on the total composition 5 to 40% by weight of an elastic resin consisting of a resin or a bisphenol A novolak-based resin, iv) 0.01 to 10% by weight of a filler, and dibutyltin dilaurate (DBTL) as a first curing accelerator for accelerating curing at room temperature, and A two-component polyurethane adhesive composition comprising a second component consisting of 5 to 20 wt% of v) a curing accelerator including an amine compound as a second curing accelerator for accelerating high temperature curing was proposed.
그리고 특허문헌 2에서는 친환경재 필러 100중량부를 기준으로 폴리에테르 폴리올 30 내지 50 중량부와, 피마자 오일 40 내지 60 중량부와, 실리카 5 내지 15 중량부 및 촉매 0.001 내지 0.003 중량부를 혼합기에 담는 단계; 상기 혼합기에서 상기 친환경재 필러, 폴리에테르 폴리올, 피마자 오일, 실리카 및 DBTDL(Dibutyl Tin Dilaurate)을 교반하는 단계; 상기 교반된 친환경제 필러, 폴리에테르 폴리올, 피마자 오일, 실리카 및 상기 DBTDL(Dibutyl Tin Dilaurate)을 100℃ 내지 200℃로 진공에서 열처리하여 수분을 제거하고 탈포하여 주제를 준비하는 단계; 분자량 350 내지 400 정도의 메틸렌 비스페닐을 함유한 디페닐메탄 디아이소시아네이트(폴리머릭 : POLYMERIC) 100 중량부로 구성된 경화제를 준비하는 단계; 및 상기 준비된 주제와 상기 경화제를 4:1 내지 6:1로 섞어 조성물을 완성하는 단계;를 포함하는 것을 특징으로 하는 2액형 무용제 우레탄 접착제 조성물 제조 방법을 제안하였다.And in Patent Document 2, based on 100 parts by weight of the eco-friendly filler, 30 to 50 parts by weight of a polyether polyol, 40 to 60 parts by weight of castor oil, 5 to 15 parts by weight of silica, and 0.001 to 0.003 parts by weight of a catalyst; stirring the eco-friendly material filler, polyether polyol, castor oil, silica and DBTDL (Dibutyl Tin Dilaurate) in the mixer; preparing a main material by heat-treating the stirred eco-friendly filler, polyether polyol, castor oil, silica and the DBTDL (Dibutyl Tin Dilaurate) in a vacuum at 100° C. to 200° C. to remove moisture and defoaming; Preparing a curing agent consisting of 100 parts by weight of diphenylmethane diisocyanate (polymeric: POLYMERIC) containing methylene bisphenyl having a molecular weight of about 350 to 400; and mixing the prepared subject and the curing agent in a ratio of 4:1 to 6:1 to complete the composition; proposed a two-part solvent-free urethane adhesive composition manufacturing method comprising a.
하지만, 상기와 같은 종래의 2액형 우레탄계 접착제는 해체성을 가지지 못하는 문제점이 있었다.However, the conventional two-component urethane-based adhesive as described above has a problem in that it does not have dismantling properties.
이를 해결하기 위하여, 특허문헌 3에서는 평소에는 우수한 접착력을 유지하고 필요한 때에는 마이크로웨이브를 사용한 간단한 조작을 통하여 접착부위의 분리가 가능하도록 하기 위해, 에스테르계 폴리올 100 중량부와, 디이소시아네이트 10 ~ 60 중량부와, 쇄연장제 2 ~ 10 중량부와, 화학발포제 10 ~ 30 중량부와, 나노금속필러 1 ~ 8 중량부와, 분해촉진제 2.5 ~ 30 중량부 및 용매를 혼합하여 제조되는 해체성 폴리우레탄 접착제의 조성물 및 이의 해체방법을 제안하였다.In order to solve this, in Patent Document 3, 100 parts by weight of an ester-based polyol and 10 to 60 parts by weight of an ester-based polyol, and 10 to 60 parts by weight of an ester-based polyol, in order to maintain excellent adhesion and, when necessary, to allow separation of the adhesive site through a simple operation using a microwave Decomposable polyurethane prepared by mixing parts, 2 to 10 parts by weight of a chain extender, 10 to 30 parts by weight of a chemical foaming agent, 1 to 8 parts by weight of a nano metal filler, 2.5 to 30 parts by weight of a decomposition accelerator, and a solvent An adhesive composition and a dismantling method thereof were proposed.
이에 대하여, 본 발명의 출원인은 상기 특허문헌 3에 비하여 더욱 우수한 효율로 구현되는 해체성을 가지는 2액형 구조용 우레탄 접착제 조성물 및 이의 해체방법을 개발함으로써 본 발명을 완성하였다.On the other hand, the applicant of the present invention has completed the present invention by developing a two-component structural urethane adhesive composition and a dismantling method thereof having a dismantling property that is realized with greater efficiency compared to Patent Document 3 above.
본 발명은 상기와 같은 문제점을 해결하기 위한 것으로, 기본적으로 사용 온도에서는 높은 모듈러스를 가지되, 해체 조건에서는 낮은 모듈러스 특성을 가지는 2액형 구조용 우레탄 접착제 조성물을 제공함으로써, 사용온도에서는 두 피착재 간에 우수한 접착력을 가지지만, 해체방법으로 유도가열 방식을 통한 가열 시, 두 피착재가 쉽게 분리될 수 있도록 함을 과제로 한다.The present invention is to solve the above problems, basically by providing a two-component structural urethane adhesive composition having a high modulus at the operating temperature, but a low modulus at the dismantling condition, excellent in use between the two adherends at the operating temperature Although it has adhesive force, the task is to make it possible to separate the two adherends easily when heated through induction heating as a dismantling method.
본 발명은 2액형 구조용 우레탄 접착제 조성물에 있어서, 이소시아네이트인 디페닐메탄 디이소시아네이트(diphenyl methanediisocyanate, MDI) 60.47 ~ 65 중량% 및 폴리카프로락톤폴리올(poIycaprolactone,PCL) 35 ~ 39.53 중량%로 이루어지는 프리 폴리머 100 중량부에 대하여, 레진믹스로써 폴리카프로락톤폴리올(poIycaprolactone,PCL) 14 ~ 20 중량부, 카프로락톤폴리올(caprolactone,CAPA) 10 ~ 15 중량부, 폴리에테르아민(polyetheramines, PEA) 4.7 ~ 5.7 중량부 및 1,4-부탄디올(1,4-butanediol, 1,4-BD) 6 ~ 8 중량부로 이루어지는 것을 특징으로 하는, 해체성을 가지는 2액형 구조용 우레탄 접착제 조성물을 과제의 해결 수단으로 한다.The present invention relates to a two-component structural urethane adhesive composition, a free polymer 100 consisting of 60.47 to 65 wt% of diphenyl methanediisocyanate (MDI) and 35 to 39.53 wt% of polycaprolactone polyol (poIycaprolactone, PCL), which is an isocyanate Based on parts by weight, 14 to 20 parts by weight of polycaprolactone polyol (poIycaprolactone, PCL), 10 to 15 parts by weight of caprolactone (CAPA), 4.7 to 5.7 parts by weight of polyetheramines (PEA) as a resin mix And 1,4-butanediol (1,4-butanediol, 1,4-BD), characterized in that consisting of 6 to 8 parts by weight, a two-component structural urethane adhesive composition having a dismantling property as a means of solving the problem.
삭제delete
한편, 본 발명은 상기와 같은 조성물의 해체방법에 있어서, 유도가열기를 이용하여 230 ~ 240℃로 가열하여 해체시키는 것을 특징으로 하는, 해체성을 가지는 2액형 구조용 우레탄 접착제 조성물의 해체방법을 과제의 다른 해결 수단으로 한다.On the other hand, the present invention is a method of dismantling a two-component structural urethane adhesive composition having dismantling properties, characterized in that dismantling by heating at 230 to 240 ° C. using an induction heater in the dismantling method of the composition as described above. as another solution to
본 발명은 기본적으로 사용 온도에서는 높은 모듈러스를 가지되, 해체 조건에서는 낮은 모듈러스 특성을 가지며, 이로 인해 유도가열 방식을 통하여 피착재를 가열할 경우 쉽게 분리될 수 있는 해체성을 가지는 효과가 있다. 보다 구체적으로 피착재로써 금속(예를 들면, 스틸(steel)이나 알루미늄(aluminium) 등)과 플라스틱(예를 들면, CFRP(carbon fiber reinforced plastic) 등)의 이종재료 간에 우수한 접착력을 나타내면서도, 유도가열기를 통한 가열 시 두 피착재가 쉽게 분리될 수 있는 효과가 있다.The present invention basically has a high modulus at a working temperature, but a low modulus at a dismantling condition, which has the effect of having the disintegration property that can be easily separated when an adherend is heated through an induction heating method. More specifically, it exhibits excellent adhesion between dissimilar materials such as metal (eg, steel or aluminum) and plastic (eg, carbon fiber reinforced plastic (CFRP)) as an adherend, while inducing When heating through a heater, there is an effect that the two adherends can be easily separated.
상기의 효과를 달성하기 위한 본 발명은 해체성을 가지는 2액형 구조용 우레탄 접착제 조성물 및 이의 해체방법에 관한 것으로서, 본 발명의 기술적 구성을 이해하는데 필요한 부분만이 설명되며 그 이외 부분의 설명은 본 발명의 요지를 흩트리지 않도록 생략될 것이라는 것을 유의하여야 한다.The present invention for achieving the above effect relates to a two-component structural urethane adhesive composition having dismantling properties and a dismantling method thereof, and only the parts necessary to understand the technical configuration of the present invention are described, and the description of other parts is the present invention It should be noted that they will be omitted so as not to obscure the gist of
이하, 본 발명에 따른 해체성을 가지는 2액형 구조용 우레탄 접착제 조성물 및 이의 해체방법을 상세히 설명하면 다음과 같다.Hereinafter, a two-component structural urethane adhesive composition having disintegrability according to the present invention and a dismantling method thereof will be described in detail as follows.
본 발명은 이소시아네이트인 디페닐메탄 디이소시아네이트(diphenyl methanediisocyanate, MDI) 60.47 ~ 65 중량% 및 폴리카프로락톤폴리올(poIycaprolactone,PCL) 35 ~ 39.53 중량%로 이루어지는 프리 폴리머 100 중량부에 대하여, 레진믹스로써 폴리카프로락톤폴리올(poIycaprolactone,PCL) 14 ~ 20 중량부, 카프로락톤폴리올(caprolactone,CAPA) 10 ~ 15 중량부, 폴리에테르아민(polyetheramines, PEA) 4.7 ~ 5.7 중량부 및 1,4-부탄디올(1,4-butanediol, 1,4-BD) 6 ~ 8 중량부로 이루어지는 것을 특징으로 한다.The present invention relates to 100 parts by weight of a free polymer consisting of 60.47 to 65% by weight of diphenyl methanediisocyanate (MDI), which is an isocyanate, and 35 to 39.53% by weight of polycaprolactone polyol (poIycaprolactone, PCL), with respect to 100 parts by weight of a resin mix. 14 to 20 parts by weight of caprolactone polyol (poIycaprolactone, PCL), 10 to 15 parts by weight of caprolactone polyol (CAPA), 4.7 to 5.7 parts by weight of polyetheramines (PEA) and 1,4-butanediol (1, 4-butanediol, 1,4-BD) is characterized in that it consists of 6 to 8 parts by weight.
상기 이소시아네이트는 폴리올과 반응하여 프리 폴리머를 합성시키는 작용을 하는 것으로, 디페닐메탄 디이소시아네이트(diphenyl methanediisocyanate, MDI)을 사용하며, 그 함량이 60.47 중량% 미만일 경우 프리 폴리머가 제대로 합성되지 못할 우려가 있으며, 65 중량%를 초과할 경우 접착제의 물성을 저하시킬 우려가 있다.The isocyanate reacts with the polyol to synthesize the free polymer, and diphenyl methanediisocyanate (MDI) is used, and if the content is less than 60.47 wt%, the free polymer may not be properly synthesized. , If it exceeds 65% by weight, there is a risk of lowering the physical properties of the adhesive.
상기 프리 폴리머에 사용되는 폴리올은 이소시아네이트와 반응하여 프리 폴리머를 합성시키는 작용을 하는 것으로, 폴리카프로락톤폴리올(poIycaprolactone,PCL)을 사용하며, 그 함량이 35 중량% 미만일 경우 프리 폴리머가 제대로 합성되지 못할 우려가 있으며, 39.53 중량%를 초과할 경우 미반응의 폴리올이 잔류하여 우레탄 합성 수율이 저하될 우려가 있다.The polyol used for the free polymer reacts with isocyanate to synthesize the free polymer, and polycaprolactone polyol (poIycaprolactone, PCL) is used, and if the content is less than 35% by weight, the free polymer cannot be properly synthesized There is a concern, and when it exceeds 39.53 wt %, unreacted polyol remains and there is a fear that the urethane synthesis yield may be lowered.
상기 레진믹스는 구조용 접착제의 성질을 부여하기 위한 것으로, 폴리카프로락톤폴리올(poIycaprolactone,PCL) 14 ~ 20 중량부와 카프로락톤폴리올(caprolactone,CAPA) 10 ~ 15 중량부를 함께 사용하며, 경화제(hardner)로써 사슬연장제인 폴리에테르아민(polyetheramines, PEA) 4.7 ~ 5.7 중량부 및 1,4-부탄디올(1,4-butanediol, 1,4-BD) 6 ~ 8 중량부를 사용한다.The resin mix is intended to impart the properties of a structural adhesive, and 14 to 20 parts by weight of polycaprolactone polyol (poIycaprolactone, PCL) and 10 to 15 parts by weight of caprolactone polyol (caprolactone, CAPA) are used together, and a hardener As a chain extender, 4.7 to 5.7 parts by weight of polyetheramines (PEA) and 6 to 8 parts by weight of 1,4-butanediol (1,4-BD) are used.
여기서, 상기 레진믹스를 이루는 각 물질의 조성이 상기 각 범위를 벗어날 경우 접착제의 성질이 제대로 부여되지 못하거나 또는 해체성을 가지지 못할 우려가 있다.Here, when the composition of each material constituting the resin mix is out of each of the above ranges, there is a fear that the properties of the adhesive may not be properly imparted or that it may not have dismantling properties.
한편, 본 발명은 상기와 같은 해체성을 가지는 2액형 구조용 우레탄 접착제 조성물의 해체방법으로써 유도가열기를 이용한다.On the other hand, the present invention uses an induction heater as a dismantling method of the two-component structural urethane adhesive composition having the above dismantling properties.
보다 구체적으로 유도가열기를 이용하여 230 ~ 240℃로 가열하여 해체시키며, 유도가열기는 특정 제품에 한정하지 않고 상기 온도범위를 가질 수 있는 이미 공지된 다양한 종류의 유도가열기 적용이 가능하다. 한편, 온도범위가 상기 범위를 벗어날 경우 해체 효율이 저하될 우려가 있다.More specifically, it is disassembled by heating to 230 ~ 240 ℃ using an induction heater, and the induction heater is not limited to a specific product, and various types of induction heaters that are already known that can have the above temperature range can be applied. On the other hand, when the temperature range is out of the above range, there is a fear that the dismantling efficiency is lowered.
이하, 본 발명을 아래 실시예에 의거하여 더욱 상세히 설명하겠는바 본 발명이 실시예에 의해 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail based on the following examples, but the present invention is not limited by the examples.
1. 2액형 구조용 우레탄 접착제의 제조1. Manufacture of two-component structural urethane adhesive
(실시예 1)(Example 1)
교반기, 냉각기, 질소 주입기가 장착된 5구 분리형 플라스크에 이소시아네이트인 MDI 60.47 중량% 및 PCL 39.53 중량%를 넣고, 80℃로 온도를 높여서 질소를 투입하면서 200rpm의 속도로 교반하여 NCO 함량이 이론치에 도달할 때까지 반응시켜서 프리 폴리머를 제조하였다(NCO/OH비 = 2.44 / NCO 함량 = 12% / 점도(cps) = 42000). 그리고 레진믹스로써 PCL 14 중량부, CAPA 10 중량부, PEA 4.7 중량부 및 1,4-BD 6 중량부를 투입하고 80℃의 온도에서 질소를 투입하면서 200rpm의 속도로 교반하여 이소시아네이트 함량이 이론치에 도달하면 반응을 종료시켜 제조하였다(NCO/OH+NH비 = 1.05 / 하드세그먼트(hard segment) = 52.8% / 오픈타임(open time) = 14분).60.47 wt% of MDI and 39.53 wt% of PCL, which are isocyanates, were put into a five-necked separate flask equipped with a stirrer, a cooler, and a nitrogen injector, and the temperature was raised to 80 ° C. and nitrogen was added while stirring at a speed of 200 rpm to reach the theoretical value of NCO content. A free polymer was prepared by reacting until And as a resin mix, 14 parts by weight of PCL, 10 parts by weight of CAPA, 4.7 parts by weight of PEA and 6 parts by weight of 1,4-BD were added and stirred at a speed of 200 rpm while nitrogen was added at a temperature of 80° C. so that the isocyanate content reached the theoretical value. When the reaction was terminated, it was prepared (NCO/OH+NH ratio = 1.05 / hard segment = 52.8% / open time = 14 minutes).
(실시예 2)(Example 2)
교반기, 냉각기, 질소 주입기가 장착된 5구 분리형 플라스크에 이소시아네이트인 MDI 65 중량% 및 PCL 35 중량%를 넣고, 80℃로 온도를 높여서 질소를 투입하면서 200rpm의 속도로 교반하여 NCO 함량이 이론치에 도달할 때까지 반응시켜서 프리 폴리머를 제조하였다(NCO/OH비 = 2.44 / NCO 함량 = 12% / 점도(cps) = 42000). 그리고 레진믹스로써 PCL 20 중량부, CAPA 15 중량부, PEA 5.7 중량부 및 1,4-BD 8 중량부를 투입하고 80℃의 온도에서 질소를 투입하면서 200rpm의 속도로 교반하여 이소시아네이트 함량이 이론치에 도달하면 반응을 종료시켜 제조하였다(NCO/OH+NH비 = 1.05 / 하드세그먼트(hard segment) = 52.8% / 오픈타임(open time) = 14분).Put 65% by weight of MDI and 35% by weight of PCL, which are isocyanates, into a five-necked separate flask equipped with a stirrer, a cooler, and a nitrogen injector, raise the temperature to 80°C, and stir at a speed of 200rpm while adding nitrogen, so that the NCO content reaches the theoretical value A free polymer was prepared by reacting until And as a resin mix, 20 parts by weight of PCL, 15 parts by weight of CAPA, 5.7 parts by weight of PEA and 8 parts by weight of 1,4-BD were added, and the isocyanate content reached the theoretical value by stirring at a speed of 200 rpm while adding nitrogen at a temperature of 80 ° C. It was prepared by terminating the reaction (NCO / OH + NH ratio = 1.05 / hard segment = 52.8% / open time (open time) = 14 minutes).
(비교예 1)(Comparative Example 1)
특허문헌 3을 참조하여, 교반기, 냉각기, 질소 주입기가 장착된 5구 분리형 플라스크에 에스테르 폴리올(Ester Polyol) 100g과 메틸렌디페닐디이소시아네이트(Diphenylmethane Diisocyanate) 25g과 메틸에틸케톤(methyl ethyl ketone) 20g를 넣고 후 80℃로 온도를 높여서 질소를 투입하면서 200rpm의 속도로 교반 하면서 NCO 함량이 이론치에 도달할 때까지 반응시켜서 이소시아네이트말단 프리폴리머를 제조하였다. 그 다음 1,4-BD 3.6g, 디부틸틴디라우레이트(dibutyltindilaurate) 0.1g를 투입하고 80℃의 온도에서 질소를 투입하면서 200rpm의 속도로 교반하여 히드록시기와 이소시아네이트의 반응이 모두 종료되어 이소시아네이트 함량이 이론치에 도달하면 반응을 종료시켜 제조하였다.Referring to Patent Document 3, 100 g of ester polyol, 25 g of methylene diphenyl diisocyanate and 20 g of methyl ethyl ketone were added to a 5-necked separate flask equipped with a stirrer, a cooler, and a nitrogen injector. After the addition, the temperature was raised to 80° C., nitrogen was added, and the reaction was conducted until the NCO content reached the theoretical value while stirring at a speed of 200 rpm to prepare an isocyanate-terminated prepolymer. Then, 3.6 g of 1,4-BD and 0.1 g of dibutyltindilaurate were added, and nitrogen was added at a temperature of 80 ° C. while stirring at a speed of 200 rpm. The reaction between the hydroxyl group and the isocyanate was completed, and the isocyanate content was decreased. When the theoretical value was reached, the reaction was terminated and prepared.
2. 2액형 구조용 우레탄 접착제의 평가2. Evaluation of two-component structural urethane adhesive
상기 실시예 및 비교예에 따른 접착제를 스틸과 CFRP, 알루미늄과 CFRP의 접착면에 각각 도포 후 접착하여 전단접착강도를 평가하였고, 이후 접착된 시편을 유도가열기를 이용하여 아래 [표 1]과 같은 조건으로 가열한 후 분리여부를 확인하였으며, 그 결과는 아래 [표 2]에 나타내었다.The adhesives according to the Examples and Comparative Examples were applied to the adhesive surfaces of steel and CFRP, aluminum and CFRP, respectively, and then adhered to evaluate the shear adhesion strength, and then the bonded specimen was treated with an induction heater as shown in Table 1 below. After heating under the same conditions, separation was checked, and the results are shown in [Table 2] below.
(MPa, ASTM D1002)Shear adhesive strength
(MPa, ASTM D1002)
분리여부after induction heating
Separation
(MPa, ASTM D1002)Shear adhesive strength
(MPa, ASTM D1002)
분리여부after induction heating
Separation
상기 [표 2]에서와 같이, 본 발명에 따른 실시예는 비교예에 비하여, 이종재료 간에 우수한 접착력을 나타내면서도, 유도가열기를 통한 가열 시 두 피착재가 쉽게 분리될 수 있는 해체성을 가짐을 알 수 있다.As shown in [Table 2], the example according to the present invention exhibits excellent adhesion between dissimilar materials compared to the comparative example, and has disintegrability in which two adherends can be easily separated when heated through an induction heater. Able to know.
상술한 바와 같이, 본 발명에 따른 해체성을 가지는 2액형 구조용 우레탄 접착제 조성물 및 이의 해체방법은 상기의 바람직한 실시 예를 통해 설명하고, 그 우수성을 확인하였지만 해당 기술 분야의 당업자라면 하기의 특허 청구 범위에 기재된 본 발명의 사상 및 영역으로부터 벗어나지 않는 범위 내에서 본 발명을 다양하게 수정 및 변경시킬 수 있음을 이해할 수 있을 것이다.As described above, the two-component structural urethane adhesive composition and its dismantling method having dismantling properties according to the present invention have been described through the above preferred embodiments, and the excellence thereof has been confirmed, but those skilled in the art are entitled to the following claims It will be understood that various modifications and variations of the present invention can be made without departing from the spirit and scope of the present invention as described in .
Claims (3)
이소시아네이트인 디페닐메탄 디이소시아네이트(diphenyl methanediisocyanate, MDI) 60.47 ~ 65 중량% 및 폴리카프로락톤폴리올(poIycaprolactone,PCL) 35 ~ 39.53 중량%로 이루어지는 프리 폴리머 100 중량부에 대하여, 레진믹스로써 폴리카프로락톤폴리올(poIycaprolactone,PCL) 14 ~ 20 중량부, 카프로락톤폴리올(caprolactone,CAPA) 10 ~ 15 중량부, 폴리에테르아민(polyetheramines, PEA) 4.7 ~ 5.7 중량부 및 1,4-부탄디올(1,4-butanediol, 1,4-BD) 6 ~ 8 중량부로 이루어지는 것을 특징으로 하는, 해체성을 가지는 2액형 구조용 우레탄 접착제 조성물.
In the two-component structural urethane adhesive composition,
With respect to 100 parts by weight of a free polymer consisting of 60.47 to 65% by weight of diphenyl methanediisocyanate (MDI), which is an isocyanate, and 35 to 39.53% by weight of polycaprolactone polyol (poIycaprolactone, PCL), polycaprolactone polyol as a resin mix (poIycaprolactone, PCL) 14 to 20 parts by weight, caprolactone polyol (caprolactone, CAPA) 10 to 15 parts by weight, polyetheramines (PEA) 4.7 to 5.7 parts by weight, and 1,4-butanediol (1,4-butanediol) , 1,4-BD) A two-component structural urethane adhesive composition having dismantling properties, characterized in that it consists of 6 to 8 parts by weight.
유도가열기를 이용하여 230 ~ 240℃로 가열하여 해체시키는 것을 특징으로 하는, 해체성을 가지는 2액형 구조용 우레탄 접착제 조성물의 해체방법.The method of disassembling the composition according to claim 1,
Dismantling method of a two-component structural urethane adhesive composition having dismantling properties, characterized in that it is disassembled by heating to 230 ~ 240 ℃ using an induction heater.
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| KR102564475B1 (en) | 2021-10-19 | 2023-08-07 | 한국신발피혁연구원 | Composition of dismantlable two component type polyurethane adhesives with high mechanical properties and adhesion strength and its dismantlement method |
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