KR20140088368A - Method for manufacturing of eco-friendly super absorbent resin by radiation - Google Patents
Method for manufacturing of eco-friendly super absorbent resin by radiation Download PDFInfo
- Publication number
- KR20140088368A KR20140088368A KR1020130000180A KR20130000180A KR20140088368A KR 20140088368 A KR20140088368 A KR 20140088368A KR 1020130000180 A KR1020130000180 A KR 1020130000180A KR 20130000180 A KR20130000180 A KR 20130000180A KR 20140088368 A KR20140088368 A KR 20140088368A
- Authority
- KR
- South Korea
- Prior art keywords
- citric acid
- carboxymethylcellulose
- radiation
- superabsorbent resin
- gel
- Prior art date
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/08—Cellulose derivatives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/075—Macromolecular gels
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/28—Treatment by wave energy or particle radiation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Dispersion Chemistry (AREA)
- Analytical Chemistry (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
Description
본 발명은 셀룰로오스계 유도체인 카복시메틸셀룰로오스(carboxymethylcellulose, CMC)에 구연산(Citric acid, CA)을 첨가한 후 방사선을 조사하여 얻은 친환경 고흡수성 수지 제조 방법 및 상기 제조방법으로 제조된 무독성 생분해성 고흡수성 수지에 관한 것이다.
The present invention relates to a process for producing an environmentally highly superabsorbent resin obtained by adding citric acid (CA) to a carboxymethylcellulose (CMC), which is a cellulose derivative, and irradiating it with radiation, and a process for producing an environment- Resin.
고흡수성 수지는 일반적인 친수성 물질보다 다량의 물을 더 많이 흡수할 수 있는 일종의 고분자를 일컬으며, 이는 수용성 고분자 내를 가교시킴으로 망상 구조를 이루게하여 수지가 물에 녹는 것을 방지하고 망 내에 많은 물을 흡수시키는 성질을 가지고있다. 시판용 고흡수성 수지 중 대표적인 예로 폴리아크릴에이트(Polyacylate)는 고흡수성 산업에서 가장 널리 사용되는 기본적 수지이며, 가교제로서 아크릴 산을 사용한다. 상기 아크릴 산은 에틸렌(ethylene)과 가솔린 생산의 부산물인 프로펜(propene)으로부터 생산된다. 따라서, 이 폴리아크릴에이트는 석유산업에서 얻어지는 물질로 생분해가 되지 않으며 독성을 띄고 있어 농업이나 위생용품과 관련된 흡수 물질에 사용하기에는 부적절하나, 일반적으로 시장에서 유통되는 대부분의 기저귀나 생리대의 고흡성 물질로 사용된다. 따라서, 환경적인 보호 및 인체 보호를 위하여 생분해성을 가지면서 무독성인 고흡수성 물질의 개발이 필요하다.A superabsorbent resin is a kind of polymer that absorbs more water than a general hydrophilic substance. This crosslinks the water-soluble polymer to form a network structure, thereby preventing the resin from dissolving in water and absorbing a large amount of water . As a representative example of a commercially available superabsorbent resin, polyacylate is the most widely used basic resin in the superabsorbent industry and acrylic acid is used as a crosslinking agent. The acrylic acid is produced from ethylene and propene, which is a by-product of gasoline production. Therefore, this polyacrylate is a material obtained from the petroleum industry and is not biodegradable and toxic. Therefore, it is not suitable for absorbing materials related to agriculture or sanitary goods. However, most of the polyacrylate is used in most diapers and sanitary napkins . Therefore, it is necessary to develop a biodegradable, non - toxic, highly water - absorbent material for environmental protection and human body protection.
이에, 본 발명자들은 유독성을 지닌 가교제 아크릴 산(acylic acid) 및 가교하기 위한 촉매제 차아인산나트륨(sodium hypophosphite, SHP)을 첨가하지 않는 친환경 고흡수성 수지를 개발하던 중에 천연 식물성 물질인 셀룰로오스로부터 수용성 유도체로 제조한 카복시메틸셀룰로오스(carboxymethylcellulose, CMC)에 천연 항산화제인 구연산(Citric acid, CA)을 배합하여 방사선을 조사하여 제조된 천연 고흡수성 수지는 무독성, 생분해 천연 고흡수성 수지임을 확인하여 본 발명을 완성하였다.
Accordingly, the present inventors have developed an eco-friendly superabsorbent resin which does not add a crosslinking agent acylic acid having a toxicity and sodium hypophosphite (SHP) as a catalyst for crosslinking, and has developed a water-soluble derivative from cellulosic, The inventors of the present invention completed the present invention by confirming that the natural superabsorbent resin prepared by mixing citric acid (CA), which is a natural antioxidant, with carboxymethylcellulose (CMC) prepared by irradiation with radiation is a nontoxic and biodegradable natural superabsorbent resin .
본 발명의 목적은 방사선에 의한 친환경 고흡수성 수지의 제조 방법을 제공하는 것이다. It is an object of the present invention to provide a method for producing an environmentally highly superabsorbent resin by radiation.
본 발명의 다른 목적은 방사선에 의한 친환경 고흡수성 수지의 제조방법으로 제조된 카복시메틸셀룰로오스/구연산 겔로 구성된 무독성 고흡수성 수지를 제공하는 것이다.
Another object of the present invention is to provide a non-toxic superabsorbent resin composed of carboxymethylcellulose / citric acid gel prepared by a process for producing an environmentally highly superabsorbent resin by radiation.
상기 목적을 달성하기 위하여, 본 발명은 In order to achieve the above object,
1) 카복시메틸셀룰로오스(Carboxymethylcellulose, CMC)와 구연산(Citric acid, CA)을 배합하여 물에 녹이는 단계;1) mixing carboxymethylcellulose (CMC) with citric acid (CA) and dissolving in water;
2) 상기 단계 1)에서 배합된 카복시메틸셀룰로오스와 구연산 반죽에 방사선을 조사하는 단계; 및2) irradiating the citric acid paste with the carboxymethylcellulose compounded in the step 1); And
3) 상기 단계 2)에서 방사선이 조사된 카복시메틸셀룰로오스/구연산 겔을 건조하는 단계를 포함하는 것을 특징으로 하는 무독성 고흡수성 수지의 제조방법을 제공한다. 3) drying the carboxymethylcellulose / citric acid gel irradiated with the radiation in the step 2). The present invention also provides a method for producing a non-toxic superabsorbent resin.
또한, 본 발명은 방사선에 의한 친환경 고흡수성 수지의 제조방법으로 제조된 카복시메틸셀룰로오스/구연산 겔로 구성된 무독성 고흡수성 수지를 제공한다.
The present invention also provides a non-toxic superabsorbent resin composed of carboxymethylcellulose / citric acid gel prepared by a process for producing an environmentally highly superabsorbent resin by radiation.
본 발명은 따른 무독성 고흡수성 수지는 유독성을 지닌 가교제 아크릴 산(acylic acid) 및 가교하기 위한 촉매제 차아인산나트륨(SHP)을 첨가하지 않고 카복시메틸셀룰로오스(CMC)와 구연산(Citric acid, CA)을 배합한 후 방사선을 조사하여 무독성 고흡수성 수지를 제조하므로 피부에 무해하고 토양 및 물에 폐기했을 시에도 전혀 오염이 되지 않으며, 높은 가교도, 고흡수성 및 높은 수분보유율을 나타내므로 일회용 흡수용품 및 농업용품에 유용하게 사용될 수 있다.
The non-toxic superabsorbent resin according to the present invention is prepared by mixing carboxymethylcellulose (CMC) and citric acid (CA) without adding a crosslinking agent acylic acid having toxicity and a catalytic sodium hypophosphite (SHP) It is harmless to the skin and does not cause any contamination even when it is discarded in soil or water. Since it exhibits high degree of crosslinking, high absorptivity and high moisture retention rate, disposable absorbent article and agricultural article . ≪ / RTI >
도 1은 카복시메틸셀룰로오스/구연산의 친환경 고흡수성 수지를 제조하는 공정을 간략하게 설명하는 흐름도를 나타낸 그림이다.
도 2는 방사선 조사된 카복시메틸셀룰로오스/구연산 겔을 동결 건조하여 건조 수지를 얻은 다음 물에 팽윤시킨 그림이다.
도 3은 구연산 농도 및 방사선 선량별에 따른 가교도를 나타낸 겔화율에 대한 그래프이다.
도 4는 10% 카복시메틸셀룰로오스/ 2% 구연산 건조 겔의 방사선 선량에 따른 하루 후 물 흡수 정도를 나타낸 그래프이다.
도 5는 10% 카복시메틸셀룰로오스/ 2% 구연산 건조 겔의 물에 침지된 시간에 따라 팽윤 정도를 나타낸 그래프이다.
도 6은 10% 카복시메틸셀룰로오스/ 2% 구연산 건조 겔의 0.9% NaCl 수용액에 침지된 시간에 따라 팽윤 정도를 나타낸 그래프이다.
도 7은 물에 팽윤된 10% 카복시메틸셀룰로오스/ 2% 구연산 겔의 수분보유율에 대한 그래프이다.BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a flow chart briefly explaining a process for producing an environmentally highly superabsorbent resin of carboxymethylcellulose / citric acid. FIG.
FIG. 2 is a drawing of radiation-induced carboxymethylcellulose / citric acid gel obtained by lyophilization to obtain a dry resin and then swelling it in water.
3 is a graph showing the gelation rate showing the degree of crosslinking depending on the concentration of citric acid and the dose of radiation.
4 is a graph showing the degree of water absorption after 10 days of radiation dose of 10% carboxymethylcellulose / 2% citric acid dry gel.
5 is a graph showing swelling degree of 10% carboxymethylcellulose / 2% citric acid dry gel with time immersed in water.
FIG. 6 is a graph showing swelling degree with time immersed in 0.9% NaCl aqueous solution of 10% carboxymethylcellulose / 2% citric acid dry gel.
Figure 7 is a graph of the moisture retention of 10% carboxymethylcellulose / 2% citric acid gel swollen in water.
이하, 본 발명을 상세히 설명한다.
Hereinafter, the present invention will be described in detail.
본 발명은 The present invention
1) 카복시메틸셀룰로오스(Carboxymethylcellulose, CMC)와 구연산(Citric acid, CA)을 소정의 배합비율로 배합한 후 물에 녹여 반죽을 생성하는 단계;1) Blending carboxymethylcellulose (CMC) and citric acid (CA) at a predetermined mixing ratio and dissolving in water to produce dough;
2) 상기 단계 1)에서 생성된 반죽에 방사선을 조사하여 카복시메틸셀룰로오스/구연산 겔을 생성하는 단계; 및2) irradiating the dough produced in step 1) above with radiation to produce a carboxymethylcellulose / citric acid gel; And
3) 상기 단계 2)에서 생성된 카복시메틸셀룰로오스/구연산 겔을 건조하는 단계를 포함하는 것을 특징으로 하는 방사선에 의한 친환경 고흡수성 수지의 제조 방법을 제공한다.3) drying the carboxymethylcellulose / citric acid gel produced in the step 2). The present invention also provides a method for producing an environmentally highly superabsorbent resin by radiation.
이하, 상기 제조방법을 각 단계별로 상세히 설명한다.Hereinafter, the above manufacturing method will be described in detail for each step.
본 발명에 따른 제조방법에 있어서, 상기 단계 1)은 카복시메틸셀룰로오스와 구연산을 적절히 배합하여 물에 녹이는 단계이다. In the preparation method according to the present invention, the step 1) is a step of appropriately mixing carboxymethylcellulose and citric acid and dissolving in water.
구체적으로, 상기 단계 1)에서 배합비율은 상기 카복시메틸셀룰로오스 1 내지 30 중량% 와 상기 구연산 1 내지 30 중량%를 배합하는 것이 바람직하고, 10 내지 13 중량% 와 상기 구연산 2 내지 10 중량%를 배합하는 것이 보다 바람직하며, 10 내지 11 중량% 와 상기 구연산 2 내지 4 중량%를 배합하는 것이 가장 바람직하다. Specifically, in the step 1), 1 to 30% by weight of the carboxymethyl cellulose and 1 to 30% by weight of the citric acid are preferably blended, and 10 to 13% by weight and 2 to 10% by weight of the citric acid are mixed More preferably 10 to 11% by weight and
본 발명에 따른 제조방법에 있어서, 상기 단계 2)는 상기 카복시메틸셀룰로오스와 구연산 반죽에 방사선을 조사하는 단계이다.In the production method according to the present invention, the step 2) is a step of irradiating the carboxymethyl cellulose and the citric acid paste with radiation.
구체적으로, 상기 단계 2)에서 방사선은 감마선, 전자선, 이온빔, 중성자선, UV 및 플라즈마로 이루어지는 군으로부터 선택되는 어느 하나인 것이 바람직하고, 감마선, 전자선, 및 중성자선으로 이루어진 군으로부터 선택되는 것이 보다 바람직하며, 전자선인 것을 가장 바람직하다. Specifically, in the step 2), it is preferable that the radiation is any one selected from the group consisting of a gamma ray, an electron beam, an ion beam, a neutron beam, UV, and plasma, and is preferably selected from the group consisting of a gamma ray, And most preferably an electron beam.
또한, 상기 단계 2)에서 방사선은 총조사량이 5 내지 100 kGy인 것이 바람직하고, 20 내지 30 kGy인 것이 보다 바람직하며, 20 kGy인 것이 가장 바람직하다. 방사선의 총조사량이 100 kGy를 초과하는 경우 카복시메틸셀룰로오스와 구연산의 가교에 방해가 되거나, 흡수 후 수지의 물성 및 흡수력을 저하시킬 수 있으므로 바람직하지 않다.In addition, in the step 2), the total dose of radiation is preferably 5 to 100 kGy, more preferably 20 to 30 kGy, and most preferably 20 kGy. When the total irradiation amount of the radiation exceeds 100 kGy, it is not preferable because it may interfere with the crosslinking between carboxymethyl cellulose and citric acid, or may lower the physical properties and absorption power of the resin after absorption.
본 발명에 따른 제조방법에 있어서, 상기 단계 2)에서 방사선이 조사된 카복시메틸셀룰로오스/구연산 겔을 건조하는 단계이다. In the production method according to the present invention, the step (2) is a step of drying the carboxymethyl cellulose / citric acid gel irradiated with the radiation.
구체적으로, 상기 단계 3)에서 건조는 열 건조, 자연 건조 및 동결 건조로 이루어지는 군으로부터 선택되는 어느 하나인 것이 바람직하나 이에 한정하지 않는다. Specifically, in the step 3), the drying may be any one selected from the group consisting of heat drying, natural drying and freeze drying, but is not limited thereto.
본 발명의 실시예에서는 본 발명의 무독성 고흡수성 수지의 제조방법으로 제조한 카복시메틸셀룰로오스/구연산 건조겔의 가교도 정도를 측정하기 위하여 전자선량에 따라 겔화율을 측정한 결과 총 중량에 10% 카복시메틸셀룰로오스/ 2% 구연산을 첨가한 반죽에 20 kGy의 전자선을 조사하여 얻은 건조겔이 가장 높은 가교도를 나타내는 것을 확인하였다(도 3 참조).In the examples of the present invention, in order to measure the degree of crosslinking of the carboxymethyl cellulose / citric acid dry gel prepared by the method for producing a non-toxic superabsorbent resin of the present invention, the gelation rate was measured according to the electron dose, It was confirmed that the dried gel obtained by irradiating 20 kGy of electron beam to the dough added with methylcellulose / 2% citric acid showed the highest degree of crosslinking (see FIG. 3).
본 발명의 실시예에서는 본 발명의 무독성 고흡수성 수지의 제조방법으로 제조한 카복시메틸셀룰로오스/구연산 건조 겔의 가교도의 정도를 측정하기 위하여 전자선량에 따라 건조겔의 팽윤도를 측정한 결과 20 kGy의 전자선 선량으로 조사된 총 중량에 10% 카복시메틸셀룰로오스/ 2% 구연산 겔의 팽윤 정도가 7000%로 자기 무게의 70배 정도를 흡수하여 고흡수 물질인 것을 확인하였다(도 4 참조).In order to measure the degree of crosslinking of the carboxymethyl cellulose / citric acid dry gel prepared by the method of the present invention, the swelling degree of the dried gel was measured according to the electron dose, The swelling degree of 10% carboxymethylcellulose / 2% citric acid gel was 7000% and absorbed about 70 times of its own weight to the total weight irradiated by the dose, thereby confirming that it was a highly absorbing substance (see FIG. 4).
본 발명의 실시예에서는 본 발명의 무독성 고흡수성 수지의 제조방법으로 제조한 카복시메틸셀룰로오스/구연산 건조 겔의 가교도의 정도를 측정하기 위하여 전자선이 조사된 건조겔의 시간에 따른 팽윤도의 변화 측정한 결과, 20 kGy의 전자선 조사된 총중량에 10 중량% 카복시메틸셀룰로오스/ 2% 구연산을 첨가한 건조겔의 물과 0.9% NaCl 용액(인조 인뇨)에서의 겔이 침지 시간이 경과함에 따라 다량의 용액을 흡수함을 확인하였다(도 5 및 도 6 참조).In the examples of the present invention, in order to measure the degree of crosslinking of the carboxymethyl cellulose / citric acid dry gel prepared by the method for producing a non-toxic superabsorbent resin of the present invention, the swelling degree of the dried gel irradiated with electron beams was measured , A gel in a dry gel water containing 10 wt% carboxymethyl cellulose / 2% citric acid and 0.9% NaCl solution (artificial urine) added to a total weight of 20 kGy irradiated with electron beams absorbed a large amount of solution as the immersion time elapsed (See Figs. 5 and 6).
본 발명의 실시예에서는 본 발명의 무독성 고흡수성 수지의 제조방법으로 제조한 카복시메틸셀룰로오스/구연산 건조 겔의 가교도의 정도를 측정하기 위하여 전자선이 조사하여 팽윤된 겔의 시간에 따른 수분 보유율의 변화 측정한 결과 총 중량에 10 중량% 카복시메틸셀룰로오스/ 2% 구연산를 첨가하여 팽윤된 겔은 7 시간 동안 약 63%까지 감소한 반면에 7시간 후로는 처음 흡수한 물의 60%까지 보유할 수 있는 것을 확인하였다(도 7).In the examples of the present invention, in order to measure the degree of crosslinking of the carboxymethyl cellulose / citric acid dry gel prepared by the method for producing a non-toxic superabsorbent resin of the present invention, measurement of changes in water retention rate of the swollen gel As a result, it was found that the swollen gel added with 10 wt% carboxymethylcellulose / 2% citric acid to the total weight decreased to about 63% for 7 hours, while it could retain up to 60% of the initial absorbed water after 7 hours 7).
따라서, 본 발명의 무독성 고흡수성 수지의 제조방법으로 제조한 카복시메틸셀룰로오스/구연산 건조 겔은 천연 식물성 물질인 셀룰로오스로부터 수용성 유도체로 제조한 카복시메틸셀룰로오스와 천연 항산화제인 구연산을 배합하여 방사선을 조사하여 제조하여 환경 친화적이고 무독성이며, 특히 총 중량에 10% 카복시메틸셀룰로오스/ 2% 구연산을 첨가한 반죽에 20 kGy의 전자선을 조사하여 얻은 건조겔이 높은 가교도, 고흡수성 및 높은 수분보유율을 나타내는 것을 실험예를 통하여 확립하여 생태 회복과 농업과 같은 응용분야에서 물보유를 효과적으로 이용할 수 있는 큰 유지 능력을 가지고 있어 유용하게 이용할 수 있음을 알 수 있다.
Therefore, the carboxymethyl cellulose / citric acid dry gel prepared by the method of the present invention can be prepared by mixing carboxymethyl cellulose, which is a water-soluble derivative, from cellulose, which is a natural plant material, with citric acid which is a natural antioxidant, It was experimentally demonstrated that dry gel obtained by irradiating 20 kGy electron beam to a dough with 10% carboxymethyl cellulose / 2% citric acid added to the total weight shows high degree of crosslinking, high absorptivity and high moisture retention It is established through examples that it can be used effectively because it has a large maintenance capability that can effectively utilize water reservoirs in applications such as ecological restoration and agriculture.
또한, 본 발명은 방사선에 의한 친환경 고흡수성 수지의 제조방법으로 제조된 카복시메틸셀룰로오스/구연산 겔로 구성된 무독성 고흡수성 수지를 제공한다.The present invention also provides a non-toxic superabsorbent resin composed of carboxymethylcellulose / citric acid gel prepared by a process for producing an environmentally highly superabsorbent resin by radiation.
상기 무독성 고흡수성 수지는 천연 식물성 물질인 셀룰로오스로부터 수용성 유도체로 제조한 카복시메틸셀룰로오스와 천연 항산화제인 구연산을 배합하여 방사선을 조사하여 제조하여 환경 친화적이고 무독성이며, 특히 총 중량에 10% 카복시메틸셀룰로오스/ 2% 구연산을 첨가한 반죽에 20 kGy의 전자선을 조사하여 얻은 건조겔이 높은 가교도, 고흡수성 및 높은 수분보유율을 나타내는 것을 확인하여 유용하게 이용될 수 있다.
The non-toxic superabsorbent resin is prepared by mixing carboxymethylcellulose, which is a water-soluble derivative, from cellulose, which is a natural plant material, with citric acid, which is a natural antioxidant, and is irradiated to produce environmentally friendly and non-toxic. Specifically, 10% carboxymethylcellulose / It was confirmed that the dry gel obtained by irradiating the dough with 2% citric acid with 20 kGy of electron beam exhibits high degree of crosslinking, high absorptivity and high moisture retention, and thus can be usefully used.
또한, 본 발명은 방사선에 의한 친환경 고흡수성 수지의 제조방법으로 제조된 카복시메틸셀룰로오스/구연산 겔로 구성된 무독성 고흡수성 수지를 포함하는 일회용 위생용품을 제공한다. The present invention also provides a disposable sanitary article comprising a non-toxic superabsorbent resin composed of carboxymethylcellulose / citric acid gel prepared by a process for producing an environmentally highly superabsorbent resin by radiation.
상기 일회용 흡수용품은 유아용 일회용 기저귀(baby diaper), 성인용 일회용 기저귀(adult diaper), 여성용 생리용품(sanitary napkin), 배변 훈련용 속팬티 및 팬티라이너(panty liner)로 이루어지는 군으로부터 선택되는 어느 하나인 것이 바람직하나 이에 한정하지 않는다.
The disposable absorbent article is any one selected from the group consisting of a baby diaper, an adult diaper, a sanitary napkin, a bowel training pant, and a panty liner But is not limited thereto.
또한, 본 발명은 방사선에 의한 친환경 고흡수성 수지의 제조방법으로 제조된 카복시메틸셀룰로오스/구연산 겔로 구성된 무독성 고흡수성 수지를 포함하는 토양보수제를 제공한다. The present invention also provides a soil remover comprising a non-toxic superabsorbent resin composed of carboxymethylcellulose / citric acid gel prepared by a process for producing an environmentally highly superabsorbent resin by radiation.
본 발명의 무독성 고흡수성 수지의 제조방법으로 제조한 카복시메틸셀룰로오스/구연산 건조 겔은 천연 식물성 물질인 셀룰로오스로부터 수용성 유도체로 제조한 카복시메틸셀룰로오스와 천연 항산화제인 구연산을 배합하여 방사선을 조사하여 제조하여 환경 친화적이고 무독성이며, 높은 가교도, 고흡수성 및 높은 수분보유율을 나타내어 일회용 위생용품 및 토양보수제로 유용하게 사용할 수 있다. The carboxymethyl cellulose / citric acid dry gel prepared by the method of the present invention is prepared by mixing carboxymethyl cellulose, which is a water-soluble derivative, from cellulose, which is a natural plant material, with citric acid, which is a natural antioxidant, Friendly, non-toxic, highly crosslinked, highly absorptive and highly water-retaining, and can be usefully used as disposable hygiene products and soil remediation agents.
추가적으로 상기 무독성 고흡수성 수지를 위생매트, 파프제 및 창상 보호제와 같은 병원용품, 냉팩, 온팩, 및 방향소취제와 같은 화장품, 콘크리트 흡입제. 지주제 및 흡수성 마대와 같은 토목용 자재, 및 인공눈, 유수분리제, 흡수성 섬유와 같은 특수용도로 사용할 수 있으나 이에 한정하지 않는다.
In addition, the non-toxic superabsorbent resin may be used as a cosmetic or a concrete inhaler such as a hospital article, a cold pack, a warm pack, and a direction deodorant such as a sanitary mat, a papermaking and a wound dressing. But not limited to, civil engineering materials such as flooring and absorbent garments, and special applications such as artificial snow, water repellent, and absorbent fibers.
단, 하기 실시 예는 본 발명을 예시하는 것일 뿐 본 발명의 내용이 하기 실시 예에 한정되는 것은 아니다.
However, the following examples are illustrative of the present invention and are not intended to limit the scope of the present invention.
<< 실시예Example > 구연산(> Citric acid ( citriccitric acidacid , , CACA ) 함량 및 전자선 선량에 따른 ) Content and electron dose 카복시메틸셀룰로오스Carboxymethylcellulose /구연산 겔 제조/ Production of citric acid gel
전체 중량에 카복시메틸셀룰로오스(carboxymethylcellulose, CMC)는 10 중량%, 구연산은 0, 1, 2, 4 및 8 중량%를 첨가하여 각각 다른 5개의 시료 카복시메틸셀룰로오스/구연산 반죽을 준비한 후 플라스틱 용기에 담아 전자선 가속기(ELV-8 Accelerator, EB-tech)로 전자선을 조사하였다. 이때, 전자선 가속기는 10 MeV를 이용하고, 조사선량 10 kGy/scan으로 설정한 후 각각의 선량에 맞게 스캔하여 총 조사량이 0, 10, 20, 30, 50 및 100 kGy가 되도록 하였다. 전자선 조사 후 얻어진 겔은 동결건조하였다.
Carboxymethylcellulose (CMC) was added to the total weight of 10% by weight and citric acid was added to 0, 1, 2, 4 and 8% by weight to prepare five different samples of carboxymethylcellulose / citric acid dough. The electron beam was irradiated with an electron beam accelerator (ELV-8 Accelerator, EB-tech). At this time, the electron beam accelerator was set to 10 kGy / scan using 10 MeV, and the total dose was scaled according to each dose so that the total dose was 0, 10, 20, 30, 50 and 100 kGy. The gel obtained after electron beam irradiation was lyophilized.
<< 실험예Experimental Example 1> 구연산( 1> citric acid ( citriccitric acidacid , , CACA ) 농도 및 전자선 조사 선량에 대한 ) Concentration and dose for electron beam irradiation 겔화율Gelation rate 분석 analysis
상기 <실시예>에서 제조한 카복시메틸셀룰로오스/구연산 건조겔의 가교도 정도를 측정하기 위하여 전자선량에 따라 겔화율을 측정하였다.In order to measure the degree of crosslinking of the carboxymethyl cellulose / citric acid dry gel prepared in the above Example, the gelation rate was measured according to the electron dose.
구체적으로, 상기 <실시예>에서 제조된 카복시메틸셀룰로오스/구연산 겔에 전자선 0, 10, 20, 30, 50 및 100 kGy 전자선을 조사하여 제조된 카복시메틸셀룰로오스/구연산 겔 샘플들을 건조시켜 5×5 mm 크기의 정사각형 형태로 절단한 다음, 건조 무게를 측정하고 이를 증류수에 48 시간 동안 침지시켜 가교되지 않은 부분을 용해시켰다. 용해되지 않은 부분을 진공 오븐에 넣어 37 ℃에서 48 시간 건조시킨 후 건조된 겔 무게를 측정하였다. 카복시메틸셀룰로오스/구연산 겔화율(gel content)은 하기 [수학식 1]에 의해 계산하였다.
Specifically, the carboxymethyl cellulose / citric acid gel prepared in the above <Example> Carboxymethylcellulose / citric acid gel samples prepared by irradiating
그 결과, 구연산이 2% 및 4%가 함유된 카복시메틸셀룰로오스/구연산 건조겔은 다른 샘플에 비하여 겔함량이 높음을 알 수 있었고, 20 kGy에서 가교된 겔들은 95% 이상의 높은 겔함량을 나타내었다. 또한, 겔함량은 20 kGy 이상에서는 전자선량이 증가할수록 점차적으로 감소함을 볼 수 있었다. 구연산 함량이 8%인 경우는 오히려 분해가 되어 겔이 전혀 형성되지 않았으며, 구연산 함량이 0%인 경우는 100 kGy에서 약 20%의 겔함량을 나타내는 것을 확인하여 전자선 조사만으로도 카복시메틸셀룰로오스 내에 가교의 가능성을 보여주었으나 구연산을 넣지 않는 경우보다 훨씬 낮은 겔화율을 나타내었다. 특히, 총 중량에 10% 카복시메틸셀룰로오스/ 2% 구연산을 첨가한 반죽에 20 kGy의 전자선을 조사하여 얻은 건조겔이 가장 높은 가교도를 나타내는 것을 확인하였다(도 3).
As a result, it was found that the gel content of carboxymethylcellulose / citric acid dried gel containing 2% and 4% citric acid was higher than those of other samples, and gels crosslinked at 20 kGy showed higher gel content than 95% . In addition, the gel content gradually decreased with increasing electron dose at 20 kGy or more. When the content of citric acid was 8%, the gel was not decomposed and no gel was formed. When the content of citric acid was 0%, the gel content was about 20% at 100 kGy. Thus, But the gelation rate was much lower than that without citric acid. In particular, it was confirmed that the dry gel obtained by irradiating 20 kGy of electron beam to the dough obtained by adding 10% carboxymethylcellulose / 2% citric acid to the total weight exhibited the highest degree of crosslinking (FIG. 3).
<< 실험예Experimental Example 2> 전자선 선량에 따른 2> Depending on electron dose 건조겔의Of dry gel 팽윤도 분석 Swelling analysis
상기 <실시예>에서 각각의 전자선 선량에 따라 얻어진 카복시메틸셀룰로오스/구연산 건조 겔의 팽윤 실험은 증류수에서 실행하여, 하기 [수학식 2]를 이용하여 팽윤도 값을 구하였다.
The swelling test of the carboxymethylcellulose / citric acid dry gel obtained according to each electron beam dose in the above Example was carried out in distilled water and the degree of swelling was calculated using the following formula (2).
그 결과, 20 kGy의 전자선 선량으로 조사된 총 중량에 10% 카복시메틸셀룰로오스/ 2% 구연산 겔의 팽윤 정도가 7000%로 자기 무게의 70배 정도를 흡수하였으며 여기에 나타내어진 모든 샘플들은 자기 무게의 40배 이상을 흡수하는 높은 흡수력을 나타내어 20 kGy의 전자선이 조사된 총 중량에 10% 카복시메틸셀룰로오스/ 2% 구연산을 첨가한 건조겔은 고흡수 물질인 것을 확인하였다(도 4).
As a result, the swelling degree of 10% carboxymethyl cellulose / 2% citric acid gel absorbed 70 times of its own weight by 7000% in the total weight irradiated with electron beam dose of 20 kGy, 40% or more. The dried gel added with 10% carboxymethyl cellulose / 2% citric acid to the total weight irradiated with 20 kGy electron beam was confirmed to be a highly absorbing substance (FIG. 4).
<< 실험예Experimental Example 3> 전자선이 조사된 3> 건조겔의Of dry gel 시간에 따른 팽윤도의 변화 분석 Analysis of change of swelling degree with time
상기 <실험예2>에서 가장 높은 팽윤도를 나타낸 20 kGy의 전자선이 조사된 총중량에 10 중량% 카복시메틸셀룰로오스/ 2% 구연산을 첨가한 건조겔을 증류수와 0.9% NaCl 용액(인조 인뇨)에서 실행하여 시간의 따른 팽윤도를 상기 [수학식 2]에 대입하여 팽윤도의 변화 값을 측정하였다.In the above Experimental Example 2, a dry gel containing 10 wt% carboxymethyl cellulose / 2% citric acid was added to distilled water and 0.9% NaCl solution (artificial urine) to the total weight of 20 kGy irradiated with the highest degree of swelling The swelling degree according to time was substituted into the above formula (2), and the change value of swelling degree was measured.
그 결과, 20 kGy의 전자선 조사된 총중량에 10 중량% 카복시메틸셀룰로오스/ 2% 구연산을 첨가한 건조겔은 물과 0.9% NaCl 용액에서 침지 시간이 경과함에 따라 다량의 용액을 흡수함을 확인하였으며 이는 주쇄에 수산기 존재와 카복시메틸셀룰로오스-나트륨(Na)의 특성상 친수성에 의한 결과로 다량의 물과 0.9% 염화나트륨(NaCl)을 흡수하는 것을 확인하였다(도 5 및 도 6).
As a result, it was confirmed that the dried gel added with 10 wt% carboxymethylcellulose / 2% citric acid absorbed a large amount of solution with immersion time in water and 0.9% NaCl solution with a total weight of 20 kGy irradiated with electron beam, As a result of the hydrophilic nature of the presence of hydroxyl groups in the main chain and the nature of carboxymethylcellulose-sodium (Na), it was confirmed that a large amount of water and 0.9% sodium chloride (NaCl) were absorbed (FIGS. 5 and 6).
<< 실험예Experimental Example 4> 4> 팽윤된Swollen 겔의Gel 시간에 따른 수분 보유율 분석 Analysis of moisture retention by time
수분 보유율은 농업적인 이용을 위하여 실온에서 최대 팽윤된 겔의 물빠짐 상태를 보기 위하여 적용되었으며, 수분 보유율(water retention, WR)은 다음과 같은 식을 통하여 계산되었다.
The water retention rate was applied to the water swelling state of the gel which was swollen at room temperature for agricultural use. The water retention (WR) was calculated by the following equation.
(Wt는 팽윤된 겔의 37 ℃에서 t 시간의 무게이고,(W t is the weight of the swollen gel at 37 ° C for t hours,
Wd는 건조 무게, Ws는 최대 팽윤된 겔의 무게이다.)
W d is the dry weight, and W s is the weight of the gel with the maximum swelling.
그 결과, 총중량에 10 중량% 카복시메틸셀룰로오스/ 2% 구연산를 첨가하여 팽윤된 겔은 7 시간 동안 약 63%까지 감소한 반면에 7시간 후로는 처음 흡수한 물의 60%까지 보유할 수 있는 것을 확인하였다(도 7).
As a result, it was confirmed that the swollen gel added with 10 wt% carboxymethylcellulose / 2% citric acid to the total weight decreased to about 63% for 7 hours, while it could hold up to 60% of the initial absorbed water after 7 hours 7).
Claims (8)
2) 상기 단계 1)에서 생성된 반죽에 방사선을 조사하여 카복시메틸셀룰로오스/구연산 겔을 생성하는 단계; 및
3) 상기 단계 2)에서 생성된 카복시메틸셀룰로오스/구연산 겔을 건조하는 단계를 포함하는 것을 특징으로 하는 방사선에 의한 친환경 고흡수성 수지의 제조 방법.
1) Blending carboxymethylcellulose (CMC) and citric acid (CA) at a predetermined mixing ratio and dissolving in water to produce dough;
2) irradiating the dough produced in step 1) above with radiation to produce carboxymethylcellulose / citric acid gel; And
3) drying the carboxymethyl cellulose / citric acid gel produced in step 2).
[2] The method according to claim 1, wherein in step 1), 1 to 30% by weight of the carboxymethyl cellulose and 1 to 30% by weight of citric acid are blended.
[2] The method according to claim 1, wherein in step 1), 10 to 13% by weight of the carboxymethyl cellulose and 2 to 10% by weight of citric acid are blended.
The method according to claim 1, wherein the radiation in step 2) is any one selected from the group consisting of gamma rays, electron beams, ion beams, neutron beams, UV and plasma.
The method according to claim 1, wherein the radiation dose in step 2) is 5 to 100 kGy.
The method according to claim 1, wherein the radiation dose in step 2) is 20 to 30 kGy.
The method for producing an environmentally superabsorbent resin according to claim 1, wherein the drying in step 3) is any one selected from the group consisting of thermal drying, natural drying and freeze drying.
A non-toxic superabsorbent resin comprising carboxymethylcellulose / citric acid gel prepared by the method of claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020130000180A KR101440486B1 (en) | 2013-01-02 | 2013-01-02 | Method for manufacturing of eco-friendly super absorbent resin by radiation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020130000180A KR101440486B1 (en) | 2013-01-02 | 2013-01-02 | Method for manufacturing of eco-friendly super absorbent resin by radiation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR20140088368A true KR20140088368A (en) | 2014-07-10 |
| KR101440486B1 KR101440486B1 (en) | 2014-09-17 |
Family
ID=51736945
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020130000180A KR101440486B1 (en) | 2013-01-02 | 2013-01-02 | Method for manufacturing of eco-friendly super absorbent resin by radiation |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR101440486B1 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101697636B1 (en) * | 2015-09-22 | 2017-01-18 | 안동대학교 산학협력단 | Preparing method of multiple carboxylic acid-esterificated starch heterocompounds using low-temperature plasma |
| KR20190049015A (en) * | 2017-11-01 | 2019-05-09 | 전주대학교 산학협력단 | Manufacturing method of carbon foam using waste marble powder |
| WO2019088472A1 (en) * | 2017-11-01 | 2019-05-09 | 전주대학교 산학협력단 | Method for manufacturing natural material carbon foam by using cellulose-based derivative |
| KR20200041644A (en) * | 2018-10-12 | 2020-04-22 | 주식회사 엘지화학 | Preparation method of super absorbent polymer and super absorbent polymer prepared therefrom |
| KR20210054397A (en) * | 2019-11-05 | 2021-05-13 | 한국원자력연구원 | Superabsorbent material and method for preparing the same |
| US11400431B2 (en) | 2019-10-29 | 2022-08-02 | Tkens, Co., Ltd. | Composition for soft anti-release moisture absorbent |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4819984B2 (en) | 1999-06-23 | 2011-11-24 | 独立行政法人日本原子力研究開発機構 | Self-crosslinking alkylcellulose derivatives and methods for producing them |
| DE60135834D1 (en) | 2001-06-08 | 2008-10-30 | Procter & Gamble | Cellulosic fibers containing radiation-activatable resin compounds |
| JP2008247975A (en) * | 2007-03-29 | 2008-10-16 | Daicel Chem Ind Ltd | Crosslinked gel and absorbent using the same |
| JP5854618B2 (en) | 2011-03-25 | 2016-02-09 | ユニ・チャーム株式会社 | Absorbing material and method for producing the same |
-
2013
- 2013-01-02 KR KR1020130000180A patent/KR101440486B1/en active IP Right Grant
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101697636B1 (en) * | 2015-09-22 | 2017-01-18 | 안동대학교 산학협력단 | Preparing method of multiple carboxylic acid-esterificated starch heterocompounds using low-temperature plasma |
| KR20190049015A (en) * | 2017-11-01 | 2019-05-09 | 전주대학교 산학협력단 | Manufacturing method of carbon foam using waste marble powder |
| WO2019088473A1 (en) * | 2017-11-01 | 2019-05-09 | 전주대학교 산학협력단 | Method for manufacturing carbon foam by using waste artificial marble powder |
| WO2019088472A1 (en) * | 2017-11-01 | 2019-05-09 | 전주대학교 산학협력단 | Method for manufacturing natural material carbon foam by using cellulose-based derivative |
| KR20190049013A (en) * | 2017-11-01 | 2019-05-09 | 전주대학교 산학협력단 | Manufacturing method of carbon foam obtained from cellulose derivation of natural substance |
| KR20200041644A (en) * | 2018-10-12 | 2020-04-22 | 주식회사 엘지화학 | Preparation method of super absorbent polymer and super absorbent polymer prepared therefrom |
| US11400431B2 (en) | 2019-10-29 | 2022-08-02 | Tkens, Co., Ltd. | Composition for soft anti-release moisture absorbent |
| KR20210054397A (en) * | 2019-11-05 | 2021-05-13 | 한국원자력연구원 | Superabsorbent material and method for preparing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| KR101440486B1 (en) | 2014-09-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101440486B1 (en) | Method for manufacturing of eco-friendly super absorbent resin by radiation | |
| CN101502667B (en) | Medical chitosan transparent hydrogel wound dressing as well as preparation and application thereof | |
| AU2006275136B2 (en) | Hydrogel | |
| WO2009022358A1 (en) | Superabsorbent polymer hydro gels and a method of preparing thereof | |
| JPH0366321B2 (en) | ||
| CN101664562A (en) | Wound repair hydrogel material and preparation method thereof | |
| JP2003160602A (en) | Production method of chitin derivative and/or chitosan derivative having crosslinking structure | |
| Gwon et al. | Humectants effect on aqueous fluids absorption of γ-irradiated PVA hydrogel followed by freeze thawing | |
| JP5071766B2 (en) | Method for producing gel using polysaccharide as raw material | |
| CN105012997B (en) | Natural polymer polyelectrolyte compound hemostatic sponge of one class containing tea oil | |
| Lukitowati et al. | Water Absorption of Chitosan, Collagen, and Chitosan/Collagen Blend Membranes Exposed to Gamma-Ray Irradiation: Water Absorption of the Membranes Exposed to Irradiation | |
| CN101244286A (en) | Hydrogel dressings and preparation thereof | |
| CN103224630A (en) | Method for preparing water-absorbing resin by ultraviolet and gamma-ray radiation ionization technique | |
| Chowdhury et al. | Radiation processed hydrogel of poly (vinyl alcohol) with biodegradable polysaccharides | |
| JP5030193B2 (en) | Superabsorbent starch gel | |
| KR101947606B1 (en) | Functional diaper and manufacturing method thereof | |
| JP4674357B2 (en) | Crosslinking of starch derivatives and methods for their production | |
| El‐Rehim et al. | Characterization of Super‐Absorbent Material Based on Carboxymethylcellulose Sodium Salt Prepared by Electron Beam Irradiation | |
| KR20180041980A (en) | Manufacturing method water-soluble hydrofiber and wound dressing using the water-soluble hydrofiber | |
| JP2965561B1 (en) | Hydrogel composition containing silk protein | |
| Wikanta et al. | Properties of sodium alginate–polyvinyl alcohol hydrogels irradiated by gamma ray for wound dressing materials | |
| JP2001226404A (en) | Fibrous water-absorbing material and method of producing the same | |
| JP2001114803A (en) | Water-absorbing agent and its production | |
| EP3954717A1 (en) | Superabsorbent polymer and method for producing the same | |
| RADULESCU et al. | The evaluation of novel wound dressings based on hydrogels |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A201 | Request for examination | ||
| E902 | Notification of reason for refusal | ||
| E701 | Decision to grant or registration of patent right | ||
| FPAY | Annual fee payment |
Payment date: 20180702 Year of fee payment: 5 |