KR102188218B1 - Flame retardant reactive polyurethane hot-melt adhesives having excellent thermal resistance and producing method of coating textile using the same - Google Patents
Flame retardant reactive polyurethane hot-melt adhesives having excellent thermal resistance and producing method of coating textile using the same Download PDFInfo
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- 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
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- 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
- C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
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- C08G18/72—Polyisocyanates or polyisothiocyanates
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- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/304—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being heat-activatable, i.e. not tacky at temperatures inferior to 30°C
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- D06M2200/30—Flame or heat resistance, fire retardancy properties
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Abstract
Description
본 발명은 내열성이 우수한 난연형 반응성 폴리우레탄 핫멜트 접착제 및 이를 이용한 코팅 원단의 제조방법에 관한 것으로, 더욱 상세하게는 방향족 폴리에스테르 폴리올과 폴리카프로락톤을 이용한 고접착성 수지에 우수한 내열성 부여가 가능한 실리콘과 디아민을 적용하여 260℃ 이상의 내열성을 가지며, 또한 반응성 난연제의 적용을 통해 산업용 및 소방용으로 적용 가능한 고형분 100%의 친환경 접착제를 용제의 휘발이 이루어지는 건조과정 없이 열용융에 의해 아라미드사와 같은 난연/고내열성 섬유 원단에 접착되어 접착력과 박리강도가 우수하고 부드러운 촉감을 갖는 내열성이 우수한 난연형 반응성 폴리우레탄 핫멜트 접착제 및 이를 이용한 코팅 원단의 제조방법에 관한 것이다.The present invention relates to a flame-retardant reactive polyurethane hot melt adhesive having excellent heat resistance and a method of manufacturing a coated fabric using the same, and more particularly, to a silicone capable of imparting excellent heat resistance to a high adhesive resin using aromatic polyester polyol and polycaprolactone. It has heat resistance of 260℃ or more by applying and diamine, and 100% solid content eco-friendly adhesive that can be applied for industrial and firefighting through the application of reactive flame retardant is flame retardant/high like aramid by heat melting without the drying process in which the solvent volatilizes. The present invention relates to a flame-retardant reactive polyurethane hot melt adhesive having excellent adhesion and peel strength and excellent heat resistance having a soft touch by being adhered to heat-resistant fiber fabric, and a method of manufacturing a coated fabric using the same.
최근 들어 제철소나 화재 현장과 같은 초고온 환경에 대응하는 안전보호복은 크게 산업용과 소방용으로 분류되고 있다. 산업용 방열복은 용융 금속류를 취급하는 산업현장에서 작업자를 보호하는 보호복으로 사용되고 있으며, 소방용 방열복은 화염이나 고온의 복사열에 접근할 수 있는 불연성 내열피복을 말한다.In recent years, safety protective clothing that responds to ultra-high temperature environments such as steel mills and fire sites is largely classified into industrial and firefighting applications. Industrial heat shields are used as protective clothes to protect workers in industrial sites handling molten metals, and fire protection heat shields are non-flammable heat resistant coatings that can access flames or high-temperature radiant heat.
상기 산업용 및 소방용 방열복은 통상 아라미드로 구성된 부직포와 단층 및 다층의 금속 알루미늄 증착 필름과 접착제로 구성되는데, 아라미드 부직포와 증착 필름으로 구성된 제품은 기존의 일반적인 용제형 접착제를 적용할 경우 낮은 내열성을 나타내며, 이에 추가하여 첨가형 난연제를 사용하는 공정으로 인해 접착 불량과 블루밍(blooming) 현상으로 인한 가공성 불량 문제를 초래되고 있다.The industrial and fire-fighting heat dissipation suit is usually composed of a non-woven fabric composed of aramid and a single-layer and multi-layer metal aluminum-deposited film and adhesive.The product composed of aramid non-woven fabric and vapor-deposited film exhibits low heat resistance when a conventional solvent-type adhesive is applied. In addition, due to the process of using an additive-type flame retardant, a problem of poor workability due to poor adhesion and blooming phenomenon is caused.
이러한 변화에 따라 산업용 및 소방용 방열복에 사용될 수 있는 접착제 소재에 대해서도 다양한 물성의 개선이 요구되고 있으며, 가장 중요한 과제는 내열성 향상이지만 방열복에 사용되는 섬유소재용 접착제 또는 핫멜트의 경우 기존의 건축용 또는 구조물용 접착제와 달리 활동성과 세탁 내구성 향상을 위한 유연성과 높은 접착성능이 요구되고 있어, 상기 핫멜트 접착제에 대한 관심과 기능성 개선에 대한 필요성이 더욱 증대되고 있다.According to these changes, various physical properties are required for adhesive materials that can be used for industrial and firefighting heat shields, and the most important task is to improve heat resistance, but in the case of fiber material adhesives or hot melts used in heat shields, existing adhesives for construction or structures In contrast, flexibility and high adhesive performance for improving activity and washing durability are required, and thus, interest in the hot melt adhesive and the need for functional improvement are further increasing.
일반적으로, 핫멜트 접착제는 열에 의해 용융시켜 적용하기 때문에 휘발성 유기용제의 배출이 매우 적어 친환경 접착제로의 사용이 증가됨에 따라 최근에는 인체에 대한 유해성이 있는 휘발성 유기화합물의 배출 이외에도 지구 온난화를 방지하기 위한 노력이 환경보호의 관점에서 제도화되고 있으며, 이런 세계적인 각국의 노력의 일환으로 이산화탄소 배출이 적은, 즉 LCA(Life Cycle Assessment)값이 낮은 수지의 사용이 요구되고 있다.In general, hot melt adhesives are applied by melting by heat, so the emission of volatile organic solvents is very small, and as the use of eco-friendly adhesives has increased, recently, in addition to the emission of volatile organic compounds that are harmful to the human body, it is intended to prevent global warming. Efforts are being institutionalized from the viewpoint of environmental protection, and as part of these global efforts, the use of resins with low carbon dioxide emissions, that is, a low LCA (Life Cycle Assessment) value, is required.
상기 핫멜트 접착제는 실온에서 고체물질이지만 열을 가하면 유체상태로 용융되어 피착재에 대해 접착력을 갖게 되며, 용융된 상태의 핫멜트 접착제를 냉각시키면 고체형태로 회복되어 응집력을 회복한다. 접착력은 표면의 구멍이나 요철에 의해 액상의 접착제가 흘러 들어가 접착력을 높이는 투모효과에 영향을 받는데, 이 효과를 잘 이용하기 위해서 핫멜트 접착제는 용융되었을 때 충분한 흐름성이 필요하므로 적절한 점도를 갖게 하기 위하여 높은 온도에서 용융시켜 사용하고 있다.The hot melt adhesive is a solid material at room temperature, but when heat is applied, it melts into a fluid state to have adhesive strength to the adherend, and when the hot melt adhesive in the molten state is cooled, it recovers to a solid form to restore cohesion. Adhesion is affected by the dropping effect of increasing adhesion by flowing liquid adhesive due to holes or irregularities on the surface.In order to utilize this effect well, hot melt adhesive needs sufficient flowability when melted, so that it has an appropriate viscosity. It is used by melting it at a high temperature.
종래의 범용 핫멜트 접착제는 주로 에틸렌비닐아세테이트(EVA)를 주성분으로 하고 점착력을 향상시키기 위한 증점착제(Tackifier) 및 점도를 낮추기 위한 왁스로 구성된다. 상기 에틸렌비닐아세테이트는 비닐아세테이트의 비율이 20 ~ 40중량%인 것이 일반적인데, 증점착제는 검 로진, 로진에스테르, C5 석유수지, C9 석유수지, 쿠마론수지, 아크릴변성 석유수지 등이 사용되며, 왁스로는 파라핀 왁스, 폴리에틸렌 왁스, 폴리프로필렌 왁스 등이 사용된다. 그러나 왁스와 에틸렌비닐아세테이트의 상용성이 좋지 않으면 점도를 효과적으로 낮추지 못할 뿐만 아니라 사용온도에서 상분리가 일어나 접착력을 현저히 감소시키고 접착제의 형태도 갖추기 어려운 문제가 발생할 수 있다.Conventional general-purpose hot melt adhesives are mainly composed of ethylene vinyl acetate (EVA) as a main component, a tackifier for improving adhesion, and a wax for lowering the viscosity. As for the ethylene vinyl acetate, it is common that the proportion of vinyl acetate is 20 to 40% by weight, and as the thickener, gum rosin, rosin ester, C5 petroleum resin, C9 petroleum resin, coumaron resin, acrylic modified petroleum resin, etc. are used, As the wax, paraffin wax, polyethylene wax, polypropylene wax, and the like are used. However, if the compatibility between the wax and the ethylene vinyl acetate is not good, not only the viscosity may not be effectively lowered, but also phase separation may occur at the temperature of use, which significantly reduces adhesive strength and makes it difficult to form an adhesive.
이러한 EVA계 접착제의 문제점을 해결하기 위해, 대한민국 공개특허 제10-2008-0088628호에서는 폴리올(A)과 폴리이소시아네이트(B)를 반응시켜 얻어지는 우레탄 프리폴리머를 함유하고, 그 폴리올(A)이 폴리올(A)의 전량에 대하여 폴리카보네이트 폴리올(a1)을 40질량%∼80질량%, 폴리테트라메틸렌글리콜(a2)을 5질량%∼40질량%, 및 지방족 폴리카르복시산 및 방향족 폴리카르복시산을 포함하는 폴리카르복시산과, 비스페놀A에 알킬렌옥사이드를 부가하여 얻어지는 폴리에테르 폴리올을 반응시켜 얻어지는 폴리에스테르 폴리올(a3)을 5질량%∼40질량% 함유하는 습기 경화성 폴리우레탄 핫멜트 접착제 및 이것을 사용한 적층 시트가 제공되며, 이 접착제는 적층 시트의 유연한 촉감을 손상시키지 않고 가혹한 세탁 조건 하에서의 세탁을 반복하여 행한 후에도 뛰어난 접착 강도를 유지할 수 있다고 한다.In order to solve the problem of the EVA-based adhesive, Korean Patent Application Laid-Open No. 10-2008-0088628 contains a urethane prepolymer obtained by reacting a polyol (A) and a polyisocyanate (B), and the polyol (A) is a polyol ( Polycarboxylic acid containing 40% by mass to 80% by mass of polycarbonate polyol (a1), 5% by mass to 40% by mass of polytetramethylene glycol (a2), and aliphatic polycarboxylic acid and aromatic polycarboxylic acid with respect to the total amount of A) And a moisture-curable polyurethane hot melt adhesive containing 5% by mass to 40% by mass of a polyester polyol (a3) obtained by reacting a polyether polyol obtained by adding an alkylene oxide to bisphenol A, and a laminated sheet using the same, It is said that this adhesive can maintain excellent adhesive strength even after repeated washing under severe washing conditions without impairing the flexible touch of the laminated sheet.
또한, 동 공개특허 제10-2011-0022764호를 보면, 아크릴수지, 폴리우레탄수지, 폴리에스테르수지, 톨루엔 디이소시아네이트 트라이머(Toluene Diisocyanate Trimer, TDI Trimer), 시클로헥실메탄 디이소시아네이트(Cyclohexylmethane diisocyanate, H12MDI), 톨루엔 디이소시아네이트(Toluene Diisocyanate, TDI), 메틸렌 디페닐 디이소시아네이트(Methylene Diphenyl Diisocyanate, MDI), 헥사메틸렌 디이소시아네이트(Hexamethylene Diisocyanate, HMDI) 및 폴리프로필렌글리콜(PPG)를 혼합하여 제1 혼합물을 제조하는 단계(단계 1); 상기 제1 혼합물에 계면활성제를 혼합하여 제2 혼합물을 만드는 단계(단계 2); 및 상기 제2 혼합물을 교반하여 친환경 접착제 조성물을 제조하는 단계(단계 3)를 포함하는 친환경 접착제 조성물의 제조방법을 개시하고 있는바, 이는 접착력이 우수하면서도 황변현상이 발생하지 않고 경화가 신속하게 이루어지며, 중금속이나 휘발성 유기화합물(VOC)을 포함하고 있지 않는다는 장점이 있다.In addition, referring to Patent Publication No. 10-2011-0022764, acrylic resin, polyurethane resin, polyester resin, toluene diisocyanate trimer (TDI Trimer), cyclohexylmethane diisocyanate (Cyclohexylmethane diisocyanate, H 12 MDI), toluene diisocyanate (TDI), methylene diphenyl diisocyanate (MDI), hexamethylene diisocyanate (HMDI) and polypropylene glycol (PPG) are mixed to form a first mixture Manufacturing a step (step 1); Mixing a surfactant with the first mixture to prepare a second mixture (step 2); And a step of preparing an eco-friendly adhesive composition by stirring the second mixture (step 3), which has excellent adhesion and does not cause yellowing and cures quickly. It has the advantage that it does not contain heavy metals or volatile organic compounds (VOC).
그리고 본 출원인은 특허 제10-1709909호를 통해 디이소시아네이트의 삼량체로 생성되는 이소시아누네이트의 화학적 가교결합을 이용하여 접착력과 구조적 강도가 발휘됨과 동시에 경화도의 증가에 의해 접착제 자체의 열 안정성과 화학적 안정성이 우수하고 이를 통해 내열성과 내후성의 향상이 가능하며, 용제를 사용하지 않는 100% 고형분의 친환경 폴리우레탄 접착제로서, 용제의 휘발이 이루어지는 건조과정 없이 열용융에 의해 섬유소재에 접착됨으로써 이를 사용한 코팅 원단은 접착력과 박리강도 등의 물성이 양호하고 부드러운 촉감과 우수한 내열성을 갖는 반응성 폴리우레탄 핫멜트 접착제를 개발한바 있다.In addition, the applicant of the present invention uses the chemical cross-linking of isocyanate produced as a trimer of diisocyanate through Patent No. 10-1709909 to demonstrate adhesion and structural strength, and at the same time, the thermal stability and chemical stability of the adhesive itself by increasing the degree of curing. It has excellent stability, and it is possible to improve heat resistance and weather resistance, and it is an eco-friendly polyurethane adhesive with 100% solid content that does not use a solvent.It is a coating using it by bonding to a fiber material by heat melting without a drying process in which solvent volatilization occurs. Fabrics have developed a reactive polyurethane hot melt adhesive that has good physical properties such as adhesion and peel strength, and has a soft touch and excellent heat resistance.
더 나아가, 본 발명에서는 방향족 폴리에스테르 폴리올과 폴리카프로락톤을 이용한 고접착성 수지에 우수한 내열성의 부여가 가능한 실리콘과 디아민을 적용하여 260℃ 이상의 우수한 내열성을 가지며, 또한 반응성 난연제의 적용을 통해 산업용 및 소방용으로 적용 가능한 고형분 100%의 친환경 접착제를 용제의 휘발이 이루어지는 건조과정 없이 열용융에 의해 아라미드사와 같은 난연/고내열성 섬유 원단에 접착함으로써 접착력과 박리강도가 우수하고 부드러운 촉감을 나타내는 내열성이 우수한 난연형 반응성 폴리우레탄 핫멜트 접착제 및 이를 이용한 코팅 원단의 제조방법을 연구하여 본 발명을 완성한 것이다.Furthermore, in the present invention, silicone and diamine, which can impart excellent heat resistance to high-adhesive resins using aromatic polyester polyol and polycaprolactone, have excellent heat resistance of 260° C. or higher, and are used for industrial and industrial use through the application of a reactive flame retardant. An eco-friendly adhesive with 100% solid content, which can be applied for firefighting, is bonded to flame-retardant/high heat-resistant fiber fabrics such as aramid by heat melting without a drying process in which solvent volatilization occurs, so that it has excellent adhesion and peel strength, and excellent heat resistance showing a soft touch. The present invention was completed by studying the type reactive polyurethane hot melt adhesive and a method of manufacturing a coated fabric using the same.
본 발명의 목적은 산업용 안전복 및 소방복 등과 같은 열 또는 화염에 노출되는 소재에 사용되는 금속증착 필름과 아라미드 부직포로 구성된 제품에 첨가형 난연제를 사용하는 공정으로 인한 접착 불량과 블루밍(blooming) 현상으로 인한 가공성 불량을 개선하기 위한 것으로, 방향족 폴리에스테르 폴리올과 폴리카프로락톤을 이용한 고접착성 수지에 우수한 내열성 부여가 가능한 실리콘과 디아민을 적용하여 강한 접착력과 내굴곡성 및 유연성을 발현하며, 또한 반응성 난연제의 적용을 통해 용제를 사용하지 않는 100% 고형분의 친환경 폴리우레탄 접착제를 열용융에 의해 섬유소재에 접착할 경우 용제의 휘발이 이루어지는 건조과정 없이 열용융에 의해 원단에 접착됨으로써 접착력 및 박리강도, 촉감 등의 물성이 양호하고 내열성이 우수한 난연형 반응성 폴리우레탄 핫멜트 접착제 및 이를 이용한 코팅 원단의 제조방법을 제공하는 것이다.An object of the present invention is due to poor adhesion and blooming due to the process of using an additive-type flame retardant in a product composed of a metal-deposited film and aramid nonwoven fabric used for materials exposed to heat or flames such as industrial safety clothing and firefighting clothing. It is to improve processability defects, by applying silicone and diamine that can impart excellent heat resistance to high-adhesive resins using aromatic polyester polyols and polycaprolactones, expressing strong adhesion, bending resistance, and flexibility, and also applying reactive flame retardants. When a 100% solid, eco-friendly polyurethane adhesive that does not use a solvent is adhered to a fiber material by heat melting, it is adhered to the fabric by heat melting without the drying process in which the solvent volatilizes, so that adhesion, peel strength, and touch It is to provide a flame-retardant reactive polyurethane hot melt adhesive having good physical properties and excellent heat resistance, and a method of manufacturing a coated fabric using the same.
본 발명에 의한 내열성이 우수한 난연형 반응성 폴리우레탄 핫멜트 접착제는 (a) 수평균분자량 1,500 ~ 3,500 범위의 폴리카프로락톤 15 ~ 25중량%; (b) 수평균분자량 2,000 ~ 3,500 범위의 방향족 폴리에스테르 폴리올 15 ~ 25중량%; (c) 내열성 향상을 위한 반응성 실리콘 3 ~ 5중량%; (d) 안정적인 난연성 부여를 위한 반응성 난연제 5 ~ 12중량%; (e) 접착제의 결정성 및 강도 조정을 위한 쇄연장제 1 ~ 2중량%; (f) 방향족 이소시아네이트 15 ~ 30중량%의 비율로 반응시켜 제조한 프리폴리머 A와, (g) 내열성 및 접착강도 향상을 위한 수평균분자량 1,000 ~ 2,000 범위의 디아민 5 ~ 20 중량%; (h) 디아민과의 프리폴리머 합성을 위한 지방족 이소시아네이트 1 ~ 3중량%의 비율로 반응시켜 제조한 프리폴리머 B를, (i) 난연성 부여를 위한 첨가형 난연제 5 ~ 10중량%와 혼합하여 이루어지는 것을 특징으로 한다.Flame-retardant reactive polyurethane hot melt adhesive having excellent heat resistance according to the present invention includes (a) 15 to 25% by weight of polycaprolactone having a number average molecular weight of 1,500 to 3,500; (b) 15 to 25% by weight of aromatic polyester polyol having a number average molecular weight of 2,000 to 3,500; (c) 3 to 5% by weight of reactive silicone for improving heat resistance; (d) 5 to 12% by weight of a reactive flame retardant for imparting stable flame retardancy; (e) 1 to 2% by weight of a chain extender for adjusting the crystallinity and strength of the adhesive; (f) a prepolymer A prepared by reacting at a ratio of 15 to 30% by weight of an aromatic isocyanate, and (g) 5 to 20% by weight of a diamine having a number average molecular weight in the range of 1,000 to 2,000 for improving heat resistance and adhesive strength; (h) Prepolymer B prepared by reacting at a ratio of 1 to 3% by weight of an aliphatic isocyanate for the synthesis of the prepolymer with diamine is mixed with 5 to 10% by weight of an additive-type flame retardant for imparting flame retardancy. .
본 발명의 바람직한 실시예에 따르면, 상기 반응성 실리콘(c)은 모노 터미네이티드 타입(mono terminated type)의 수평균분자량 1,000 ~ 2,000 범위를 가지는 반응성 디메틸실록산 디올 또는 말단에 아민기를 가지는 아민당량이 250 ~ 270g/NH인 반응성 디메틸실록산 디아민을 1종 이상 사용하며, 상기 반응성 난연제(d)는 수평균분자량 250 ~ 500인 디에틸 N,N-비스(2-하이드록시에틸) 아미노메틸 포스포네이트 또는 테트라브로모 프탈레이트 디올 타입의 반응성 난연제 중에서 선택되는 1종 이상을 사용한다. 또한, 상기 프리폴리머 A와 프리폴리머 B의 중량비율은 8 : 2 ~ 9 : 1이며, 활성수소 원자화합물 대비 디이소시아네이트의 최종 반응비율(OH/NCO 비율)은 당량비로 1.2 ~ 1.7의 값을 갖도록 조정된 것을 특징으로 하고 있다.According to a preferred embodiment of the present invention, the reactive silicone (c) is a reactive dimethylsiloxane diol having a number average molecular weight of 1,000 to 2,000 of a mono-terminated type or an amine equivalent having an amine group at the terminal of 250 One or more reactive dimethylsiloxane diamines of ~ 270 g/NH are used, and the reactive flame retardant (d) is diethyl N,N-bis(2-hydroxyethyl) aminomethyl phosphonate having a number average molecular weight of 250 ~ 500 or At least one selected from among tetrabromophthalate diol-type reactive flame retardants is used. In addition, the weight ratio of the prepolymer A and the prepolymer B is 8: 2 ~ 9: 1, and the final reaction ratio (OH/NCO ratio) of diisocyanate to the active hydrogen atom compound is adjusted to have a value of 1.2 ~ 1.7 as an equivalent ratio. It is characterized by that.
그리고 본 발명에 의한 코팅 원단의 제조방법은 상기 내열성이 우수한 난연형 반응성 폴리우레탄 핫멜트 접착제를 80 ~ 120℃의 온도로 용융시키고 섬유 원단에 5 ~ 50g/㎡의 양으로 도포한 다음, 온도 30 ~ 50℃, 상대습도 70 ~ 100%의 조건에서 12 ~ 48시간 동안 숙성시켜 제조되는 것으로, 상기 난연형 반응성 폴리우레탄 핫멜트 접착제의 난연성은 V-0등급(UL94 수직법)이며, 상기 코팅 원단은 내열성 260 ~ 300℃, 박리강도 11 ~ 15N/5cm인 것을 특징으로 한다.And the manufacturing method of the coated fabric according to the present invention melts the flame-retardant reactive polyurethane hot melt adhesive having excellent heat resistance at a temperature of 80 to 120°C, and then applies it to the fabric in an amount of 5 to 50 g/m 2, and then at a temperature of 30 to It is manufactured by aging for 12 to 48 hours at 50°C and 70 to 100% relative humidity, and the flame retardancy of the flame retardant reactive polyurethane hot melt adhesive is V-0 grade (UL94 vertical method), and the coated fabric is heat resistant. It is characterized in that 260 ~ 300 ℃, peel strength 11 ~ 15N / 5cm.
본 발명의 내열성이 우수한 난연형 반응성 폴리우레탄 핫멜트 접착제는 방향족 폴리에스테르 폴리올과 폴리카프로락톤의 조성으로 우레아 가교결합을 이용한 고접착성 수지를 사용하고 우수한 내열성 부여가 가능한 실리콘과 디아민을 적용하여 우수한 가공성과 유연성을 바탕으로 경화도가 증가되어 강한 접착력과 구조적 강도를 발휘하며, 아울러 반응성 실리콘과 반응성 난연제의 적용을 통해 접착제 자체의 열 안정성 및 난연성이 우수하고 내열성과 내후성이 향상되는 효과가 있다.The flame-retardant reactive polyurethane hot melt adhesive with excellent heat resistance of the present invention uses a high-adhesive resin using urea crosslinking with a composition of aromatic polyester polyol and polycaprolactone, and has excellent processability by applying silicone and diamine that can impart excellent heat resistance. The degree of curing is increased based on the flexibility and strong adhesion and structural strength. In addition, the heat stability and flame retardancy of the adhesive itself are excellent through the application of reactive silicone and reactive flame retardant, and heat resistance and weather resistance are improved.
또한, 본 발명의 난연형 반응성 폴리우레탄 핫멜트 접착제는 용제를 사용하지 않는 100% 고형분의 친환경 폴리우레탄 접착제로서 열용융에 의해 섬유소재에 접착되어 용제의 휘발이 이루어지는 건조과정 없이 접착력과 박리강도 등의 물성 및 가공성이 양호하고 부드러운 촉감과 우수한 내열성을 갖는 코팅 원단을 제조할 수 있는 장점이 있다.In addition, the flame-retardant reactive polyurethane hot-melt adhesive of the present invention is an eco-friendly polyurethane adhesive with 100% solid content that does not use a solvent. It is adhered to the fiber material by heat melting to evaporate the solvent without the drying process, such as adhesion and peel strength. It has the advantage of being able to manufacture a coated fabric having good physical properties and processability, a soft touch and excellent heat resistance.
이하에서는 본 발명에 의한 내열성이 우수한 난연형 반응성 폴리우레탄 핫멜트 접착제 및 이를 이용한 코팅 원단의 제조방법에 대하여 설명하기로 하되, 이는 본 발명이 속하는 기술분야에서 통상의 지식을 가진 사람이 용이하게 실시할 수 있을 정도로 예시하기 위한 것이지, 이로 인해 본 발명의 기술적인 사상 및 범주가 한정되는 것을 의미하지는 않는다.Hereinafter, a method of manufacturing a flame-retardant reactive polyurethane hot melt adhesive having excellent heat resistance according to the present invention and a coating fabric using the same will be described, which can be easily implemented by a person having ordinary knowledge in the technical field to which the present invention belongs. It is intended to illustrate to the extent possible, and this does not mean that the technical spirit and scope of the present invention are limited.
일반적으로, 폴리우레탄 수지는 중합체 중에 이소시아네이트기(-NCO)와 수산기(-OH)의 반응에 의해서 생성된 우레탄결합을 기본으로 하여 생성된 수지로서 그 원료는 폴리올, 이소시아네이트, 체인확장제 등을 사용하며, 통상적으로 각종 용제가 첨가되어 용액중합방법으로 제조된다. 이에 따라 폴리우레탄 수지의 특징은 피막강도, 접착강도가 우수하기 때문에 얇은 코팅막의 제조가 가능하고 코팅피막의 탄력성이 풍부하여 촉감이 부드럽고 다공질막 필름으로 제조할 수 있어 투습성, 통기성을 부여할 수 있을 뿐만 아니라 내한성이 우수하며, 가소제를 사용하지 않고 가공하기 때문에 가소제로 인하여 발생되는 작업성 문제가 적다.In general, polyurethane resins are resins produced based on urethane bonds generated by the reaction of isocyanate groups (-NCO) and hydroxyl groups (-OH) in a polymer, and the raw materials thereof are polyols, isocyanates, chain extenders, etc. , In general, various solvents are added to prepare a solution polymerization method. Accordingly, the characteristics of polyurethane resin are excellent film strength and adhesive strength, so it is possible to manufacture a thin coating film, and because the elasticity of the coating film is abundant, it can be made into a porous film film that has a soft touch and can give moisture permeability and breathability. In addition, it has excellent cold resistance, and since it is processed without using a plasticizer, there are few workability problems caused by the plasticizer.
폴리올(Polyol)은 이소시아네이트(Isocyanate)와 함께 반응하여 폴리우레탄을 제조하는데 사용되는 활성수소화합물로서 분자 중에 하이드록실기, 카르복실기, 아민기 등의 활성수소기를 2개 이상 가진 것을 말한다. 이들 폴리올은 그 분자량에 따라 사용용도가 구분되는데, 에틸렌 글리콜(Ethylene glycol), 글리세린(Glycerine), 부탄디올(Butanediol), 트리메틸올 프로판(Trimethylol propane) 등과 저분자량 폴리올은 쇄연장제 또는 가교제로 사용되며, 평균분자량 8,000까지의 고분자량 폴리올은 실제 폴리우레탄 제조용으로 사용된다.Polyol is an active hydrogen compound used to prepare polyurethane by reacting with isocyanate, and it refers to having two or more active hydrogen groups such as hydroxyl group, carboxyl group, and amine group in the molecule. These polyols are used according to their molecular weight, and low molecular weight polyols such as ethylene glycol, glycerin, butanediol, and trimethylol propane are used as chain extenders or crosslinkers. , High molecular weight polyols with an average molecular weight of up to 8,000 are actually used for polyurethane production.
위와 같이, 폴리올은 분자구조, 분자량, 작용기(functionality) 그리고 OH-value에 따라 다양한 종류가 사용되고 있으며, 폴리우레탄의 물성에 직접적인 영향을 미친다. 예를 들면, 폴리에스테르 폴리올을 사용한 폴리우레탄은 폴리에테르 폴리올을 사용한 폴리우레탄에 비하여 인장강도, 경도와 신율이 높고 난연성이 우수할 뿐만 아니라 내화학성, 내약품 특성이 우수하여 산화에 강하다. 또한, 폴리에스테르 원단과의 접착력이 우수한 반면에 폴리에테르 폴리올과는 달리 가수분해하는 성질이 있어 내수성이 약하다는 것이 단점이다. 그러나 폴리에테르 폴리올을 사용한 폴리우레탄은 탄성이 우수하고 고온 다습한 환경 하에서도 사용이 가능하고 산과 알칼리에 대한 우수한 내구성을 보여준다.As described above, polyols are used in various types according to molecular structure, molecular weight, functionality and OH-value, and have a direct effect on the physical properties of polyurethane. For example, polyurethane using polyester polyol has higher tensile strength, hardness and elongation than polyurethane using polyether polyol, and has excellent flame retardancy, as well as excellent chemical resistance and chemical resistance, so it is strong against oxidation. In addition, while having excellent adhesion to polyester fabrics, unlike polyether polyols, it has a property of hydrolyzing, so its water resistance is weak. However, polyurethane using polyether polyol has excellent elasticity, can be used in high temperature and high humidity environments, and shows excellent durability against acids and alkalis.
상기와 같은 기본 개념을 바탕으로 조성되는 난연형 반응성 폴리우레탄 핫멜트 접착제는, (a) 수평균분자량 1,500 ~ 3,500 범위의 폴리카프로락톤 15 ~ 25중량%; (b) 수평균분자량 2,000 ~ 3,500 범위의 방향족 폴리에스테르 폴리올 15 ~ 25중량%; (c) 내열성 향상을 위한 반응성 실리콘 3 ~ 5중량%; (d) 안정적인 난연성 부여를 위한 반응성 난연제 5 ~ 12중량%; (e) 접착제의 결정성 및 강도 조정을 위한 쇄연장제 1 ~ 2중량%; (f) 방향족 이소시아네이트 15 ~ 30중량%의 비율로 반응시켜 제조한 프리폴리머 A와, (g) 내열성 및 접착강도 향상을 위한 수평균분자량 1,000 ~ 2,000 범위의 디아민 5 ~ 20 중량%; (h) 디아민과의 프리폴리머 합성을 위한 지방족 이소시아네이트 1 ~ 3중량%의 비율로 반응시켜 제조한 프리폴리머 B를, (i) 난연성 부여를 위한 첨가형 난연제 5 ~ 10중량%와 혼합하여 구성된다.The flame-retardant reactive polyurethane hot melt adhesive formed based on the basic concept as described above includes (a) 15 to 25% by weight of polycaprolactone having a number average molecular weight of 1,500 to 3,500; (b) 15 to 25% by weight of aromatic polyester polyol having a number average molecular weight of 2,000 to 3,500; (c) 3 to 5% by weight of reactive silicone for improving heat resistance; (d) 5 to 12% by weight of a reactive flame retardant for imparting stable flame retardancy; (e) 1 to 2% by weight of a chain extender for adjusting the crystallinity and strength of the adhesive; (f) a prepolymer A prepared by reacting at a ratio of 15 to 30% by weight of an aromatic isocyanate, and (g) 5 to 20% by weight of a diamine having a number average molecular weight in the range of 1,000 to 2,000 for improving heat resistance and adhesive strength; (h) Prepolymer B prepared by reacting at a ratio of 1 to 3% by weight of an aliphatic isocyanate for synthesis of the prepolymer with diamine, and (i) 5 to 10% by weight of an additive type flame retardant for imparting flame retardancy.
본 발명의 폴리우레탄 접착제를 제조하기 위한 폴리올로는 목적물인 반응성 폴리우레탄 핫멜트 접착제의 점도와 접착력 등의 특성을 고려하여 접착력이 우수한 수평균분자량 2,000 ~ 3,500 범위의 방향족 폴리에스테르 폴리올(a)과 유동성이 좋은 수평균분자량 1,500 ~ 3,500 범위의 폴리카프로락톤(b)을 혼합하여 사용하였다. 상기 폴리올은 접착제 총중량을 기준으로 방향족 폴리에스테르 폴리올(a) 15 ~ 25중량%와 폴리카프로락톤(b) 15 ~ 25중량%의 범위로 혼합하는 것이 강한 접착력과 양호한 유동성을 발휘하기에 적합하며, 상기 범위를 벗어나면 점도와 촉감 그리고 수지 자체의 접착력이 떨어지게 된다.Polyols for preparing the polyurethane adhesive of the present invention include aromatic polyester polyols (a) having an excellent number average molecular weight in the range of 2,000 to 3,500 with excellent adhesion in consideration of characteristics such as viscosity and adhesion of the target reactive polyurethane hot melt adhesive and fluidity. Polycaprolactone (b) having a good number average molecular weight of 1,500 to 3,500 was mixed and used. The polyol is suitable for exhibiting strong adhesion and good fluidity to be mixed in the range of 15 to 25% by weight of aromatic polyester polyol (a) and 15 to 25% by weight of polycaprolactone (b) based on the total weight of the adhesive, If it is out of the above range, the viscosity, the touch, and the adhesive strength of the resin itself fall.
상기 반응성 실리콘(c)은 아래 화학식 1과 같은 모노 터미네이티드 타입(mono terminated type)의 수평균분자량 1,000 ~ 2,000 범위를 가지는 반응성 디메틸실록산 디올 또는 아래 화학식 2와 같은 말단에 아민기를 가지는 아민당량이 250 ~ 270g/NH인 반응성 디메틸실록산 디아민을 사용하는 것이 내열성 향상에 효과적이라는 사실을 발견하였으며, 그 사용량은 접착제 총중량을 기준으로 3 ~ 5중량% 범위로 첨가하는 것이 상기 폴리올과의 반응성으로 인한 접착력 저하가 발생되지 않는다.The reactive silicone (c) is a reactive dimethylsiloxane diol having a number average molecular weight ranging from 1,000 to 2,000 of a mono-terminated type as shown in Formula 1 below, or an amine equivalent having an amine group at the terminal as shown in Formula 2 below. It was found that using a reactive dimethylsiloxane diamine of 250 to 270 g/NH is effective in improving heat resistance, and the amount of the amount added in the range of 3 to 5% by weight based on the total weight of the adhesive is adhesive strength due to reactivity with the polyol. No deterioration occurs.
[화학식 1][Formula 1]
[화학식 2][Formula 2]
또한, 본 발명은 난연성 부여를 위해 상업적으로 판매되는 다양한 첨가형 난연제를 사용할 수 있으나, 첨가형 난연제는 그 사용량이 10중량%를 초과할 경우 표면으로의 블루밍 현상이 발생되고 접착력의 저하가 확인되므로, 본 발명에서는 첨가형 난연제(i)를 최종적인 접착제 총중량을 기준으로 5 ~ 10중량% 이내로 사용하며, 그로 인하여 부족한 난연성은 반응성 난연제(d)를 적용하였다.In addition, the present invention can use various additive-type flame retardants commercially sold to impart flame retardancy, but when the amount of the additive-type flame retardant exceeds 10% by weight, a blooming phenomenon to the surface occurs and a decrease in adhesion is confirmed. In the present invention, the additive-type flame retardant (i) is used within 5 to 10% by weight based on the total weight of the final adhesive, and thus, a reactive flame retardant (d) is applied for insufficient flame retardancy.
상기 반응성 난연제(d)는 아래 화학식 3과 같은 수평균분자량 250 ~ 500인 디에틸 N,N-비스(2-하이드록시에틸) 아미노메틸 포스포네이트 또는 아래 화학식 4와 같은 테트라브로모 프탈레이트 디올 타입의 반응성 난연제 중에서 선택되는 1종 이상을 접착제 총중량을 기준으로 5 ~ 12중량% 이내로 사용하는 것이 폴리올과의 반응성과 접착제의 물성 저하를 고려할 때 바람직하다.The reactive flame retardant (d) is a diethyl N,N-bis(2-hydroxyethyl) aminomethyl phosphonate having a number average molecular weight of 250 to 500 as shown in Formula 3 below or a tetrabromophthalate diol type as shown in Formula 4 below. It is preferable to use one or more selected from among the reactive flame retardants of 5 to 12% by weight or less based on the total weight of the adhesive in consideration of reactivity with polyol and deterioration of physical properties of the adhesive.
[화학식 3][Formula 3]
[화학식 4][Formula 4]
또한, 본 발명에서의 쇄연장제(e)는 통상 모노에틸렌 글리콜, 1,3-프로판디올, 1,4-부탄디올, 1,6-헥산디올 중에서 선택되는 어느 1종 이상의 폴리올을 적정한 비율로 사용하여 반응시키면 본 발명에서 요구되는 수지특성을 얻을 수 있는데, 접착제의 결정성 및 강도 조정을 위해서는 1,6-헥산디올을 사용하는 것이 가장 바람직하다.In addition, as the chain extender (e) in the present invention, one or more polyols selected from monoethylene glycol, 1,3-propanediol, 1,4-butanediol, and 1,6-hexanediol are usually used in an appropriate ratio. When the reaction is performed, the resin properties required in the present invention can be obtained. In order to adjust the crystallinity and strength of the adhesive, it is most preferable to use 1,6-hexanediol.
상기와 같이, 본 발명에서는 프리폴리머 A를 제조하기 위해 폴리카프로락톤(a) 15 ~ 25중량%, 방향족 폴리에스테르 폴리올(b) 15 ~ 25중량%, 반응성 실리콘(c) 3 ~ 5중량%, 반응성 난연제(d) 5 ~ 12중량%, 쇄연장제(e) 1 ~ 2중량%를 혼합한 후 상기 폴리올과의 반응을 위해 사용되는 방향족 이소시아네이트(Aromatic isocyanate)(f)는 통상의 폴리우레탄 제조와 같이 접착제 총중량을 기준으로 15 ~ 30중량% 범위로 함유하는데, 바람직하게는 디페닐메탄 디이소시아네이트(MDI), 폴리카르보디이미드 변성 디페닐메탄 디이소시아네이트(변성 MDI), 톨루엔 디이소시아네이트(TDI) 또는 이들의 혼합물로 이루어지는 그룹 중에서 선택된 것을 사용할 수 있으며, 가장 바람직하게는 내열성과 접착강도가 우수한 MDI에 변성 MDI를 15 ~ 30mol%의 비율로 혼합하여 사용하는 것이 반응성에서 가장 유리하다고 할 수 있다.As described above, in the present invention, in order to prepare prepolymer A, polycaprolactone (a) 15 to 25% by weight, aromatic polyester polyol (b) 15 to 25% by weight, reactive silicone (c) 3 to 5% by weight, reactive After mixing 5 to 12% by weight of a flame retardant (d) and 1 to 2% by weight of a chain extender (e), the aromatic isocyanate (f) used for the reaction with the polyol is used in the production of conventional polyurethane. Likewise, it is contained in the range of 15 to 30% by weight based on the total weight of the adhesive, preferably diphenylmethane diisocyanate (MDI), polycarbodiimide modified diphenylmethane diisocyanate (modified MDI), toluene diisocyanate (TDI) or One selected from the group consisting of a mixture thereof may be used, and most preferably, it can be said that it is most advantageous in terms of reactivity to mix and use modified MDI in a ratio of 15 to 30 mol% to MDI having excellent heat resistance and adhesive strength.
다음으로, 본 발명에서는 내열성 향상과 접착제의 접착강도를 높이기 위해 우레아 결합을 형성하는 디아민(g)을 프리폴리머 B로 합성하여 최종 수지에 혼합하여 사용하였으며, 이는 결합력이 높은 아민결합의 특성과 상대적으로 서서히 경화되어 기재의 표면에 강한 부착력을 부여하는 지방족 이소시아네이트(h)의 특성을 이용한 프리폴리며 B를 제조하여 상기 프리폴리며 A와 블렌딩함으로써 고내구성, 고접착성의 특성을 구현할 수 있게 된다.Next, in the present invention, in order to improve heat resistance and increase the adhesive strength of the adhesive, diamine (g), which forms a urea bond, was synthesized as a prepolymer B and mixed with the final resin, which was used by mixing with the amine bond having high bonding strength. It is possible to realize the characteristics of high durability and high adhesiveness by preparing B and blending with the prepoly A by preparing a prepoly and B using the characteristics of an aliphatic isocyanate (h) that is gradually cured to give strong adhesion to the surface of the substrate.
이러한 반응에 사용되는 디아민(g)은 수평균분자량 1,000 ~ 2,000 범위의 폴리프로필렌 글리콜이나 폴리에틸렌글리콜 등으로부터 유도된 폴리아민을 접착제 총중량을 기준으로 5 ~ 20중량% 사용하여 반응성을 높일 수 있고 이를 통해 우수한 내열성 및 접착강도를 확보할 수 있으며, 가장 바람직하게는 아래 화학식 5와 같은 폴리옥시프로필렌 디아민이 적합하다.Diamine (g) used in this reaction can increase reactivity by using a polyamine derived from polypropylene glycol or polyethylene glycol having a number average molecular weight of 1,000 to 2,000, based on the total weight of the adhesive, in an amount of 5 to 20% by weight. Heat resistance and adhesive strength can be secured, and most preferably polyoxypropylene diamine as shown in Formula 5 below is suitable.
[화학식 5][Formula 5]
상기 프리폴리머 B에 사용되는 지방족 이소시아네이트(h)로는 4,4'-메틸렌 디시클로헥실 디이소시아네이트(H12MDI), 이소포론디이소시아네이트 (Isophorone diisocyanate), 테트라메틸 크실렌 디이소시아네이트(Tetramethyl xylene diisocyanate), 헥사메틸렌 디이소시아네이트(Hexamethylene diisocyanate) 중에서 선택되는 어느 1종 이상의 지방족 이소시아네이트를 사용하는 것이 바람직하고, 이중 4,4'-메틸렌 디시클로헥실 디이소시아네이트(H12MDI)를 1 ~ 3중량% 범위로 사용하는 것이 가장 바람직하다.The aliphatic isocyanate (h) used in the prepolymer B is 4,4'-methylene dicyclohexyl diisocyanate (H 12 MDI), isophorone diisocyanate, tetramethyl xylene diisocyanate, and hexa It is preferable to use one or more aliphatic isocyanates selected from methylene diisocyanate (Hexamethylene diisocyanate), of which 4,4'-methylene dicyclohexyl diisocyanate (H 12 MDI) is used in the range of 1 to 3% by weight. It is most preferred.
마지막으로, 코팅 원단에 적용시 안정적인 난연성의 발현을 위해 구조적으로 적용되는 반응성 난연제 외에 첨가형으로 일반적으로 사용되는 인계 및 브롬계 난연제가 사용될 수 있으며, 바람직하게는 아래 화학식 6과 같은 레조시놀 비스 디페닐포스페이트와 같은 액상 난연제가 가장 적합하다. 상기 첨가형 난연제(i)는 그 사용량이 10중량%를 초과할 경우 표면으로의 블루밍 현상이 발생되고 접착력이 저하될 우려가 있으므로 접착제 총중량을 기준으로 5 ~ 10중량% 이내로 사용하여야 한다.Finally, phosphorus-based and bromine-based flame retardants generally used as additives in addition to the structurally applied reactive flame retardants for stable flame retardancy when applied to coated fabrics may be used, preferably resorcinol bis di Liquid flame retardants such as phenylphosphate are most suitable. The additive-type flame retardant (i) should be used within 5 to 10% by weight based on the total weight of the adhesive, since there is a possibility that a blooming phenomenon to the surface may occur and the adhesive strength may decrease when the amount of the additive type flame retardant (i) exceeds 10% by weight.
[화학식 6][Formula 6]
이상과 같이, 본 발명에서의 내열성이 우수한 난연형 반응성 폴리우레탄 핫멜트 접착제는 유연성과 접착력, 내열성과 난연성을 고려하여 혼합되는 프리폴리머 A와 프리폴리머 B의 중량비율은 8 : 2 ~ 9 : 1의 범위가 적합하며, 폴리우레탄 제조를 위해 프리폴리머에 적용되는 폴리올 혼합물과 쇄연장제로 이루어지는 활성수소 원자화합물 대비 디이소시아네이트의 최종 반응비율(OH/NCO 비율)은 당량비로 1.0 ~ 2.1, 보다 바람직하기로는 1.2 ~ 1.7의 값을 가지도록 조정하는 것이 좋다.As described above, in the flame-retardant reactive polyurethane hot melt adhesive having excellent heat resistance in the present invention, the weight ratio of prepolymer A and prepolymer B mixed in consideration of flexibility and adhesion, heat resistance and flame retardancy is in the range of 8:2 to 9:1. It is suitable, and the final reaction ratio (OH/NCO ratio) of diisocyanate to the active hydrogen atom compound consisting of the polyol mixture and the chain extender applied to the prepolymer for the production of polyurethane is 1.0 to 2.1 in the equivalent ratio, more preferably 1.2 to 1.7 It is good to adjust it so that it has a value of.
그리고 본 발명의 코팅 원단의 제조방법은 상기 내열성이 우수한 난연형 반응성 폴리우레탄 핫멜트 접착제를 80 ~ 120℃의 온도로 용융시키고 섬유 원단에 5 ~ 50g/㎡의 양으로 도포한 다음, 온도 30 ~ 50℃, 상대습도 70 ~ 100%의 조건에서 12 ~ 48시간 동안 숙성시켜 제조함으로써 내열성과 접착강도, 그리고 높은 박리강도와 부드러운 촉감을 최대로 발휘할 수 있는데, 이 코팅 원단에 있어 상기 접착제의 난연성은 V-0등급(UL94 수직법)을 가지며, 상기 코팅 원단은 내열성 260 ~ 300℃, 박리강도 11 ~ 15N/5cm 정도의 탁원한 물성을 갖게 된다.And the manufacturing method of the coated fabric of the present invention melts the flame-retardant reactive polyurethane hot-melt adhesive with excellent heat resistance at a temperature of 80 to 120°C, and applies it to the fiber fabric in an amount of 5 to 50 g/m 2, and then at a temperature of 30 to 50 By aging for 12 to 48 hours under conditions of ℃ and relative humidity of 70 to 100%, heat resistance, adhesive strength, high peel strength and soft touch can be maximized. In this coated fabric, the flame retardancy of the adhesive is V It has a -0 grade (UL94 vertical method), and the coated fabric has excellent physical properties with heat resistance of 260 to 300°C and peel strength of 11 to 15N/5cm.
이하에서는 본 발명에 의한 내열성이 우수한 난연형 반응성 폴리우레탄 핫멜트 접착제를 실험한 실시예를 살펴보기로 하되, 본 발명이 속하는 기술분야에서 통상의 지식을 가진 사람이 쉽게 실시할 수 있을 정도의 바람직한 실시예를 통하여 본 발명을 설명한다.Hereinafter, an experiment in which a flame-retardant reactive polyurethane hot melt adhesive having excellent heat resistance according to the present invention was tested will be described, but a preferred implementation that can be easily performed by a person of ordinary skill in the art to which the present invention belongs. The present invention will be described through examples.
[실시예, 비교예 1 ~ 4][Examples, Comparative Examples 1 to 4]
1리터 3구 환류 반응기에 질소 분위기 하에서 폴리카프로락톤, 방향족 폴리에스테르 폴리올, 반응성 실리콘, 쇄연장제, 난연성 디올과 산화방지제를 투입하고 진공 하에서 60℃에서 혼합 교반 한 후 방향족 이소시아네이트를 투입하고 90 ~ 100℃의 온도에서 3 ~ 5시간 동안 반응을 실시한다. 이후 미반응 이소시아네이트의 제거를 위해 진공 하에서 1시간 동안 반응시키며, NCO%와 점도를 확인 후 프리폴리머 A를 제조한다. 다음으로, 별도의 1리터 3구 환류 반응기에 디아민과 지방족 이소시아네트를 투입한 후 3시간 동안 프리폴리머 A와 동일하게 반응을 실시한 다음, 반응이 완료되면 프리폴리머 A, B를 일정 비율로 혼합하고 여기에 첨가형 난연제를 혼입하여 교반한다.Polycaprolactone, aromatic polyester polyol, reactive silicone, chain extender, flame retardant diol and antioxidant are added to a 1-liter 3-neck reflux reactor, mixed and stirred at 60°C under vacuum, and then aromatic isocyanate is added to 90 ~ The reaction is carried out for 3 to 5 hours at a temperature of 100°C. After that, to remove unreacted isocyanate, it is reacted for 1 hour under vacuum, and after checking NCO% and viscosity, prepolymer A is prepared. Next, after adding diamine and aliphatic isocyanate to a separate 1-liter 3-neck reflux reactor, the reaction was carried out in the same manner as for prepolymer A for 3 hours, and when the reaction was completed, prepolymers A and B were mixed in a predetermined ratio and then Addition type flame retardant is mixed and stirred.
각 구성성분의 배합을 달리하는 난연형 반응성 폴리우레탄 핫멜트 접착제에 대한 제조를 아래 표 1과 같은 조성으로 실시하였다.The preparation of a flame-retardant reactive polyurethane hot melt adhesive having different formulations of each component was carried out in the composition shown in Table 1 below.
(반응형 난연제)FR-diol
(Reactive flame retardant)
(첨가형 난연제)Flame retardant
(Additive flame retardant)
[실험예][Experimental Example]
상기 실시예 1 및 비교예 1 내지 4에 따라 각각 제조된 핫멜트 접착제에 대하여 접착강도(박리강도), 난연성, 내열성, 촉감 등을 아래와 같은 방법으로 측정하고 그 결과를 표 2에 나타내었다.For the hot melt adhesives prepared according to Example 1 and Comparative Examples 1 to 4, adhesive strength (peel strength), flame retardancy, heat resistance, and touch were measured by the following methods, and the results are shown in Table 2.
○ 접착강도○ Adhesive strength
상기 핫멜트 접착제의 접착강도(박리강도) 시험을 위한 시험편으로는 Poly Dewspo 50D을 사용하였다. 핫멜트 접착제는 100℃의 온도로 용융시킨 후 #152 Gravure roll을 사용하여 도포량이 25g/㎡ 정도가 되도록 원단의 표면에 전사하였으며, 고무롤과 합포롤을 사용하여 Dewspo 원단에 압착하여 접착을 실시하였다. 이때 시편은 5개를 사용하였고 시험기는 당사에서 보유하고 있는 만능인장시험기를 사용하였다. 시험기와 시험편의 파괴하중은 용량의 5 ~ 85% 이내로 하였으며, 접착 후 40℃의 온도와 70%의 상대습도에서 12시간 숙성시킨 후 5회에 걸쳐 박리강도를 측정하였다.Poly Dewspo 50D was used as a test piece for the adhesive strength (peel strength) test of the hot melt adhesive. The hot melt adhesive was melted at a temperature of 100°C, and then transferred to the surface of the fabric so that the applied amount was about 25g/m2 using a #152 Gravure roll, and bonded by pressing it onto the Dewspo fabric using a rubber roll and a fabric roll. At this time, 5 specimens were used, and the testing machine used a universal tensile tester owned by our company. The breaking load of the tester and the test piece was within 5 to 85% of the capacity, and after bonding, the peel strength was measured over 5 times after aging for 12 hours at a temperature of 40°C and a relative humidity of 70%.
○ 난연성○ Flame retardant
상기 핫멜트 접착제는 UL94 수직법을 이용하여 아래 내열성 시편과 유사한 방법으로 넓이 1.3cm, 길이 12cm의 시편을 만들어 수직으로 접염 시의 난연성을 확인하였다.For the hot melt adhesive, a specimen having a width of 1.3 cm and a length of 12 cm was made in a manner similar to that of the heat-resistant specimen below using the UL94 vertical method, and the flame retardancy was confirmed during vertical welding.
○ 내열성○ Heat resistance
상기 핫멜트 접착제의 내열성 측정방법으로는 이형지와 핫멜트 접착제를 이용하여 0.5㎜ 두께의 필름을 제작한 후 5 ~ 10㎎의 시료를 TGA에 투입하여20℃/min의 승온속도로 30 ~ 600℃까지 질소기류 하에서 측정하여 시료의 잔존 중량 95%가 되는 지점의 온도를 열분해온도로 하고 샘플들의 내열성을 비교하였다As a method of measuring the heat resistance of the hot melt adhesive, a film of 0.5 mm thickness is prepared using release paper and hot melt adhesive, and then 5 to 10 mg of sample is added to TGA, and the temperature is increased to 30 to 600°C at a heating rate of 20°C/min. Measured under an airflow, the temperature at the point where the residual weight of the sample becomes 95% was the thermal decomposition temperature, and the heat resistance of the samples was compared.
○ 촉감○ touch
상기 핫멜트 접착제와 아라미드 원단을 합포하여 전문가 10인을 선정하여 그 촉감의 평균치를 측정하였다(◎: 매우 양호, ○: 양호, △: 보통, ×불량).The hot melt adhesive and aramid fabric were combined, and 10 experts were selected to measure the average value of the touch (◎: very good, ○: good, △: normal, x bad).
상기 표 2에서와 같이, 실시예 1 및 비교예 1 내지 4에 따라 각각 제조된 핫멜트 접착제에 대한 실험 결과를 비교하면, 우레아 결합이 적용된 프리폴리머 B와 반응성 실리콘이 적용된 실시예 1과 비교예 1, 3의 경우 내열성이 증가하는 경향이 확인되었으나, 반응성 난연제를 제외한 비교예 1의 경우에는 첨가형 난연제의 함량이 증가함에 따라 박리강도가 저하되는 현상이 관찰되었다.As shown in Table 2, when comparing the experimental results for the hot melt adhesives each prepared according to Example 1 and Comparative Examples 1 to 4, the prepolymer B to which urea bonding was applied and the reactive silicone were applied to Examples 1 and 1, In the case of 3, it was observed that the heat resistance tends to increase, but in the case of Comparative Example 1 excluding the reactive flame retardant, a phenomenon in which the peel strength decreased as the content of the additive-type flame retardant increased.
한편, 프리폴리머 B가 제외된 비교예 2와 과량으로 적용된 비교예 3의 경우에는 사슬 내의 우레아 결합 부족에 따른 내열성의 저하되는 현상(비교예 2)과 우레아 결합의 증가에 따른 코팅층이 딱딱해져 촉감이 급격히 저하되는 현상(비교예 3)이 각각 관찰되었다. 또한, 반응성 실리콘의 제외에 따른 결과는 비교예 4와 같이 내열성이 저하되는 현상으로 확인된다.On the other hand, in the case of Comparative Example 2 in which the prepolymer B was excluded and Comparative Example 3 applied in an excessive amount, the heat resistance decreased due to the lack of urea bonds in the chain (Comparative Example 2) and the coating layer became hard due to the increase of urea bonds, resulting in a touch Phenomenon (Comparative Example 3) of rapid decline was observed, respectively. In addition, the result of the exclusion of the reactive silicone was confirmed as a phenomenon that the heat resistance is lowered as in Comparative Example 4.
상기 실험결과로부터, 본 발명에 따라 제조된 실시예 1이 상대적으로 가장 우수한 내열성과 박리강도, 그리고 가장 양호한 촉감을 갖는다는 사실을 확인할 수 있다.From the above experimental results, it can be confirmed that Example 1 prepared according to the present invention has relatively the best heat resistance, peel strength, and the best touch.
따라서 본 발명의 내열성이 우수한 난연형 반응성 폴리우레탄 핫멜트 접착제는 본 발명의 기술적 사상을 벗어나지 않는 범위 내에서 여러 가지로 치환, 변형 및 변경이 가능한 것으로, 특히 가공성이 용이한 장점이 있어 초고온 환경에 노출되는 각종 섬유소재의 표면 가공은 물론, 각종 의류, 자동차, 건축자재 등에 코팅되거나 필름형태로의 적용이 가능한 친환경 소재로서 다양한 용도와 형태로 사용되어 질 수 있다.Therefore, the flame-retardant reactive polyurethane hot melt adhesive having excellent heat resistance of the present invention can be substituted, transformed, and changed in various ways within the scope of the technical idea of the present invention. In particular, it has the advantage of easy processability and is exposed to ultra-high temperature environments. As an eco-friendly material that can be coated or applied in a film form, as well as surface processing of various textile materials to be processed, it can be used in various uses and forms.
Claims (6)
(b) 수평균분자량 2,000 ~ 3,500 범위의 방향족 폴리에스테르 폴리올 15 ~ 25중량%;
(c) 내열성 향상을 위한 반응성 실리콘 3 ~ 5중량%;
(d) 안정적인 난연성 부여를 위한 반응성 난연제 5 ~ 12중량%;
(e) 접착제의 결정성 및 강도 조정을 위한 쇄연장제 1 ~ 2중량%;
(f) 방향족 이소시아네이트 15 ~ 30중량%;
의 비율로 반응시켜 제조한 프리폴리머 A와,
(g) 내열성 및 접착강도 향상을 위한 수평균분자량 1,000 ~ 2,000 범위의 디아민 5 ~ 20 중량%;
(h) 디아민과의 프리폴리머 합성을 위한 지방족 이소시아네이트 1 ~ 3중량%;
의 비율로 반응시켜 제조한 프리폴리머 B를,
(i) 난연성 부여를 위한 첨가형 난연제 5 ~ 10중량%;
와 혼합하여 이루어지는 것을 특징으로 하는 내열성이 우수한 난연형 반응성 폴리우레탄 핫멜트 접착제.(a) 15 to 25% by weight of polycaprolactone having a number average molecular weight of 1,500 to 3,500;
(b) 15 to 25% by weight of aromatic polyester polyol having a number average molecular weight of 2,000 to 3,500;
(c) 3 to 5% by weight of reactive silicone for improving heat resistance;
(d) 5 to 12% by weight of a reactive flame retardant for imparting stable flame retardancy;
(e) 1 to 2% by weight of a chain extender for adjusting the crystallinity and strength of the adhesive;
(f) 15 to 30% by weight of aromatic isocyanate;
Prepolymer A prepared by reacting at a ratio of,
(g) 5 to 20% by weight of diamine having a number average molecular weight in the range of 1,000 to 2,000 for improving heat resistance and adhesive strength;
(h) 1 to 3% by weight of an aliphatic isocyanate for synthesis of a prepolymer with diamine;
Prepolymer B prepared by reacting at a ratio of,
(i) 5 to 10% by weight of an additive flame retardant for imparting flame retardancy;
Flame-retardant reactive polyurethane hot melt adhesive having excellent heat resistance, characterized in that it is mixed with
상기 반응성 실리콘(c)은 모노 터미네이티드 타입(mono terminated type)의 수평균분자량 1,000 ~ 2,000 범위를 가지는 반응성 디메틸실록산 디올 또는 말단에 아민기를 가지는 아민당량이 250 ~ 270g/NH인 반응성 디메틸실록산 디아민을 1종 이상 사용하는 것을 특징으로 하는 내열성이 우수한 난연형 반응성 폴리우레탄 핫멜트 접착제.The method of claim 1,
The reactive silicone (c) is a reactive dimethylsiloxane diol having a number average molecular weight in the range of 1,000 to 2,000 of a mono-terminated type or a reactive dimethylsiloxane diamine having an amine equivalent of 250 to 270 g/NH having an amine group at the terminal. Flame-retardant reactive polyurethane hot melt adhesive having excellent heat resistance, characterized in that at least one is used.
상기 반응성 난연제(d)는 수평균분자량 250 ~ 500인 디에틸 N,N-비스(2-하이드록시에틸) 아미노메틸 포스포네이트 또는 테트라브로모 프탈레이트 디올 타입의 반응성 난연제 중에서 선택되는 1종 이상을 사용하는 것을 특징으로 하는 내열성이 우수한 난연형 반응성 폴리우레탄 핫멜트 접착제.The method of claim 1,
The reactive flame retardant (d) is one or more selected from diethyl N,N-bis(2-hydroxyethyl) aminomethyl phosphonate or tetrabromophthalate diol type reactive flame retardant having a number average molecular weight of 250 to 500. Flame-retardant reactive polyurethane hot melt adhesive with excellent heat resistance, characterized in that it is used.
상기 프리폴리머 A와 프리폴리머 B의 중량비율은 8 : 2 ~ 9 : 1이며, 활성수소 원자화합물 대비 디이소시아네이트의 최종 반응비율(OH/NCO 비율)은 당량비로 1.2 ~ 1.7의 값을 갖도록 조정된 것을 특징으로 하는 내열성이 우수한 난연형 반응성 폴리우레탄 핫멜트 접착제.The method of claim 1,
The weight ratio of the prepolymer A and the prepolymer B is 8: 2 ~ 9: 1, and the final reaction ratio (OH/NCO ratio) of the diisocyanate to the active hydrogen atom compound is adjusted to have a value of 1.2 ~ 1.7 as an equivalent ratio. Flame retardant reactive polyurethane hot melt adhesive with excellent heat resistance.
상기 난연형 반응성 폴리우레탄 핫멜트 접착제의 난연성은 V-0등급(UL94 수직법)이며, 상기 코팅 원단은 내열성 260 ~ 300℃, 박리강도 11 ~ 15N/5cm인 것을 특징으로 하는 코팅 원단의 제조방법.The method of claim 5,
The flame retardancy of the flame-retardant reactive polyurethane hot melt adhesive is V-0 grade (UL94 vertical method), and the coating fabric has a heat resistance of 260 to 300°C and a peel strength of 11 to 15N/5cm.
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