KR20190096485A - Environmentally friendly conductive composite based on waterborne polyurethane, manufacturing method thereof and use using the same - Google Patents
Environmentally friendly conductive composite based on waterborne polyurethane, manufacturing method thereof and use using the same Download PDFInfo
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Abstract
Description
본 발명은 수분산성 폴리우레탄 기반의 친환경성 전도성 복합체, 그의 제조방법 및 그를 이용한 용도에 관한 것으로서, 더욱 상세하게는, 친환경 특성의 수분산성 폴리우레탄 기반에 나노셀룰로오스 및 전도성 폴리머가 안정적으로 복합화된 복합체로서 상기 나노셀룰로오스로부터 생분해성능과 인장강도 등의 물성이 향상되고, 상기 전도성 폴리머에 의해 전도성이 부여됨으로써, 친환경성 및 고기능을 요구하는 섬유제품과 전류가 흐르게 되면 배향성이 좋아져 재생에 도움되는 척수재생 또는 신경조직 재생용의 메디칼 재료로 유용한, 수분산성 폴리우레탄 기반의 친환경성 전도성 복합체, 그의 제조방법 및 그를 이용한 용도에 관한 것이다. The present invention relates to an environment-friendly conductive composite based on a water-dispersible polyurethane, a method for manufacturing the same, and a use thereof, and more particularly, a composite in which nanocellulose and a conductive polymer are stably complexed to an aqueous dispersion-based polyurethane having eco-friendly properties. As the physical properties such as biodegradation performance and tensile strength are improved from the nanocellulose, and conductivity is imparted by the conductive polymer, fiber products requiring eco-friendliness and high performance and current flow through the spinal cord regeneration which helps regeneration. Or it relates to a water-dispersible polyurethane-based eco-friendly conductive composite, a method for preparing the same and the use using the same, useful as a medical material for nerve tissue regeneration.
현재 폴리우레탄을 이용하여 인공피혁을 제조할 때, 발포제로 사용되는 CFC의 규제, 폐기물의 처리 및 재활용 등과 같은 환경문제의 발생으로 대체물에 대한 요구가 꾸준히 요구되어왔다. Currently, when manufacturing artificial leather using polyurethane, there has been a constant demand for alternatives due to the occurrence of environmental problems such as regulation of CFCs used as blowing agent, disposal and recycling of waste.
이러한 요구에 따라, 유성 폴리우레탄을 수성화시켜 친환경적인 수분산성 폴리우레탄을 대안으로 사용하고자 하는 노력이 진행되고 있으며, 폴리우레탄 골격 중에 친수성기를 도입하여 자기 유화성 수지를 만든 후 수중에서 분산시키는 방법, 소수성 폴리우레탄을 다량의 유화제를 사용하여 분산시키는 방법, 이소시아네이트기와 물 사이의 반응이 억제되며 수중분산 상태에서 높은 안정성을 보이는 고유화성 안정성 폴리이소시아네이트 조성물, 방향족-지방족 이소시아네이트가 하이브리드된 수분산 폴리우레탄 제조방법 등이 다수 보고된바 있다. In accordance with these demands, efforts have been made to use an environmentally friendly water-dispersible polyurethane as an alternative by water-based oily polyurethane, and a method of introducing a hydrophilic group into a polyurethane skeleton to make a self-emulsifying resin and dispersing it in water. , A method of dispersing hydrophobic polyurethane using a large amount of emulsifier, the reaction between isocyanate and water is suppressed, the uniquely stable polyisocyanate composition which shows high stability in dispersion state, the water-dispersed polyurethane hybridized aromatic-aliphatic isocyanate Many methods have been reported.
기존의 유성 폴리우레탄은 톨루엔, 아세톤, 메틸에틸케톤, 시클로헥산 등과 같은 다량의 유기용매의 사용으로 환경문제의 심각성이 제기될 뿐 아니라 기본적으로 포르말린을 함유하고 있어, 국제적으로 유아용은 30ppm, 성인용은 70ppm의 허용치를 두고 있으나 선진국들은 친환경성 및 고기능을 요구하는 섬유제품에 있어 더욱 엄격한 기준을 요구하고 있다.Existing oil-based polyurethanes not only raise the seriousness of the environmental problem by using a large amount of organic solvents such as toluene, acetone, methyl ethyl ketone, and cyclohexane, but also contain formalin. Although 70 ppm is allowed, developed countries are demanding more stringent standards for textile products that require eco-friendliness and high performance.
따라서 친환경적 제품으로 인정되고 있는 수분산성 폴리우레탄을 이용한 섬유코팅방법(특허문헌 1)이 제시된바 있고, 수성우레탄을 이용한 코팅기술을 접목하되 그라파이트를 분산시킨 섬유코팅제를 이용한 보온성, 방수성, 마찰 대전성을 향상시킨 섬유제품(특허문헌 2)과 수성 폴리우레탄에 도전성 제제로서 카본블랙을 사용한 도전성 인공피혁(특허문헌 3)을 제공하고 있다. Therefore, a fiber coating method using a water-dispersible polyurethane (Patent Document 1), which is recognized as an environmentally friendly product, has been proposed, and a coating technology using an aqueous urethane is applied, but thermal insulation, waterproofness, and triboelectric chargeability using a fiber coating agent in which graphite is dispersed. There is provided a conductive artificial leather (Patent Document 3) using carbon black as a conductive agent in a textile product (Patent Document 2) and an aqueous polyurethane which have been improved.
그러나 수분산성 폴리우레탄은 분자량 조절의 어려움이 있고 유성 폴리우레탄 사용대비 물성이 저하되어 아직까지 충분한 대체효과를 기대할 수 없다. However, the water-dispersible polyurethane is difficult to control the molecular weight, and the physical properties are lowered compared to the use of the oil-based polyurethane can not expect a sufficient replacement effect yet.
이와 같이 수분산성 폴리우레탄의 문제점을 해결하기 위해, 나노셀룰로오스 결정을 제조하여 폴리우레탄의 물성을 보완하고자 하는 연구가 진행되고 있다(비특허문헌 1). 이때, 나노셀룰로오스를 보강재로 사용할 경우, 경량 특성으로 인한 에너지 절약과 함께 친환경 특성에 의한 사용자에게 안락함을 제공하면서 인체에도 상대적으로 안전한 소재로 알려져 있다. In order to solve the problem of the water-dispersible polyurethane as described above, research is being conducted to prepare nanocellulose crystals to supplement the physical properties of the polyurethane (Non-Patent Document 1). In this case, when the nano cellulose is used as a reinforcing material, it is known as a relatively safe material to the human body while providing comfort to the user by eco-friendly properties while saving energy due to light weight properties.
그러나 아직까지 나노셀룰로오스의 제조, 분산, 복합체 내에서의 보강효과 분석에 대한 연구가 상대적으로 부족할 뿐 아니라, 상기 발명에서는 나노셀룰로오스를 황산법을 이용하여 제조함으로써, 강산을 사용함으로써 발생되는 제조공정상의 문제와 환경상의 문제 등이 제기되고 있다. However, not only studies on the preparation, dispersion, and analysis of reinforcing effects in composites have yet been relatively lacking, but in the present invention, nanocellulose is manufactured by using a sulfuric acid method, and thus a problem in manufacturing process caused by the use of strong acids. And environmental issues are being raised.
이에, 본 발명자들은 수분산성 폴리우레탄에 기반한 복합체의 종래 문제점을 개선하고자 노력한 결과, 수분산성 폴리우레탄과 나노셀룰로오스로 이루어진 친환경성의 예비복합체에, 전도성 폴리머를 투입하여 복합화하여, 생분해성과 전도성 물성을 구비한 수분산성 폴리우레탄/나노셀룰로오스/전도성 폴리머로 이루어진 복합체 제조를 확인함으로써, 본 발명을 완성하였다. Accordingly, the present inventors have tried to improve the conventional problem of the water-based polyurethane-based composite, as a result of the composite into the eco-friendly pre-composite consisting of a water-dispersible polyurethane and nanocellulose, by combining the conductive polymer, having biodegradability and conductive properties The present invention was completed by confirming the preparation of a composite consisting of one water dispersible polyurethane / nanocellulose / conductive polymer.
본 발명의 목적은 수분산성 폴리우레탄 기반에 나노셀룰로오스 및 전도성 폴리머가 복합화된 친환경성 전도성 복합체를 제공하는 것이다. It is an object of the present invention to provide an eco-friendly conductive composite in which nanocellulose and a conductive polymer are combined on a water-dispersible polyurethane base.
본 발명의 다른 목적은 수분산성 폴리우레탄과 나노셀룰로오스로 이루어진 친환경성의 예비복합체에, 전도성 폴리머를 투입하여 전도성을 부여한 복합체의 제조방법을 제공하는 것이다. Another object of the present invention is to provide a method for producing a composite in which conductivity is imparted by introducing a conductive polymer into an environmentally friendly precomposite composed of a water dispersible polyurethane and nanocellulose.
본 발명의 또 다른 목적은 수분산성 폴리우레탄 기반에 나노셀룰로오스 및 전도성 폴리머가 복합화된 친환경성 전도성 복합체를 이용한 용도를 제공하는 것이다. Still another object of the present invention is to provide a use of an environmentally friendly conductive composite in which nanocellulose and a conductive polymer are combined on a water-dispersible polyurethane base.
본 발명은 수분산성 폴리우레탄과 나노셀룰로오스로 이루어진 친환경성의 예비복합체 100 중량부에 대하여, 전도성 폴리머 1.0 내지 10 중량부가 복합화된, 수분산성 폴리우레탄/나노셀룰로오스/전도성 폴리머로 이루어진 친환경성 전도성 복합체를 제공한다. The present invention provides an eco-friendly conductive composite made of a water-dispersible polyurethane / nanocellulose / conductive polymer, in which 1.0 to 10 parts by weight of a conductive polymer is combined with respect to 100 parts by weight of an eco-friendly precomposite composed of a water-dispersible polyurethane and nanocellulose. do.
상기 예비복합체에서 수분산성 폴리우레탄과 나노셀룰로오스가 1: 0.01 내지 0.3 중량비율로 이루어진 것이 바람직하다. It is preferable that the water dispersible polyurethane and the nanocellulose in the precomposite are composed of a weight ratio of 1: 0.01 to 0.3.
상기에서 나노셀룰로오스는 10 내지 30nm 크기의 반결정성 입자이고, 상기 나노셀룰로오스는 70 시간 이후 80%의 생분해성능이 발현되고, 이를 포함한 최종 복합체의 경우에도 생분해능이 부여된다. The nanocellulose is a semicrystalline particle of 10 to 30nm size, the nanocellulose is expressed in 80% biodegradability after 70 hours, even in the case of the final composite including the biodegradation is given.
본 발명의 복합체에 포함되는 전도성 폴리머는 폴리티오펜(PEDOT:PSS), 폴리아세틸렌, 폴리피롤 및 폴리아닐린으로 이루어진 군에서 선택되는 어느 하나인 것이다. The conductive polymer included in the composite of the present invention is any one selected from the group consisting of polythiophene (PEDOT: PSS), polyacetylene, polypyrrole and polyaniline.
본 발명은 1) 수분산성 폴리우레탄의 합성단계에 나노셀룰로오스 분산액을 투입하여 인시츄(In-situ)로 수분산성 폴리우레탄 합성과 동시에 수분산성 폴리우레탄과 나노셀룰로오스로 이루어진 친환경성의 예비복합체를 생성하고, The present invention 1) by adding a nano cellulose dispersion in the synthesis step of the water-dispersible polyurethane and in-situ to produce a water-dispersible polyurethane and at the same time to create an eco-friendly pre-composite consisting of water-dispersible polyurethane and nanocellulose ,
2) 상기 예비복합체에 전도성 폴리머 분산액을 투입하여 복합화한, 수분산성 폴리우레탄/나노셀룰로오스/전도성 폴리머로 이루어진 친환경성 전도성 복합체의 제조방법을 제공한다. 2) It provides a method for producing an environmentally friendly conductive composite consisting of a water-dispersible polyurethane / nano cellulose / conductive polymer compounded by adding a conductive polymer dispersion to the pre-composite.
본 발명의 제조방법에 있어서, 상기 1) 단계에서 나노셀룰로오스는 마이크로 셀룰로오스로부터 수산화나트륨(NaOH)와 우레아(Urea)를 이용하여 pH 8수준으로 재생된 것이다. In the production method of the present invention, the nanocellulose in step 1) is regenerated to
또한, 상기 1) 단계 이후 고점도 용매를 더 투입할 수 있다. In addition, a high viscosity solvent may be further added after the step 1).
본 발명의 제조방법에 있어서, 상기 2) 단계는 전도성 폴리머 분산액에 3차 아민류를 더 포함하여 수행하는 것이 바람직하다.In the preparation method of the present invention, step 2) is preferably performed by further including tertiary amines in the conductive polymer dispersion.
나아가, 본 발명은 상기의 수분산성 폴리우레탄 기반에 나노셀룰로오스 및 전도성 폴리머가 복합화된 친환경성 전도성 복합체를 이용한 용도를 제공한다. Furthermore, the present invention provides a use of an environmentally friendly conductive composite in which nanocellulose and a conductive polymer are combined on the water-dispersible polyurethane base.
구체적으로, 상기의 친환경성 전도성 복합체 함유 분산액을 이용한 섬유제품을 제공한다.Specifically, it provides a fiber product using the environment-friendly conductive composite-containing dispersion.
또한, 상기의 친환경성 및 전도성을 구현한 복합체를 이용한 척추재생 및 신경조직 재생재료를 제공한다. In addition, the present invention provides a spinal regeneration and neural tissue regeneration material using a complex that implements the environmental friendliness and conductivity.
본 발명에 의하면, 친환경 특성의 수분산성 폴리우레탄 기반에 나노셀룰로오스 및 전도성 폴리머를 안정적으로 복합화한 복합체를 제공할 수 있다. According to the present invention, it is possible to provide a composite in which nanocellulose and a conductive polymer are stably complexed on a water-dispersible polyurethane base having eco-friendly properties.
본 발명에서 사용되는 나노셀룰로오스는 종래 황산법이 아닌 수산화나트륨(NaOH)와 우레아(Urea)를 사용하여 생분해성이 높은 재생 나노셀룰로오스 입자를 제조함으로써, 생분해성이 높은 나노셀룰로오스 입자로 복합화함으로써, 복합체에 생분해성능을 부여할 수 있다. The nanocellulose used in the present invention is manufactured by using biodegradable nanocellulose particles having high biodegradability by producing highly biodegradable regenerated nanocellulose particles using sodium hydroxide (NaOH) and urea (Urea) instead of the conventional sulfuric acid method. Biodegradation can be imparted.
또한, 본 발명의 전도성 폴리머를 복합화하여 복합체에 전도성을 부여함으로써, 친환경성 및 인장강도 향상과 더불어 전도성이 부여되므로, 이를 섬유제품 또는 메디칼 용도에 유용히 적용할 수 있다. In addition, since the conductive polymer of the present invention is complexed to impart conductivity to the composite, conductivity and imparting conductivity are improved, which can be usefully applied to textile products or medical applications.
도 1은 본 발명의 나노셀룰로오스를 나타낸 TEM 사진이고,
도 2는 본 발명의 나노셀룰로오스의 X-선 회절피크를 통한 결정화도이고,
도 3은 본 발명의 예비복합체에 대한 단계별 X-선 분석결과를 도시한 것이고,
도 4는 본 발명의 예비복합체에 있어서 나노셀룰로오스 함량별 가수분해능 결과이고,
도 5는 본 발명의 전도성 폴리머 사용에 따른 색상을 나타낸 것이고,
도 6은 본 발명의 예비복합체에 있어서 전도성 폴리머 복합화 단계별 인장강도 물성결과이고,
도 7은 본 발명의 제조방법 중 단계 1)에서 사용되는 나노셀룰로오스 입자의 제조공정을 모식적으로 도시한 것이고,
도 8은 본 발명의 친환경성 전도성 복합체 분산액을 직물에 처리한 후 직물의 인장강도를 도시한 것이고,
도 9는 도 8의 결과에서 마모 이후 직물의 인장강도 변화를 도시한 것이다. 1 is a TEM photograph showing a nanocellulose of the present invention,
2 is a crystallization degree through the X-ray diffraction peak of the nanocellulose of the present invention,
Figure 3 shows the results of the step X-ray analysis of the precomposite of the present invention,
4 is a hydrolysis result of each nanocellulose content in the precomposite of the present invention,
5 shows the color according to the use of the conductive polymer of the present invention,
6 is a tensile strength physical property results of the conductive polymer compounding step in the precomposite of the present invention,
FIG. 7 schematically illustrates a manufacturing process of the nanocellulose particles used in step 1) of the manufacturing method of the present invention.
Figure 8 shows the tensile strength of the fabric after treating the environmentally friendly conductive composite dispersion of the present invention,
9 shows the change in tensile strength of the fabric after wear in the results of FIG. 8.
이하, 본 발명을 상세히 설명하고자 한다. Hereinafter, the present invention will be described in detail.
본 발명은 수분산성 폴리우레탄 기반에 나노셀룰로오스 및 전도성 폴리머가 복합화된 친환경성 전도성 복합체를 제공한다.The present invention provides an eco-friendly conductive composite in which nanocellulose and a conductive polymer are combined on a water-dispersible polyurethane base.
구체적으로, 수분산성 폴리우레탄과 나노셀룰로오스로 이루어진 친환경성의 예비복합체 100 중량부에 대하여, 바람직하게는 전도성 폴리머 1.0 내지 10 중량부, 더욱 바람직하게는 0.1 내지 7.5 중량부가 수분산성 폴리우레탄/나노셀룰로오스/전도성 폴리머로 이루어진 친환경성 전도성 복합체를 제공한다.Specifically, with respect to 100 parts by weight of the environmentally friendly precomposite consisting of water-dispersible polyurethane and nanocellulose, preferably 1.0 to 10 parts by weight of conductive polymer, more preferably 0.1 to 7.5 parts by weight of water dispersible polyurethane / nanocellulose / It provides an environmentally friendly conductive composite made of a conductive polymer.
도 1은 본 발명의 나노셀룰로오스를 나타낸 TEM 사진으로서, 예비복합체에 포함된 나노셀룰로오스는 10 내지 30nm 나노크기의 구형 입자이다. 상기 나노셀룰로오스의 입자크기가 나노 단위로 작아질수록, 수분산성 폴리우레탄과의 계면결합력이 증가되므로 복합화에 유리하다. Figure 1 is a TEM photograph showing the nanocellulose of the present invention, the nanocellulose contained in the precomposite is a spherical particle of 10 to 30nm nanosize. As the particle size of the nanocellulose is smaller in nano units, the interfacial bonding force with the water-dispersible polyurethane is increased, which is advantageous for the compounding.
본 발명의 나노셀룰로오스는 마이크로셀룰로오스(MCC)로부터 수산화나트륨(NaOH)와 우레아(Urea)를 이용하여 pH 8수준으로 재생된 나노셀룰로오스(RCNs)로서 결정화도가 낮은 반결정성의 입자특성을 갖는다. The nanocellulose of the present invention is nanocellulose (RCNs) regenerated to
도 2는 본 발명의 나노셀룰로오스의 X-선 회절피크를 통한 결정화도를 나타낸 것으로서, 종래 황산을 이용하여 얻어진 나노입자는 결정형태(셀룰로오스 II)를 보인 반면, 본 발명의 재생된 나노셀룰로오스의 결정화도는 반결정성 결정상태를 보이고 있다. Figure 2 shows the degree of crystallization through the X-ray diffraction peak of the nanocellulose of the present invention, while the nanoparticles obtained using conventional sulfuric acid showed a crystalline form (cellulose II), the crystallinity of the regenerated nanocellulose of the present invention is It shows semicrystalline state.
본 발명에서 예비복합체라 함은 수분산성 폴리우레탄의 합성단계에 나노셀룰로오스 분산액을 투입하여, 상기 수분산성 폴리우레탄의 합성과 동시에 나노셀룰로오스와 복합화된 것을 의미한다.In the present invention, the precomposite means that the nanocellulose dispersion is added to the synthesis step of the water-dispersible polyurethane, and simultaneously synthesized with the water-dispersible polyurethane and nanocellulose.
도 3은 본 발명의 예비복합체에 대한 단계별 X-선 분석결과를 도시한 것이다. Figure 3 shows the results of the step X-ray analysis of the precomposite of the present invention.
구체적으로, 도 3으로부터, 마이크로셀룰로오스(MCC: 셀룰로오스 I 결정형태) 대비, 상기 마이크로셀룰로오스(MCC)로부터 재생된 나노셀룰로오스 입자(RCNs)는 결정화도가 낮은 반결정성 결정상태로 대비된다. Specifically, from FIG. 3, compared to microcellulose (MCC: cellulose I crystalline form), nanocellulose particles (RCNs) regenerated from the microcellulose (MCC) are contrasted in a semicrystalline crystalline state with low crystallinity.
또한, 수분산성 폴리우레탄 고유의 X-선 회절피크로부터, 나노셀룰로오스의 농도가 증가할수록 X-선 피크세기가 증가하는 경향을 보임으로써, 수분산성 폴리우레탄의 합성과 동시에 수분산성 폴리우레탄과 나노셀룰로오스간의 복합화를 확인할 수 있다. In addition, from the inherent X-ray diffraction peaks of the water-dispersible polyurethane, as the concentration of the nanocellulose increases, the X-ray peak intensity tends to increase, thereby simultaneously synthesizing the water-dispersible polyurethane and the nano-cellulose. You can see the complexity of the liver.
도 4는 본 발명의 예비복합체에 있어서 나노셀룰로오스 함량별 가수분해능 결과로서, 수분산성 폴리우레탄 자체는 생분해성능이 관찰되지 않으나, 나노셀룰로오스(CNs)는 70 시간 이후 80%의 생분해성능이 발현된다. Figure 4 is a hydrolyzable result of each nanocellulose content in the precomposite of the present invention, the water-dispersible polyurethane itself is not observed biodegradation, nanocellulose (CNs) is expressed 80% biodegradation after 70 hours.
따라서, 수분산성 폴리우레탄과 나노셀룰로오스로 이루어진 예비복합체의 경우, 나노셀룰로오스의 함량에 따라 가수분해능 증가를 확인할 수 있다. 이러한 결과로부터, 수분산성 폴리우레탄 기반에 나노셀룰로오스가 안정적으로 복합화되고 그에 따라 예비복합체에 생분해성능이 부여됨을 확인할 수 있다. Therefore, in the case of the precomposite composed of the water-dispersible polyurethane and the nanocellulose, it is possible to confirm the increase in the hydrolyzability according to the content of the nanocellulose. From these results, it can be confirmed that nanocellulose is stably complexed on the basis of the water dispersible polyurethane, and thus biodegradability is given to the precomposite.
이상의 예비복합체에서 수분산성 폴리우레탄과 나노셀룰로오스가 1: 0.01 내지 0.3 중량비율, 더욱 바람직하게는 1: 0.03 내지 0.202 중량비율로 복합화되는 것이 바람직하다. 상기 나노셀룰로오스의 중량비율이 0.01 미만이면, 자기분해능(생분해성능)과 강도, 초기 탄성율 등의 나노셀룰로오스 첨가로 인해 기대되는 물성 향상에 미흡하고 0.3 중량비율을 초과하면, 복합화 과정에서의 혼용성에 문제가 있다. In the above precomposite, it is preferable that the water dispersible polyurethane and the nanocellulose are compounded in a weight ratio of 1: 0.01 to 0.3, more preferably 1: 0.03 to 0.202. If the weight ratio of the nanocellulose is less than 0.01, it is insufficient to improve the expected physical properties due to the addition of nanocellulose such as self-degradability (biodegradability), strength, and initial elastic modulus, and if it exceeds 0.3 weight ratio, there is a problem in compatibility in the compounding process. There is.
본 발명은 상기 예비복합체에, 전도성 폴리머가 복합화되어 수분산성 폴리우레탄/나노셀룰로오스/전도성 폴리머로 이루어진 친환경성 전도성 복합체로 완성된다. The present invention is a composite of the conductive polymer in the pre-complex, the environmentally friendly conductive composite consisting of water-dispersible polyurethane / nano cellulose / conductive polymer is completed.
본 발명에서 사용되는 전도성 폴리머는 폴리티오펜(PEDOT:PSS), 폴리아세틸렌, 폴리피롤 및 폴리아닐린으로 이루어진 군에서 선택되는 어느 하나이며, 더욱 바람직하게는 폴리티오펜(PEDOT:PSS) 수분산액을 사용하는 것이다. The conductive polymer used in the present invention is any one selected from the group consisting of polythiophene (PEDOT: PSS), polyacetylene, polypyrrole and polyaniline, and more preferably using an aqueous polythiophene (PEDOT: PSS) aqueous dispersion. will be.
도 5는 본 발명의 전도성 폴리머 사용에 따른 색상을 나타낸 것으로서, PEDOT:PSS 수분산액 기본의 파란색으로 그대로 구현하는 반면, 카본 블랙을 사용한 경우는 색상이 블랙으로 한정되는 문제가 있어, 본 발명은 전도성 유기 폴리머를 사용하는 것이 바람직하며, 단, 카본블랙 또는 그래파이트 등의 카본 소재의 전도성 재료는 제외한다. Figure 5 shows the color according to the use of the conductive polymer of the present invention, while the PEDOT: PSS is implemented in blue as the base of the aqueous dispersion, while using carbon black there is a problem that the color is limited to black, the present invention is conductive It is preferable to use an organic polymer, except for carbon conductive materials such as carbon black or graphite.
도 6은 본 발명의 예비복합체에 있어서 전도성 폴리머 복합화 단계별 인장강도 물성결과로서, 수분산성 폴리우레탄에 나노셀룰로오스 입자의 첨가량이 증가할수록 예비복합체의 인장강도가 증가함으로써, 상기 나노셀룰로오스 입자로 인한 강화효과를 확인할 수 있다. 6 is a result of tensile strength properties of conductive polymers in each of the precomposites according to the present invention. As the amount of nanocellulose particles added to the water-dispersible polyurethane increases, the tensile strength of the precomposites increases, thereby enhancing the effect of the nanocellulose particles. You can check.
또한, 상기 예비복합체에 전도성 폴리머인 PEDOT:PSS 수분산액을 첨가한 경우, 인장강도 물성이 현저히 증가하므로, 복합체 합성여부 및 그로부터 복합체의 물성향상을 확인할 수 있다. In addition, when the PEDOT: PSS aqueous dispersion, which is a conductive polymer, is added to the precomposite, tensile strength properties are significantly increased, and thus the composite can be synthesized and the physical properties of the composite can be confirmed therefrom.
따라서, 본 발명은 복합체에 전도성을 부여하기 위하여, 전도성 폴리머를 혼합하여 복합화하며, 그로 인해 인장강도 등의 물성이 향상된다. 이때, 전도성(Ω-1cm-1)은 1.25×10-4 내지 2.2×10-1, 더욱 바람직하게는 1.2×10-3 내지 2.2×10-1로 나타난다. Therefore, in the present invention, in order to impart conductivity to the composite, the conductive polymer is mixed and complexed, thereby improving physical properties such as tensile strength. In this case, the conductivity (Ω −1 cm −1 ) is represented by 1.25 × 10 −4 to 2.2 × 10 −1 , more preferably 1.2 × 10 −3 to 2.2 × 10 −1 .
또한, 본 발명은 1) 수분산성 폴리우레탄의 합성단계에 나노셀룰로오스 분산액을 투입하여 인시츄(In-situ)로 수분산성 폴리우레탄 합성과 동시에 수분산성 폴리우레탄과 나노셀룰로오스로 이루어진 친환경성의 예비복합체를 생성하고, In addition, the present invention 1) by incorporating the nano-cellulose dispersion in the synthesis step of the water-dispersible polyurethane in-situ (synthesis) water-soluble polyurethane and at the same time an environmentally friendly pre-composite consisting of water-dispersible polyurethane and nanocellulose Create,
2) 상기 예비복합체에 전도성 폴리머 분산액을 투입하고 복합화하여 제조되는, 수분산성 폴리우레탄/나노셀룰로오스/전도성 폴리머로 이루어진 친환경성 전도성 복합체의 제조방법을 제공한다. 2) It provides a method for producing an environmentally friendly conductive composite consisting of a water-dispersible polyurethane / nano cellulose / conductive polymer prepared by injecting and complexing a conductive polymer dispersion in the pre-composite.
본 발명의 제조방법에 있어서, 상기 1) 단계는 생분해성이 높은 나노셀룰로오스 입자를 제조하기 위하여, 마이크로 셀룰로오스로부터 수산화나트륨(NaOH)와 우레아(Urea)를 이용하여 재생셀룰로오스를 제조한다. In the production method of the present invention, step 1) is to prepare regenerated cellulose using sodium hydroxide (NaOH) and urea (Urea) from the micro cellulose in order to produce a high biodegradable nanocellulose particles.
도 7은 본 발명의 제조방법 중 단계 1)에서 사용되는 나노셀룰로오스 입자의 제조공정을 모식적으로 도시한 것으로서, 7% 수산화나트륨(NaOH)와 12% 우레아(Urea)를 이용하여 용액을 실온에서 2 시간 동안 교반하고, -20℃에서 12 시간 동안 냉동기에 보관 후 원심분리를 통해 재생셀룰로오스의 침전 및 분리공정을 거친다. 이후 얻어진 용액의 pH 값을 초음파 처리 후 약 8 수준으로 조정함으로써, 수분산성 폴리우레탄의 pH 값(pH 9)과 유사하게 조정함으로써, 복합화에 유리하도록 한다. 7 is a view schematically showing a manufacturing process of the nanocellulose particles used in step 1) of the manufacturing method of the present invention, using 7% sodium hydroxide (NaOH) and 12% urea (Urea) at room temperature Stir for 2 hours, store in a freezer at -20 ℃ for 12 hours and then precipitate and separate the regenerated cellulose through centrifugation. The pH value of the resulting solution is then adjusted to about 8 levels after sonication, similar to the pH value (pH 9) of the water dispersible polyurethane, to favor compounding.
또한, 수분산성 폴리우레탄과의 계면결합력이 증가되어 복합화에 유리하도록 10 내지 30nm 나노크기를 가지는 구형의 나노셀룰로오스 입자를 사용하는 것이다. In addition, it is to use spherical nanocellulose particles having a nano-size of 10 to 30nm to increase the interfacial bonding force with the water-dispersible polyurethane is advantageous to the composite.
이때, 상기 1) 단계에서 수분산성 폴리우레탄의 합성단계에 나노셀룰로오스 분산액의 투입단계는 폴리테트라메틸렌글리콜(PTMG)를 포함하는 폴리올과 디메틸올프로피온산(DMPA)을 포함하는 이오노머간의 몰비를 조절하여 프리폴리머의 혼합단계, IPDI(Isophoron di-isocyanate)를 포함하는 디이소시아네이트를 혼합하는 중합반응단계 및 상기로부터 프리폴리머의 이소시아네이트기와 우레아와의 반응으로 합성된 올리고머를 알킬화제를 혼합하여 분산하는 단계 중 어느 한 단계에 투입하여 인시츄(In-situ)로 수분산성 폴리우레탄 합성하는 동시에 수분산성 폴리우레탄과 나노셀룰로오스를 복합화한, 친환경성의 예비복합체를 생성하는 것이다. At this time, the step of injecting the nanocellulose dispersion into the synthesis step of the water-dispersible polyurethane in step 1) is a prepolymer by controlling the molar ratio between the polyol containing polytetramethylene glycol (PTMG) and the ionomer containing dimethylolpropionic acid (DMPA) In the mixing step of the above, the polymerization reaction step of mixing diisocyanate containing IPDI (Isophoron di-isocyanate) and the oligomer synthesized by the reaction of isocyanate group and urea of the prepolymer from the above step of mixing and dispersing the alkylating agent In-situ is used to synthesize water dispersible polyurethane, and at the same time, to produce an eco-friendly precomposite complex of water dispersible polyurethane and nanocellulose.
이때, 수분산성 폴리우레탄을 합성하는 단계에, 나노셀룰로오스 분산액 투입단계를 달리하여 제조한 결과, 필름을 제조하여 투명도를 비교한 결과, 단계별 사용용매에 따라 DMF> 아세톤> 물 순서로 나타나고, 인장강도는 DMF = 아세톤> 물 순서로 확인된다[미도시].At this time, in the step of synthesizing the water-dispersible polyurethane, the nanocellulose dispersion was added in a different step, as a result of preparing a film to compare the transparency, according to the solvent used step by step appears in the order of DMF> acetone> water, tensile strength Is identified in the order of DMF = acetone> water [not shown].
상기 단계 1)에서 제조된 예비복합체 분산액에 고점도 용매를 더 투입함으로써 전도성을 향상시킬 수 있다. 이에, 본 발명의 실시예에서는 EG, DMSO 및 그들의 혼합형태로 이루어진 군에서 선택된 용매를 더 투입하여 전도도를 향상시킨다. The conductivity may be improved by further adding a high viscosity solvent to the precomposite dispersion prepared in step 1). Thus, in the embodiment of the present invention further improve the conductivity by further adding a solvent selected from the group consisting of EG, DMSO and their mixed form.
또한, 본 발명의 제조방법에 있어서, 상기 2) 단계는 전도성 폴리머 분산액에 3차 아민류를 더 포함하는데, 전도성 폴리머의 강산성으로 인해 수분산 폴리우레탄과 전도성 폴리머의 상 분리를 방지하기 위함이다. 즉, 상기 3차 아민류를 첨가함으로써, 수분산성 폴리우레탄와 전도성 폴리머의 pH가 각각 9 및 2 정도로 pH 값의 차이가 커서 복합화 과정에서 융합 또는 응고되는 문제를 방지할 수 있다. 이때, 본 발명의 실시예에서는 트리메틸아민을 사용하여 설명하고 있으나, 이에 한정되지 아니하고, 당해 분야에 공지된 3차 아민류는 특별한 제한없이 사용할 수 있다. In addition, in the manufacturing method of the present invention, step 2) further includes tertiary amines in the conductive polymer dispersion, in order to prevent phase separation of the water-dispersed polyurethane and the conductive polymer due to the strong acidity of the conductive polymer. That is, by adding the tertiary amines, the pH of the water-dispersible polyurethane and the conductive polymer is 9 and 2, respectively, so that the difference in pH value is large, thereby preventing the problem of fusion or solidification during the compounding process. In this case, the embodiment of the present invention is described using trimethylamine, but is not limited thereto, and tertiary amines known in the art may be used without particular limitation.
나아가, 본 발명은 수분산성 폴리우레탄/나노셀룰로오스/전도성 폴리머로 이루어진 친환경성 전도성 복합체를 이용한 섬유제품을 제공한다. Furthermore, the present invention provides a fiber product using an environmentally friendly conductive composite made of a water dispersible polyurethane / nanocellulose / conductive polymer.
도 8은 본 발명의 친환경성 전도성 복합체 분산액을 직물에 처리한 후 직물의 인장강도를 도시한 것이고, 도 9는 마모 후 직물의 인장강도를 도시한 것이다. Figure 8 shows the tensile strength of the fabric after treating the environmentally friendly conductive composite dispersion of the present invention, Figure 9 shows the tensile strength of the fabric after wear.
도 8의 결과로부터, 분산액을 미처리한 직물의 인장강도 대비, 본 발명의 친환경성 전도성 복합체 분산액을 직물에 처리한 경우, 인장강도의 현저한 결과를 확인할 수 있으며, 특히 나노셀룰로오스의 첨가 유무에 따라 인장강도 개선의 결과가 달라짐을 확인함으로써, 나노셀룰로오스 첨가로 인해 인장강도 향상을 부여할 수 있다. From the results of Figure 8, compared to the tensile strength of the non-dispersed fabric, when the environmentally friendly conductive composite dispersion of the present invention treated the fabric, the remarkable result of the tensile strength can be confirmed, in particular the tensile depending on the addition of nanocellulose By confirming that the result of the strength improvement is different, it is possible to give a tensile strength improvement due to the addition of nanocellulose.
도 9는 마모횟수에 따른 전도도 감소현상 역시 나노셀룰로오스의 첨가로 인해 인장강도가 유지됨으로 확인할 수 있다. Figure 9 shows that the conductivity reduction according to the number of wear is also confirmed that the tensile strength is maintained due to the addition of nanocellulose.
또한, 본 발명은 수분산성 폴리우레탄/나노셀룰로오스/전도성 폴리머로 이루어진 친환경성 전도성 복합체를 이용한 척추재생 또는 신경조직재생 재료를 제공한다. In addition, the present invention provides a spinal regeneration or nerve tissue regeneration material using an environmentally friendly conductive composite made of a water dispersible polyurethane / nanocellulose / conductive polymer.
이상에서 살펴본 바와 같이, 본 발명의 수분산성 폴리우레탄 기반에 나노셀룰로오스 및 전도성 폴리머가 복합화됨으로써, 친환경성과 전도성이 부여되므로, 척수 및 신경세포는 배향성이 있어서 약간 전류가 흐르게 되면 배향성이 좋아져 재생에 유리하다. As described above, since nanocellulose and a conductive polymer are combined with the water-dispersible polyurethane base of the present invention, environmentally friendly and conductive properties are provided, spinal cord and neurons are oriented so that the orientation becomes better when a little current flows, which is advantageous for regeneration. Do.
특히, 본 발명의 친환경성 전도성 복합체를 구성하는 수분산성 폴리우레탄이 대표적 친환경성 재료이고, 나노셀룰로오스가 종래의 황산법이 아닌, 수산화나트륨(NaOH)와 우레아(Urea)를 이용하여 pH를 조정하여 재생한 친환경성 재료이고, 상기 나노셀룰로오스의 생분해성능을 이용함으로써, 메디칼 용도에 적합하다. In particular, the water-dispersible polyurethane constituting the eco-friendly conductive composite of the present invention is a representative eco-friendly material, the nano cellulose is regenerated by adjusting the pH using sodium hydroxide (NaOH) and urea (Urea), not the conventional sulfuric acid method It is an environmentally friendly material and is suitable for medical use by utilizing the biodegradability of the nanocellulose.
이하, 실시예를 통하여 본 발명을 보다 상세히 설명하고자 한다. Hereinafter, the present invention will be described in more detail with reference to Examples.
본 실시예는 본 발명을 보다 구체적으로 설명하기 위한 것이며, 본 발명의 범위가 이들 실시예에 한정되는 것은 아니다. This embodiment is intended to illustrate the present invention in more detail, and the scope of the present invention is not limited to these examples.
<실시예 1∼8> 친환경성 전도성 복합체 제조<Examples 1 to 8> Eco-friendly conductive composites
단계 1: 예비복합체의 합성Step 1: Synthesis of Precomplex
도 7에 도시된 바와 같이, 7% 수산화나트륨(NaOH)와 12% 우레아(Urea)를 이용하고 5%의 마이크로 셀룰로오스(MCC) 함유용액을 실온에서 2 시간 동안 교반하고, -20℃에서 12 시간 동안 냉동기에 보관하였다. 이후 원심분리를 통해 재생셀룰로오스의 침전 및 분리공정을 거치고, 얻어진 용액을 초음파처리하고, pH 값을 약 8로 조정하여 준비하였다. As shown in Figure 7, using 7% sodium hydroxide (NaOH) and 12% urea (Urea) and 5% micro cellulose (MCC) containing solution was stirred for 2 hours at room temperature, 12 hours at -20 ℃ While stored in the freezer. Thereafter, the precipitated and separated process of regenerated cellulose was carried out through centrifugation, and the obtained solution was sonicated and prepared by adjusting the pH value to about 8.
상기 제조된 나노셀룰로오스 분산액을 하기 수분산성 폴리우레탄의 합성단계의 1,2,3 단계 중 어느 하나에 투입할 수 있으며, 현 단계에서는 1단계에 투입하여 인시츄(In-situ)로 수분산성 폴리우레탄과 나노셀룰로오스로 이루어진 친환경성의 예비복합체를 합성하였다. The prepared nano cellulose dispersion may be added to any one of 1,2,3 steps of the synthesis step of the water-dispersible polyurethane, and in the present step, water-dispersible poly in situ ( In-situ ) An eco-friendly precomposite composed of urethane and nanocellulose was synthesized.
단계 2: 복합체의 합성Step 2: Synthesis of Complex
단계 1에서 합성된 예비복합체에 대하여, 전도성 폴리머(PEDOT/PSS) 분산액을 하기 표 1에 기재된 바와 같이, 배합하여 복합체를 제조하였다. For the precomposite synthesized in
이때, 복합체의 전도성 향상을 위하여, 고점도 용매 EG, DMSO 단독 또는 그들의 혼합형태를 사용하고, 3차 아민(Trimethylamine)을 배합하여 친환경성 전도성 복합체를 제조하였다. At this time, in order to improve the conductivity of the composite, using a high viscosity solvent EG, DMSO alone or a mixed form thereof, by mixing a tertiary amine (Trimethylamine) to prepare an environmentally friendly conductive composite.
<실시예 9> 친환경성 전도성 복합체를 이용한 인공피혁 제조Example 9 Manufacture of Artificial Leather Using Eco-Friendly Conductive Composite
상기 표 1에서 전도도가 가장 우수한 실시예 1의 복합체를 사용하되, 이를 함유한 분산액을 제조하고, 폴리에스테르 직물을 침지 후 건조하여 인공피혁을 제조하였다.Using the composite of Example 1, the most excellent conductivity in Table 1, to prepare a dispersion containing it, and immersed and dried polyester fabric to produce artificial leather.
이후, 마모횟수별 전도도 변화를 측정하였다. Then, the change in conductivity according to the number of wear was measured.
도 8은 직물에 처리유무에 따른 직물의 인장강도 변화를 도시한 것으로서, 수분산성 폴리우레탄(WPU)/나노셀룰로오스(NC)/전도성 폴리머(PEDOT/PSS)로 이루어진 복합체의 경우, 인장강도가 개선되었으며, 상기 표 2에서 확인되는 바와 같이, 전도도 개선효과와 동일하게 확인되었다. Figure 8 shows the change in the tensile strength of the fabric with or without treatment in the fabric, in the case of a composite made of water-dispersible polyurethane (WPU) / nanocellulose (NC) / conductive polymer (PEDOT / PSS), the tensile strength is improved And, as confirmed in Table 2, the same as the conductivity improving effect was confirmed.
또한, 도 9는 마모횟수 1000회 이후 직물의 인장강도를 도시한 결과 역시 WPU/NC/ PEDOT/PSS로 이루어진 복합체의 경우 우수한 인장강도가 확인되었으며, 상기 표 2에서도 마모횟수가 증가할수록 전도도 감소경향은 보이나, 나노셀룰로오스(NC)가 함유된 복합체의 경우 전도도 감소폭이 작아 전도성 유지를 확인하였다. In addition, Figure 9 shows the tensile strength of the fabric after 1000 times the number of wear was also confirmed excellent tensile strength in the case of a composite composed of WPU / NC / PEDOT / PSS, also in the table 2 as the number of wear increases the tendency to decrease the conductivity Silver is visible, but in the case of a composite containing nanocellulose (NC), the conductivity decreases, and the conductivity is confirmed to be small.
이상에서 본 발명은 기재된 구체예에 대해서만 상세히 설명되었지만 본 발명의 기술사상 범위 내에서 다양한 변형 및 수정이 가능함은 당업자에게 있어서 명백한 것이며, 이러한 변형 및 수정이 첨부된 특허청구범위에 속함은 당연한 것이다.Although the present invention has been described in detail only with respect to the described embodiments, it will be apparent to those skilled in the art that various modifications and variations are possible within the technical scope of the present invention, and such modifications and modifications are within the scope of the appended claims.
Claims (11)
전도성 폴리머 1.0 내지 10 중량부가 복합화된, 수분산성 폴리우레탄/나노셀룰로오스/전도성 폴리머로 이루어진 친환경성 전도성 복합체.For 100 parts by weight of an environmentally friendly precomposite consisting of a water dispersible polyurethane and nanocellulose,
Eco-friendly conductive composite consisting of a water dispersible polyurethane / nanocellulose / conductive polymer having 1.0 to 10 parts by weight of a conductive polymer.
2) 상기 예비복합체에 전도성 폴리머 분산액을 투입하여 복합화한,
수분산성 폴리우레탄/나노셀룰로오스/전도성 폴리머로 이루어진 친환경성 전도성 복합체의 제조방법.1) Synthesis of the water-dispersible polyurethane into the synthesis step of the nanocellulose dispersion in-situ to produce a water-dispersible polyurethane at the same time to create an eco-friendly pre-composite consisting of water-dispersible polyurethane and nanocellulose,
2) complexing by adding a conductive polymer dispersion to the precomposite,
Method for producing an environmentally friendly conductive composite consisting of water-dispersible polyurethane / nanocellulose / conductive polymer.
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KR20220132828A (en) * | 2021-03-24 | 2022-10-04 | 동아대학교 산학협력단 | Manufacturing method of anionic water-dispersible polyurethane dispersion and biodegradable polyurethane film prepared therefrom |
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