KR101116291B1 - Method for manufacture high water permeable solvent free polyurethane adhesive - Google Patents
Method for manufacture high water permeable solvent free polyurethane adhesive Download PDFInfo
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- KR101116291B1 KR101116291B1 KR1020090110273A KR20090110273A KR101116291B1 KR 101116291 B1 KR101116291 B1 KR 101116291B1 KR 1020090110273 A KR1020090110273 A KR 1020090110273A KR 20090110273 A KR20090110273 A KR 20090110273A KR 101116291 B1 KR101116291 B1 KR 101116291B1
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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
- 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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Abstract
본 발명은 투습성이 우수한 폴리에틸렌글리콜과 물리적 특성이 우수한 폴리카보네이트디올 등을 공중합체 폴리올로 사용하여 합성시킨 것을 특징으로 하는 투습성이 우수한 무용제형 폴리우레탄 접착제의 제조방법에 관한 것으로, 폴리에틸렌글리콜의 단점인 낮은 융점, 내수성, 접착력 등의 물성 보강을 위하여 폴리카보네이트디올을 사용하여 공중합시킴으로써, 내구성, 내수성, 접착력 등의 물성을 향상시켜 투습방수용 원단의 섬유용 접착제의 용도에 적합하도록 한 것이 장점이다. The present invention relates to a method for preparing a solvent-free polyurethane adhesive having excellent moisture permeability, characterized by synthesizing polyethylene glycol having excellent moisture permeability and polycarbonate diol having excellent physical properties as a copolymer polyol. Copolymerization using polycarbonate diol for reinforcing physical properties such as low melting point, water resistance, adhesion, and the like, improves the properties such as durability, water resistance, adhesion, and the like to make it suitable for the use of the adhesive for fibers of the moisture-permeable waterproof fabric.
무용제형 접착제, 습기경화, 폴리우레탄, 폴리에틸렌글리콜, 폴리카보네이트디올, 투습성 Solvent free adhesive, moisture cure, polyurethane, polyethylene glycol, polycarbonate diol, moisture permeability
Description
본 발명은 투습성이 우수한 무용제형 폴리우레탄 접착제의 제조방법에 관한 것으로, 보다 구체적으로는 투습성이 우수한 폴리에틸렌글리콜과 물리적 특성이 우수한 폴리카보네이트디올 등을 공중합체 폴리올로 사용하여 합성시킨 폴리우레탄 수지의 접착제로서, 내구성, 내수성, 접착력 등의 물성이 우수하여 투습방수 원단에 사용되는 섬유용 접착제의 용도에 적합한 것을 특징으로 하는 투습성이 우수한 무용제형 폴리우레탄 접착제의 제조방법에 관한 것이다. The present invention relates to a method for producing a solvent-free polyurethane adhesive having excellent moisture permeability, and more specifically, an adhesive of a polyurethane resin synthesized by using polyethylene glycol having excellent moisture permeability and polycarbonate diol having excellent physical properties as a copolymer polyol. The present invention relates to a method for producing a solvent-free polyurethane adhesive having excellent moisture permeability, characterized by being excellent in physical properties such as durability, water resistance, adhesion, and the like, suitable for the use of an adhesive for fibers used in a moisture-permeable waterproof fabric.
일반적으로 폴리우레탄 수지는 분자중에 우레탄 결합을 가진 것으로서 주로 디이소시아네이트(diisocyanate)류와 폴리올(polyol) 화합물과의 반응에 의해 합성된 고분자 화합물로서, 내마모성, 내유성 및 내용제성에 뛰어나고, 탄성이 우수하 므로 접착제, 코팅제, 사출물, 페인트, 잉크, 도료, 발포체, 신발부품, 의류, 의료용 고분자 등 다양한 분야에서 적용되어지고 있다. In general, a polyurethane resin is a polymer compound having a urethane bond in a molecule and mainly synthesized by a reaction between diisocyanates and a polyol compound. It is excellent in wear resistance, oil resistance and solvent resistance, and has excellent elasticity. It is applied in various fields such as adhesives, coatings, injection moldings, paints, inks, paints, foams, shoe parts, clothing, and medical polymers.
그리고 폴리우레탄 접착제의 경우에는 거의 대부분 상당량의 유기용제를 함유한 형태로 사용되고 있지만 용제계 폴리우레탄 접착제는 지구 환경문제에 대한 관심이 높아지면서 탈용제화가 시급하게 요구되고 있다. 탈용제화란 이론적으로는 용제계 접착제의 용제를 제거하는 것을 의미하지만 현실적으로는 탈용제화가 용이하지 않으며, 그 수법으로는 액상 무용제화, 수성화, 핫멜트(hot melt)화 등이 검토되고 있다.In the case of polyurethane adhesives, almost all of them are used in a form containing a considerable amount of organic solvents, but solvent-based polyurethane adhesives are urgently required to be desolventized due to growing interest in global environmental problems. Desolvation theoretically means removing the solvent of the solvent-based adhesive, but in reality, desolvation is not easy. As a method thereof, liquid-solvent-free, aqueous, hot melt, and the like have been studied.
또한 습기경화형 폴리우레탄 접착제의 경우에는 말단에 NCO기를 가지며, 습기 경화형 핫멜트 우레탄 폴리머가 일반적이다. 핫멜트 폴리우레탄 접착제의 성상은 사용되는 용도에 따라 다양하며, 예를 들면 섬유분야에서는 촉감을 중요시하기 때문에 저 모듈러스(modulus)의 연질형이 바람직한 반면에 건축재료 분야에서는 강성(剛性)이 있는 경질형이 바람직하다. 핫멜트 폴리우레탄 접착제의 특징은 폴리아미드계나 폴리에스터계 및 EVA계 핫멜트 접착제 등에 비해 저온에서의 도포가 가능하면서도 습기경화반응에 의해 내열성이나 내구성이 우수하며, 순간 접착성을 가지고 있다. In addition, in the case of a moisture-curable polyurethane adhesive, the terminal has an NCO group, and a moisture-curable hot melt urethane polymer is generally used. The properties of the hot-melt polyurethane adhesives vary depending on the application used. For example, soft modulus of low modulus is desirable because the texture is important in the textile field, whereas rigid modulus of rigid material is preferred in the field of building materials. This is preferred. Hot Melt Polyurethane Adhesive is characterized in that it can be applied at low temperature compared to polyamide, polyester and EVA hot melt adhesives, and has excellent heat resistance and durability by moisture curing reaction, and has instantaneous adhesiveness.
그리고 나일론 및 폴리에스터 원단에 투습용 폴리우레탄 수지를 도포하거나, 필름을 전사하여 투습방수 특성이 우수한 기능성 의류를 제조할 수 있다. 투습용 폴리우레탄 수지는 친수성이 우수한 폴리에틸렌글리콜을 주원료를 사용하여 폴리우레탄 수지를 합성한다. 합성된 폴리우레탄 수지는 친수무공형(hydrophilic direct coating)의 투습 기능을 발현한다. 상기 방법으로 제조된 폴리우레탄 수지는 투습성은 우수하지만, 내수성 및 내구성, 접착강도가 취약한 문제점이 있다. And it is possible to produce a functional garment excellent in moisture-permeable waterproof properties by applying a moisture-permeable polyurethane resin to the nylon and polyester fabric, or by transferring the film. The moisture-permeable polyurethane resin synthesizes a polyurethane resin using polyethylene glycol having excellent hydrophilicity as a main raw material. The synthesized polyurethane resin exhibits a hydrophilic direct coating moisture permeation function. Polyurethane resin prepared by the above method is excellent in moisture permeability, but has a problem in that the water resistance and durability, the adhesive strength is weak.
무용제형 폴리우레탄 접착제에 대한 기술로서, 폴리우레탄의 경우 국내 등록특허공보 제10-0635293호에 유기 폴리이소시아네이트와 방향족 설폰산 금속염의 기를 함유하는 폴리에스터 폴리올 및 방향족 설폰산 금속염을 함유하지 않고 또한 수산기가가 10~350인 지방족 폴리올을 포함하는 조성물로부터 얻을 수 있는 폴리우레탄 수지의 수성 분산체를 함유하는 접착제가 제안되어 있고, 이와 같은 접착제는 초기 접착력이 크고 또한 경시와 더불어 접착력이 증가하고, 내열성 등의 내구성이 우수하여 수성 접착제로서 유용한 것으로 알려져 있고, 또한 국내 등록특허공보 제10-0217298호에 폴리올과 이소시아네이트 성분 및 쇄연장제로 합성한 수성 폴리우레탄계 접착제의 제조방법이 제안되어 있고, 이와 같은 방법에 의해 제조된 수성 폴리우레탄계 접착제를 신발용 접착제로 사용한 경우 초기 접착력 뿐만 아니라 상태 접착력 및 내열, 내수 접착력이 우수한 것으로 알려져 있으며, 또한 국내 공개특허공보 특2002-0003640호에 폴리올 혼합물과 폴리이소시아네이트를 축합 반응시켜 이소시아네이트기 말단의 폴리우레탄 프리폴리머를 제조한 후 물에 분산시킨 수분산물을 폴리아민을 이용하여 쇄연장하여 일액형 수성 폴리우레탄 접착제 조성물 의 제조방법이 제안되어 있고, 이 접착제의 경우에는 진공 열성형 접착시 경화제를 첨가하지 않고도 우수한 내수성 및 내열접착력을 제공할 수 있는 것으로 알려져 있다.As a technology for a solvent-free polyurethane adhesive, in the case of a polyurethane, in Korea Patent Publication No. 10-0635293, it does not contain a polyester polyol and an aromatic sulfonic acid metal salt containing a group of an organic polyisocyanate and an aromatic sulfonic acid metal salt, An adhesive containing an aqueous dispersion of a polyurethane resin obtainable from a composition containing an aliphatic polyol having a value of 10 to 350 has been proposed, and such an adhesive has a large initial adhesive force and an increase in adhesion with time, and heat resistance. It is known to be useful as an aqueous adhesive due to its excellent durability, and a method for producing an aqueous polyurethane-based adhesive synthesized from Korean Patent Publication No. 10-0217298 with a polyol, an isocyanate component and a chain extender is proposed. Water-based polyurethane adhesive prepared by When used as an adhesive for shoes, it is known to be excellent in initial adhesion as well as state adhesion, heat resistance, and water resistance. Also, the polyol mixture and the polyisocyanate are condensed and reacted with a polyurethane prepolymer at the end of an isocyanate group in Korea Patent Publication No. 2002-0003640. A method for producing a one-component aqueous polyurethane adhesive composition has been proposed by chain extension of an aqueous product dispersed in water using a polyamine after the preparation, and in the case of this adhesive, excellent water resistance without adding a curing agent during vacuum thermoforming bonding is proposed. And it is known that it can provide a heat-resistant adhesive force.
그리고 국내 등록특허공보 제10-0241587호에 폴리올, 디이소시아네이트, 쇄연장제 및 촉매의 성분으로 구성되는 무용제형 우레탄 접착제가 제안되어 있고, 이와 같은 우레탄 접착제의 경우에는 접착력이 매우 우수하고 0℃ 이하의 저온에서 내충격성이 우수함을 특징으로 하고, 또한 국내 등록특허공보 제10-0314818호에 이소시아네이트 화합물, 폴리에스테르 폴리올, 사슬 연장제, 열안정제 및 첨가제로 이루어진 폴리우레탄 접착제가 제안되어 있고, 이와 같은 접착제의 경우에는 우수한 접착성을 나타내고 내열성, 내가수분해성 및 안정성이 우수하여 신발 및 가죽 제품의 접착제로서 사용하기에 적합한 것이 특징이다. In addition, there is proposed a solvent-free urethane adhesive composed of polyol, diisocyanate, chain extender and a catalyst component in Korean Patent Publication No. 10-0241587. In the case of such a urethane adhesive, the adhesive force is very excellent and is 0 ° C. or lower. It is characterized by excellent impact resistance at low temperature, and in the Korean Patent Publication No. 10-0314818, a polyurethane adhesive composed of an isocyanate compound, a polyester polyol, a chain extender, a heat stabilizer and an additive is proposed. In the case of an adhesive, it has excellent adhesiveness and is excellent in heat resistance, hydrolysis resistance and stability, and is suitable for use as an adhesive for shoes and leather products.
상기와 같은 무용제형 폴리우레탄 접착제들의 경우에는 접착제의 고유 특성이 접착력의 우수성과 함께 내열성, 내구성 등의 물성이 향상되는 특성이 향상되는 특성이 있지만 투습성에 대한 물성을 고려하지 않은 점이 있었다.In the case of the non-solvent-type polyurethane adhesives as described above, there is a characteristic that the intrinsic properties of the adhesive are improved in the physical properties such as heat resistance, durability, etc. together with the superiority of the adhesive, but the physical properties of moisture permeability were not considered.
따라서, 상기와 같은 문제점을 해결하기 위한 본 발명은 무용제형 습기경화 폴리우레탄 수지를 원쇼트 프로세스(one shot process)를 이용하여 합성시킴으로써, 합성방법이 간단한 프로세스 공정인 것을 특징으로 하는 투습성이 우수한 무용제형 폴리우레탄 접착제 조성물 및 이를 이용한 폴리우레탄 접착제의 제조방법을 제공함을 과제로 한다. Therefore, the present invention for solving the above problems by synthesizing a solvent-free moisture-curable polyurethane resin using a one-shot process (one shot process), the synthesis method is a dance having excellent moisture permeability, characterized in that the simple process process It is an object of the present invention to provide a formulation polyurethane adhesive composition and a method for producing a polyurethane adhesive using the same.
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상기 과제를 해결하기 위하여, 본 발명은 디올 화합물의 혼합물에 촉매를 첨가한 다음 질소분위기에서 95℃에서 30분 혼합하는 단계와;In order to solve the above problems, the present invention comprises the steps of adding a catalyst to a mixture of diol compounds and then mixing for 30 minutes at 95 ℃ in a nitrogen atmosphere;
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상기 혼합물에 디이소시아네이트를 투입하여 93~97℃의 온도에서 20~60 분간 합성반응하는 단계;를 거쳐 합성되어지는 것을 특징으로 하는 투습성이 우수한 무용제형 폴리우레탄 접착제의 제조방법을 과제 해결 수단으로 한다.A method for producing a solvent-free polyurethane adhesive having excellent moisture permeability, which is synthesized through the step of adding diisocyanate to the mixture for 20 to 60 minutes at a temperature of 93 to 97 ° C., is a problem solving means. .
상기의 과제 해결 수단에 의한 본 발명은 투습기능성이 우수하면서 내구성, 내수성, 접착력이 우수한 무용제형 폴리우레탄 접착제 제조 방법에 관한 것으로, 폴리에틸렌글리콜의 단점인 낮은 융점, 내수성, 접착력 등의 물성 보강을 위하여 폴리카보네이트디올을 사용하여 공중합시킴으로써, 내구성, 내수성, 접착력 등의 물성을 향상시켜 투습방수용 원단의 섬유용 접착제의 용도에 적합하도록 한 것이 장점이다. The present invention by the above problem solving means relates to a method for producing a solvent-free polyurethane adhesive excellent in moisture permeability and excellent in durability, water resistance, adhesion, in order to reinforce physical properties such as low melting point, water resistance, adhesive strength, which is a disadvantage of polyethylene glycol By copolymerizing with polycarbonate diol, it is advantageous to improve physical properties such as durability, water resistance, adhesion, and the like to be suitable for the use of the adhesive for fibers of the moisture-permeable waterproof fabric.
상기와 같은 효과를 달성하기 위해 본 발명은 투습성이 우수한 무용제형 폴리우레탄 접착제의 제조방법에 관한 것으로, 이하 본 발명에 따른 바람직한 실시 예를 상세히 설명하되, 하기의 설명에서는 본 발명을 이해하는데 필요한 부분만이 설명되며 그 이외 부분의 설명은 본 발명의 요지를 흩트리지 않도록 생략될 것이라는 것을 유의하여야 한다.In order to achieve the above effects, the present invention relates to a method for preparing a solvent-free polyurethane adhesive having excellent moisture permeability, and will be described in detail below with reference to a preferred embodiment according to the present invention, in the following description necessary parts to understand the present invention It is to be noted that only the details are described and the description of other parts will be omitted so as not to distract from the gist of the present invention.
이하, 본 발명에 따른 투습성이 우수한 무용제형 폴리우레탄 접착제 조성물에 대하여 상세히 설명하면 아래의 다음과 같다.Hereinafter, the solvent-free polyurethane adhesive composition excellent in moisture permeability according to the present invention will be described in detail as follows.
본 발명은 디올 화합물의 혼합물과 디이소시아네이트 화합물 및 촉매로 이루어진 폴리우레탄 접착제 조성물에 있어서, The present invention provides a polyurethane adhesive composition comprising a mixture of diol compounds, a diisocyanate compound and a catalyst,
상기 디올 화합물의 혼합물은 폴리에틸렌글리콜 20~50 몰%, 폴리에스터폴리올 20~70 몰%, 폴리카보네이트디올 10~30 몰%로 이루어지고,The mixture of the diol compound is made of polyethylene glycol 20-50 mol%, polyester polyol 20-70 mol%, polycarbonate diol 10-30 mol%,
상기 디올 화합물의 혼합물 100 중량부에 대하여, 촉매로서, 디부틸틴디라우레이트(dibutyltin dilaurate, DBTDL) 0.01~0.03 중량부와, 0.01 to 0.03 parts by weight of dibutyltin dilaurate (DBTDL) as a catalyst, based on 100 parts by weight of the mixture of diol compounds,
상기 폴리에스터폴리올과 디이소시아네이트의 공중합체에 NCO/OH 비가 2~3이 되도록 디이소시아네이트가 함유된 것을 특징으로 하는 투습성이 우수한 무용제형 폴리우레탄 접착제 조성물에 관한 것이다. The present invention relates to a solvent-free polyurethane adhesive composition having excellent moisture permeability, characterized in that diisocyanate is contained in the copolymer of polyester polyol and diisocyanate so that NCO / OH ratio is 2-3.
본 발명에서 디올 화합물의 혼합물은 투습성이 우수한 폴리에틸렌글리콜과 물리적 특성이 우수한 폴리에스터폴리올과 폴리카보네이트디올의 혼합물로서 이루어지고, 이 혼합물을 디이소시아네이트 화합물과 반응시켜 투습성이 우수한 폴리우레탄 접착제를 합성시킨 것이 특징이다.In the present invention, the mixture of the diol compound is a mixture of polyethylene glycol having excellent moisture permeability and polyester polyol having excellent physical properties and polycarbonate diol, and the mixture is reacted with a diisocyanate compound to synthesize a polyurethane adhesive having excellent moisture permeability. It is characteristic.
그리고 본 발명에서 폴리에틸렌글리콜(polyethylene glycol)은 내수성, 기계적 물성 등은 취약하지만 투습성이 우수한 화합물로서, 폴리에틸렌글리콜의 수평균 분자량은 1,000~2,000인 것이 바람직하다. In the present invention, polyethylene glycol is a compound having weak water resistance and mechanical properties but excellent moisture permeability, and preferably has a number average molecular weight of 1,000 to 2,000 polyethylene glycol.
본 발명에서 폴리에틸렌글리콜의 혼합량은 20~50 몰%인 것이 바람직하며, 폴리에틸렌글리콜의 혼합량이 20 몰% 미만이 될 경우에는 폴리우레탄 접착제의 투습성이 저하할 우려가 있고, 폴리에틸렌글리콜의 혼합량이 50 몰%를 초과할 경우에는 폴리우레탄 접착제의 내수성, 기계적 물성 등이 저하할 우려가 있다.In the present invention, it is preferable that the mixing amount of polyethylene glycol is 20 to 50 mol%, and when the mixing amount of polyethylene glycol is less than 20 mol%, the moisture permeability of the polyurethane adhesive may decrease, and the mixing amount of polyethylene glycol is 50 mol When exceeding%, there exists a possibility that the water resistance, mechanical properties, etc. of a polyurethane adhesive may fall.
그리고 본 발명에서 상기 폴리에스터 폴리올(polyester polyol)은 접착력을 향상시키는 화합물로서, 폴리에스터 폴리올의 수평균 분자량은 1,000~5,000인 것이 바람직하다. And in the present invention, the polyester polyol (polyester polyol) is a compound that improves the adhesion, the number average molecular weight of the polyester polyol is preferably 1,000 to 5,000.
또한 상기 폴리에스터 폴리올의 혼합량은 20~70 몰%인 것이 바람직하며, 폴 리에스터 폴리올의 혼합량이 20 몰% 미만이 될 경우에는 폴리우레탄 접착제의 접착력이 저하할 우려가 있고, 폴리에스터 폴리올의 혼합량이 70 몰%를 초과할 경우에는 상대적으로 폴리에틸렌글리콜의 혼합량이 적어짐에 따라 투습성이 저하할 우려가 있다.In addition, it is preferable that the blending amount of the polyester polyol is 20 to 70 mol%, and when the blending amount of the polyester polyol is less than 20 mol%, there is a fear that the adhesive strength of the polyurethane adhesive may decrease, and the blending amount of the polyester polyol When it exceeds 70 mol%, the moisture permeability may fall as the amount of polyethylene glycol relatively decreases.
본 발명에서 사용 가능한 폴리에스터 폴리올 화합물은 디메틸프탈레이트(DMT), 아디프산(adipic acid) 및 세바신산(sebacic acid) 중에서 선택된 1종 또는 2종의 산과 부탄디올(Buthanediol), 헥산디올(Hexanediol) 중에서 선택된 1종 또는 2종의 글리콜을 에스테르화 반응시켜 제조한 화합물인 것을 사용하는 것이 바람직하다. The polyester polyol compound usable in the present invention is selected from one or two acids selected from dimethylphthalate (DMT), adipic acid and sebacic acid, butanediol, and hexanediol. It is preferable to use what is a compound manufactured by esterifying the selected 1 type or 2 types of glycols.
또한 본 발명에서 상기 폴리카보네이트디올(polycarbonate diol) 화합물은 접착력, 내구성, 내수성, 기계적 물성 등이 우수한 화합물로서, 투습성이 우수한 폴리에틸렌글리콜의 단점인 낮은 융점, 내수성, 접착력 등의 물성을 보완시켜 주는 작용을 하며, 폴리카보네이트디올의 수평균 분자량은 1,000~2,000인 것이 바람직하다.In the present invention, the polycarbonate diol compound As a compound with excellent adhesion, durability, water resistance, mechanical properties, etc., it has a function of supplementing the properties of low melting point, water resistance, adhesion, etc. which are disadvantages of polyethylene glycol with excellent moisture permeability, and polycarbonate diol has a number average molecular weight of 1,000 to 2,000. Is preferably.
상기 폴리카보네이트디올의 혼합량은 10~30 몰%인 것이 바람직하며, 폴리카보네이트디올의 혼합량이 10 몰% 미만인 경우에는 폴리에틸렌글리콜의 취약점인 융점, 내수성, 접착력 등의 물성을 제대로 보완시키지 못 할 우려가 있고, 폴리카보네이트디올의 혼합량이 30 몰%를 초과할 경우에는 접착력, 기계적 물성 등은 증가 하나 상대적으로 폴리에틸렌글리콜의 혼합향이 적어짐에 따라 투습성의 물성이 저하할 우려가 있다.It is preferable that the mixing amount of the polycarbonate diol is 10 to 30 mol%, and when the mixing amount of the polycarbonate diol is less than 10 mol%, there is a concern that it may not properly compensate for physical properties such as melting point, water resistance and adhesive strength, which are weak points of polyethylene glycol. In addition, when the mixing amount of polycarbonate diol exceeds 30 mol%, the adhesive strength, mechanical properties, etc. are increased, but there is a concern that the moisture permeability of the polyethylene glycol decreases as the mixing aroma of polyethylene glycol decreases.
본 발명에서 사용 가능한 폴리카보네이트디올 화합물은 국내 등록특허공보 제10-0204696호에 기재되어진 바와 같은 종류의 폴리카보네이트디올 화합물로써, 폴리카보네이트디올은 아래에 도시된 구조단위(a), (b) 및 (c)중에서 선택된 하나 이상의 성분을 함유하는 디올 화합물과 디알킬카보네이트, 디아릴카보네이트 또는 알킬렌카보네이트 중에서 선택된 카보네이트 화합물을 사용하여 에스테르 교환반응으로 합성하여 제조한 폴리카보네이트디올을 사용하는 것이 바람직하다. The polycarbonate diol compound usable in the present invention is a polycarbonate diol compound of the kind described in Korean Patent Publication No. 10-0204696, and the polycarbonate diol is a structural unit (a), (b) and Preference is given to using polycarbonate diols prepared by synthesis by transesterification using a diol compound containing at least one component selected from (c) and a carbonate compound selected from dialkyl carbonates, diaryl carbonates or alkylene carbonates.
상기 디올 화합물은 아래에 도시된 구조단위(a), (b) 및 (c)중에서 선택된 하나 이상의 성분을 함유한다. 일반식(a)의 그룹을 제공할 수 있는 화합물의 예는 1,6-헥산디올, 1,7-헥탄디올, 1,8-올탄디올, 1,9-노난디올 및 1,10-데칸디올이며, 이들 중에서 1,9-노난디올이 바람직하다.The diol compound contains at least one component selected from structural units (a), (b) and (c) shown below. Examples of compounds which can provide the group of formula (a) include 1,6-hexanediol, 1,7-hexanediol, 1,8-oltandiol, 1,9-nonanediol and 1,10-decanediol Among them, 1,9-nonanediol is preferable.
그리고 구조단위(b) 및 (c)의 그룹을 제공할 수 있는 화합물의 예는 각각 2-메틸-1,8-옥탄디올 및 3-메틸-1,5-펜탄디올이다. And examples of compounds which can provide groups of structural units (b) and (c) are 2-methyl-1,8-octanediol and 3-methyl-1,5-pentanediol, respectively.
-(CH2)r- (a)-(CH 2 ) r- (a)
상기에서 r은 6~10의 정수이다. R is an integer of 6-10 in the above.
또한 본 발명에서 상기 디올 화합물의 혼합물에 첨가하는 디이소시아네이트는 폴리에스터폴리올과 디이소시아네이트의 NCO/OH 비가 2~3이 되도록 디이소시아네이트를 첨가하는 것이 바람직하다. 상기에서 NCO/OH 비가 2 미만이 될 경우에는폴리우레탄이 충분히 합성되지 않을 우려가 있고, NCO/OH 비가 3을 초과할 경우에는 반응에 참여하지 않은 과량의 디이소시아네이트는 공기중 수분과 반응하여 쉽게 경화되어질 우려가 있다. In the present invention, the diisocyanate added to the mixture of the diol compounds is preferably added to the diisocyanate so that the NCO / OH ratio of the polyester polyol and the diisocyanate is 2-3. In the above case, when the NCO / OH ratio is less than 2, the polyurethane may not be sufficiently synthesized. When the NCO / OH ratio exceeds 3, the excess diisocyanate that does not participate in the reaction may easily react with moisture in the air. There is a risk of curing.
그리고 본 발명에서 상기 디이소시아네이트는 4,4'-디페닐메탄 디이소시아네이트(MDI), ｐ-페닐렌 디이소시아네이트, 톨릴렌 디이소시아네이트 1.5-나프틸렌 디이소시아네이트, 크실렌 디이소시네이트, 헥사메틸렌디이소시아네이트, 이소포론 디이소시아네이트 및 4,4'-디사이클로헥실메탄 디이소시아네이트 중에서 1종 또는 그 이상을 선택하여 사용하는 것이 바람직하며, 이들 중에서 4,4'-디페닐메탄 디이 소시아네이트(MDI)가 특히 바람직하다.In the present invention, the diisocyanate is 4,4'-diphenylmethane diisocyanate (MDI), ｐ-phenylene diisocyanate, tolylene diisocyanate 1.5-naphthylene diisocyanate, xylene diisocyanate, hexamethylene diisocyanate, Preference is given to using one or more selected from isophorone diisocyanate and 4,4'-dicyclohexylmethane diisocyanate, of which 4,4'-diphenylmethane diisocyanate (MDI) is particularly preferred. Do.
그리고 본 발명에서 사용하는 촉매인 디부틸틴디라우레이트(dibutyltin dilaurate, DBTDL)는 상기 디올 화합물의 혼합물 100 중량부에 대하여, 0.01~0.03 중량부를 첨가하는 것이 바람직하다. 촉매의 첨가량이 0.01 중량부 미만이 될 경우에는 상기 디올 화합물의 혼합물과 디이소시아네이트가 제대로 반응되지 않을 우려가 있고, 촉매의 첨가량이 0.03 중량부를 초과할 경우에는 합성반응에 특별한 영향을 미치지 않는다.And dibutyltin dilaurate (DBTDL) is a catalyst used in the present invention, it is preferable to add 0.01 to 0.03 parts by weight based on 100 parts by weight of the mixture of the diol compound. When the addition amount of the catalyst is less than 0.01 part by weight, there is a fear that the mixture of the diol compound and the diisocyanate may not react properly. When the addition amount of the catalyst exceeds 0.03 part by weight, the synthesis reaction is not particularly affected.
상기와 같은 조성비를 갖는 본 발명에 따른 투습성이 우수한 무용제형 폴리우레탄 접착제 조성물을 이용하여 폴리우레탄 접착제를 합성하는 방법을 상세히 설명하면 아래의 내용과 같다.The method of synthesizing a polyurethane adhesive using the solvent-free polyurethane adhesive composition having excellent moisture permeability according to the present invention having the composition ratio as described above is as follows.
본 발명은 디올 화합물의 혼합물과 디이소시아네이트 화합물 및 촉매로 이루어진 폴리우레탄 접착제의 제조방법에 있어서, The present invention provides a method for producing a polyurethane adhesive consisting of a mixture of diol compounds, a diisocyanate compound and a catalyst,
수분을 제거한 디올 화합물의 혼합물과 촉매를 질소분위기에서 95℃에서 30분 혼합하는 단계와;Mixing the mixture of the diol compound having been dehydrated and the catalyst at 95 ° C. for 30 minutes in a nitrogen atmosphere;
상기 혼합물에 디이소시아네이트를 투입하여 93~97℃의 온도에서 20~60 분간 합성반응하는 단계;를 거쳐 합성되어지고,Adding a diisocyanate to the mixture for 20-60 minutes at a temperature of 93-97 ° C .;
그리고, 상기 디올 화합물의 혼합물은 수평균 분자량이 1,000~2,000인 폴리에틸렌글리콜 20~50 몰%, 수평균 분자량이 1,000~5,000인 폴리에스터폴리올 20~70 몰%, 수평균 분자량이 1,000~2,000인 폴리카보네이트디올 10~30 몰%로 이루어지는 것을 특징으로 한다. In addition, the mixture of the diol compound is 20 to 50 mol% of polyethylene glycol having a number average molecular weight of 1,000 to 2,000, 20 to 70 mol% of a polyester polyol having a number average molecular weight of 1,000 to 5,000, and a poly having a number average molecular weight of 1,000 to 2,000 It is characterized by consisting of 10 to 30 mol% carbonate diol.
본 발명에 따른 폴리우레탄 접착제의 제조방법에 사용되어지는 화합물에 대해서는 상기에서 이미 상세히 설명한 바 있으므로 여기서는 그 설명을 생략하기로 한다.Since the compound used in the method for producing a polyurethane adhesive according to the present invention has been described in detail above, the description thereof will be omitted.
본 발명에 따른 폴리우레탄 접착제의 제조방법은 상기 무용제형 습기경화 폴리우레탄 수지를 원쇼트 프로세스(one shot process)를 이용하여 합성시킴으로써, 합성방법이 간단한 프로세스 공정인 것이 특징이다. The method for producing a polyurethane adhesive according to the present invention is characterized in that the synthesis method is a simple process process by synthesizing the non-solvent moisture-curable polyurethane resin using a one shot process.
그리고 본 발명에서 폴리우레탄의 합성조건은 93~97℃에서 20~60 분간 반응 합성시키는 것이 바람직하며, 상기에서 한정한 합성조건 미만이 될 경우에는 폴리우레탄 합성이 충분히 되지않을 우려가 있고, 상기에서 한정한 합성조건을 초과할 경우에는 반응수율이 저하할 우려가 있다.And in the present invention, the synthetic conditions of the polyurethane is preferably reacted and synthesized for 20 to 60 minutes at 93 ~ 97 ℃, if less than the above synthetic conditions there is a fear that the polyurethane synthesis is not enough, When the limited synthetic conditions are exceeded, the reaction yield may be lowered.
이하, 본 발명의 구성을 아래 실시예에 의거하여 더욱 상세히 설명하겠는바 본 발명이 하기의 실시 예에 의해서만 반드시 한정되는 것은 아니다.Hereinafter, the configuration of the present invention will be described in more detail based on the following examples, but the present invention is not necessarily limited only to the following examples.
1. 투습성이 우수한 무용제형 폴리우레탄 접착제 제조1. Preparation of solvent-free polyurethane adhesive with excellent moisture permeability
아래 [표 1]의 내용과 같이 수분을 제거한 수평균 분자량이 1,000~2,000인 폴리에틸렌글리콜과 수평균 분자량이 1,000~5,000인 폴리에스터폴리올 및 수평균 분자량이 1,000~2,000인 폴리카보네이트디올의 혼합물에 DBTDL 촉매를 첨가하고, 질소분위기에서 95℃ 온도에서 30분 혼합한 다음 상기 혼합물에 디이소시아네이트(MDI)를 투입하여 95℃에서 30 분간 합성반응시켜 폴리우레탄 접착제를 제조하였다. DBTDL in a mixture of polyethylene glycol having a number average molecular weight of 1,000 to 2,000, a polyester polyol having a number average molecular weight of 1,000 to 5,000, and a polycarbonate diol having a number average molecular weight of 1,000 to 2,000, as shown in Table 1 below. A catalyst was added, the mixture was mixed for 30 minutes at 95 ° C. in a nitrogen atmosphere, and then diisocyanate (MDI) was added to the mixture to synthesize a polyurethane adhesive at 95 ° C. for 30 minutes.
(20)1.0
20
(24)1.2
(24)
(30)1.5
(30)
(40)2.0
40
(50)2.5
50
(20)1.0
20
Polyester Diol (mole)
(70)3.5
(70)
(60)3.0
(60)
(50)2.5
50
(36)1.8
(36)
(20)1.0
20
(80)4.0
(80)
(80)4.0
(80)
Polycarbonate Diol (mole)
(10)0.5
10
(16)0.8
(16)
(20)1.0
20
(24)1.2
(24)
(30)1.5
(30)
(20)1.0
20
R ratio(NCO/OH)Diisocyanate (MDI) (mole)
R ratio (NCO / OH)
210
2
210
2
210
2
210
2
210
2
210
2
210
2
주 1) 상기 폴리에틸렌글리콜, 폴리에스터폴리올 및 폴리카보네이트디올의 혼합물 100 중량부에 대하여 첨가한 양임.Note 1) The amount is added based on 100 parts by weight of the mixture of polyethylene glycol, polyester polyol and polycarbonate diol.
2. 무용제형 폴리우레탄 접착제의 평가 2. Evaluation of Solvent-free Polyurethane Adhesive
실시예 1~5 및 비교예 1, 2의 무용제형 폴리우레탄 접착제에 대한 접착강도와 투습도를 평가한 결과는 아래 [표 2]의 내용과 같다. The results of evaluating the adhesive strength and moisture permeability for the solvent-free polyurethane adhesives of Examples 1 to 5 and Comparative Examples 1 and 2 are as shown in Table 2 below.
주 1) 접착강도 : 습도 60%, 40℃에서 48시간 방치 후 만능시험기로 측정함.Note 1) Adhesion strength: Measured by universal testing machine after leaving for 48 hours at 60% humidity and 40 ℃.
2) 투습도 : 투습컵 시험법, 측정원단은 폴리에스터(Polyester) 원단에 접착제 코팅 후 투습방수용 TPU 필름을 합지하여 원단 제작함. 2) Water vapor permeability: The moisture permeation cup test method, and the measuring fabric is made of polyester by coating the adhesive TPU film for waterproofing and then waterproofing the fabric.
상기 [표 2]에 기재되어 있는 바와 같은 구성성분에 의해 합성시켜 제조한 실시예 1 내지 5 및 비교예 1, 2의 폴리우레탄 접착제에 대한 접착강도 및 투습도를 시험한 결과, 실시예 1 내지 5는 비교예 1, 2에 비해 접착강도 및 투습도의 성능이 모두 우수함을 확인할 수 있었다.As a result of testing the adhesive strength and moisture permeability of the polyurethane adhesives of Examples 1 to 5 and Comparative Examples 1 and 2 prepared by synthesizing with the components as described in the above [Table 2], Examples 1 to 5 It was confirmed that the excellent performance of both the adhesive strength and moisture permeability compared to Comparative Examples 1 and 2.
그리고 실시예 1 내지 5의 폴리우레탄 접착제에서, 투습도의 경우에는 폴리에틸렌글리콜의 함량이 높을수록 투습도가 향상됨을 알 수 있었고, 폴리에틸렌글리콜의 혼합량이 증가함에 따라 취약해지는 내수성, 기계적 물성의 저하를 방지하기 위하여 폴리에스터폴리올과 폴리카보네이트디올를 적절한 혼합시켜 접착강도를 향상시킬 수 있도록 한 것임을 알 수 있었다. And in the polyurethane adhesives of Examples 1 to 5, in the case of moisture permeability, it was found that the higher the content of polyethylene glycol, the better the moisture permeability, and to prevent a decrease in water resistance and mechanical properties that become weak as the amount of polyethylene glycol is increased. In order to improve the adhesive strength by properly mixing the polyester polyol and polycarbonate diol.
또한 비교예 1, 2에 있어서는 비교예 1의 경우 폴리에틸렌글리콜을 혼합하지 않음에 따라 실시예 1 내지 5에 비해 접착력은 우수하나 투습도의 물성이 대단히 낮음을 알 수 있었고, 비교예 2의 경우에는 폴리카보네이트디올이 혼합되지 않음에 따라 투습도는 우수하나 접착력이 실시예 1 내지 5에 비해 대단히 낮음을 알 수 있었다.In addition, in Comparative Examples 1 and 2, the polyethylene glycol was not mixed in Comparative Example 1, but the adhesion was superior to Examples 1 to 5, but the physical properties of the moisture permeability were very low. As the carbonate diol was not mixed, the moisture permeability was excellent but the adhesion was very low compared to Examples 1 to 5.
상술한 바와 같이, 본 발명에 따른 투습성이 우수한 무용제형 폴리우레탄 접착제 조성물 및 이를 이용한 폴리우레탄 접착제의 제조방법을 상기의 바람직한 실시 예를 통해 설명하고, 그 우수성을 확인하였지만 해당 기술분야의 당업자라면 하기의 특허청구범위에 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 non-solvent-type polyurethane adhesive composition excellent in moisture permeability according to the present invention and a method for producing a polyurethane adhesive using the same have been described through the above-described preferred embodiment, the superiority was confirmed by those skilled in the art It will be understood that various modifications and changes can be made in the present invention without departing from the spirit and scope of the invention as set forth in the claims.
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| KR101322761B1 (en) * | 2012-12-12 | 2013-11-07 | 한국신발피혁연구원 | The manufacturing method of polyurethane coating resin composition |
| KR101420171B1 (en) * | 2013-02-01 | 2014-07-21 | 주식회사 알토켐 | Adhesive resin composition having high heat-resistance and method of manufacturing the same |
| KR102121014B1 (en) * | 2018-11-09 | 2020-06-09 | 한국신발피혁연구원 | Hotmelt polyurethane adhesive with hydroxyl group having excellent coating property and adhesion property |
| CN109776028A (en) * | 2019-03-11 | 2019-05-21 | 东莞市浩展高分子材料有限公司 | A kind of gluing stone porous pavement material and its construction method |
| JP2023528248A (en) * | 2020-06-03 | 2023-07-04 | ダウ グローバル テクノロジーズ エルエルシー | Solvent-based laminating adhesive |
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| JP2008075007A (en) * | 2006-09-22 | 2008-04-03 | Lintec Corp | Marking adhesive sheet |
| KR20080088628A (en) * | 2006-12-01 | 2008-10-02 | 디아이씨 가부시끼가이샤 | Moisture curable polyurethane hot melt adhesive and laminated sheet using the same |
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| JP2008075007A (en) * | 2006-09-22 | 2008-04-03 | Lintec Corp | Marking adhesive sheet |
| KR20080088628A (en) * | 2006-12-01 | 2008-10-02 | 디아이씨 가부시끼가이샤 | Moisture curable polyurethane hot melt adhesive and laminated sheet using the same |
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