KR102259576B1 - Super Absorbent Polymer Fiber Yarn Comprising Kappa Carrageenan, and Producing Method Thereof - Google Patents

Abstract

The present invention relates to a method for producing a superabsorbent polymer fiber yarn made from natural ingredients, and more specifically, to a spinning stock solution made from a raw material containing k-Carrageenan (KC) and spinning in a crosslinking solution. By manufacturing SAP (Super Absorbent Polymer, superabsorbent resin) fiber yarn by this method, it has a high water absorption rate, is environmentally friendly, is harmless to the human body, and is a natural high-quality material that can be widely used not only for hygiene products, but also for medicine and agriculture. It relates to the production of absorbent polymer fiber yarn. To this end, the present invention provides a spinning dope preparation step of adding distilled water to a raw material containing a kappa carrageenan component to make a mixed solution, and then heating the mixed solution with stirring to prepare a spinning dope; A spinning step of obtaining a SAP yarn by crosslinking while spinning the spinning solution wet in a coagulation tank containing a KCl solution; a dehydration step of impregnating the SAP yarn in an ethanol treatment tank to remove moisture while transferring; And it is preferable to include a drying step of stretching and drying while transferring the SAP yarn that has undergone the dehydration step in a drying furnace.

Description

Super Absorbent Polymer Fiber Yarn Comprising Kappa Carrageenan, and Producing Method Thereof

The present invention relates to a superabsorbent polymer fiber yarn prepared from natural ingredients and a method for manufacturing the same, and more specifically, to a spinning dope made from a raw material containing a kappa carrageenan (KC) component and spun in a crosslinking solution. By manufacturing SAP (Super Absorbent Polymer, superabsorbent resin) fiber yarns as a natural ingredient, it is environmentally friendly and harmless to the human body while having a high water absorption rate. It is a natural ingredient that can be widely used for medicine and agriculture as well as hygiene products. It relates to a super absorbent polymer fiber yarn and a method for manufacturing the same.

SAP (Super Absorbent Polymer), a polymer material that absorbs water, is a polymer material that can absorb moisture hundreds of times its own weight. It is mainly used for hygiene products such as baby diapers, feminine hygiene products, and adult diapers. It has been mainly used, and recently, the field of application is expanding to various industrial fields such as packs for cold storage and heat retention, moisture retention agents and soil modifiers for agriculture, and packaging materials for food.

Super absorbent polymer, that is, SAP, is a polymer that exhibits the absorption of fluid due to the introduction of a hydrophilic group in a three-dimensional network structure or single chain structure through cross-linking between polymer chains. It absorbs a large amount of liquid inside the structure and expands to make it hydro Refers to a cross-linked polymer that forms a gel and is capable of holding absorbed liquid under constant pressure. Representative synthetic SAP types include cross-linked hydroalkyl (meth) acrylic acid, N-vinyl pyrrolidone, ethyl oxide, acrylamide, (meth) acrylic acid, and poly (vinyl alcohol), and cross-linked poly (acrylic acid) (PAA). occupy a large portion of the market. However, since synthetic SAP, that is, petroleum-based SAP, is not biodegradable, it must be landfilled or incinerated when discarded after use, thereby exacerbating environmental pollution. In addition, given the global energy problem of oil depletion, the need to replace the existing petroleum-based SAP with biodegradable eco-friendly polymers is increasingly emerging.

Many of the products using SAP are hygiene products such as diapers for women, infants and adults, which come in direct contact with the human body, so concerns about various harmful effects on the human body are increasing. In particular, petrochemical-based SAP is toxic if it remains in SAP even if a trace amount of non-polymerized monomer remains in SAP. Most of the cross-linking agents currently used are also harmful to the human body. Therefore, even a trace amount of unreacted cross-linking agent remaining in SAP is harmful to the human body. Harmfulness has always been raised as a problem. In order to solve this problem, the development of nature-friendly premium hygiene products has been very active both at home and abroad, but the performance of the product such as absorption capacity, water holding capacity and absorbency under pressure is very low compared to existing chemical products. There is an urgent need to develop SAP technology, which is a biodegradable eco-friendly material with excellent performance.

On the other hand, kappa carrageenan (k-Carrageenan, KC) prepared from red algae called Eucheuma cottonii or simply Kappaphycus alvarezii, also known as Cottonii, is an emulsifier. It is widely used in the food industry as a thickener and a variety of cheeses and dairy products, as well as in a number of product fields such as pet food, fruit jam, toothpaste and ice cream. In addition, kappa carrageenan not only has a high water absorption rate, but also has appropriate mechanical strength, biocompatibility, and biodegradability, so it can be attracting attention as a natural high molecular weight superabsorbent resin. However, there is still no technology to make practical SAP using kappa carrageenan.

Korean Patent Publication No. 10-2016-0034317 (2016.03.29.) Korean Patent Publication No. 10-2013-0096857 (2013.09.02)

The present invention, devised to solve the above problems, is to produce a SAP (Super Absorbent Polymer) fiber yarn by making a spinning dope with a raw material containing kappa carrageenan (KC) component and crosslinking it while spinning, thereby providing a high absorption rate for moisture. An object of the present invention is to provide a superabsorbent polymer fiber yarn of natural ingredients, which is environmentally friendly and harmless to the human body, which can be widely used for sanitary products as well as for medicine and agriculture, and a method for manufacturing the same.

The super absorbent polymer fiber yarn of natural ingredients according to the present invention devised to solve the above problems is obtained by mixing the finished product of kappa carrageenan powder or the raw material of Kappaphycus alvarezii with distilled water, stirring and heating the mixed solution by spinning it in KCl solution. After crosslinking, it is preferable to make a superabsorbent polymer fiber yarn of natural ingredients that is dehydrated and dried by impregnating it in an ethanol solution, and the concentration of the finished product of kappa carrageenan powder or the raw material of Cotony is 4wt% to 6wt%. It is possible, and the molar concentration of the KCl solution is also preferably characterized in that 0.05M to 0.5M. In addition, the ethanol solution may be a super absorbent polymer fiber yarn of natural ingredients, characterized in that it is a 93 to 97% ethanol solution.

In addition, in the method for producing a superabsorbent polymer fiber yarn of natural ingredients according to the present invention, distilled water is added to the raw material containing the kappa carrageenan component to make a mixed solution, and then the mixed solution is stirred and heated so that the concentration of the raw material is 4 wt. % to 6wt% of a spinning dope preparation step of making a spinning dope; A spinning step of obtaining a SAP (Super Absorbent Polymer) yarn by crosslinking while wet spinning the spinning solution in a coagulation tank containing a KCl solution having a molar concentration of 0.05M to 0.5M; a dehydration step of removing moisture while transferring the SAP yarn by impregnating it in an ethanol treatment tank containing an ethanol solution; and a drying step of stretching and drying while transferring the SAP yarn that has undergone the dehydration step in a drying furnace; It is preferred to include a.

In addition, in addition to the above characteristics, the raw material may be a natural superabsorbent polymer fiber yarn manufacturing method, characterized in that the finished product of kappa carrageenan powder manufactured by processing seaweed, or the raw material is cotony ( Kappaphycus cottonii, Kappaphycus alvarezii) raw material, and before the spinning dope preparation step, the raw material processing step of washing the raw material of Cotony with distilled water to remove salt and drying the raw material; Further comprising, the molar concentration of the KCl solution is also possible as a method for producing a superabsorbent polymer fiber yarn of natural ingredients, characterized in that 0.1M to 0.5M.

In addition, in the method for producing a superabsorbent polymer fiber yarn of a natural component according to the present invention, in addition to the above-described characteristics, in the spinning solution manufacturing step, the heating of the mixed solution is heated so that 90° C. or higher is maintained for 18 to 22 minutes. It is also preferable to further include a feature that, in the spinning step, the spinning while maintaining the temperature of the spinning dope solution at 80 ℃ or more, the KCl solution further comprising maintaining 15 ℃ to 25 ℃ It is also preferable

And, in addition to the above-described characteristics, in the spinning step, it is also possible to use a method for producing a superabsorbent polymer fiber yarn of a natural component further comprising a feature of spinning so that the diameter of the SAP yarn is 500 μm to 800 μm, In addition, the ethanol solution is also possible as a method for producing a super absorbent polymer fiber yarn of natural ingredients further comprising a feature of 93 to 97% ethanol solution.

As described above, the SAP fiber manufactured by the method for producing a natural ingredient superabsorbent polymer fiber yarn according to the present invention is harmless to the human body and can be disposed of through biodegradation by being manufactured using natural ingredients such as cotony or kappa carrageenan as the main raw material. There is an effect of obtaining SAP fibers with environmental friendliness to

In addition, the method for producing a superabsorbent polymer fiber yarn made of natural ingredients according to the present invention uses KCl, which is harmless to the human body, as a crosslinking agent, and applies the molar concentration of KCl to the optimal concentration, so that the absorption rate and absorption rate are excellent, and it can have appropriate strength. there is an effect

In addition, when the method for manufacturing a superabsorbent polymer fiber yarn of natural ingredients according to the present invention is applied, since SAP is manufactured as a fiber yarn through a continuous process, it is possible to secure the efficiency of the manufacturing process such as increasing the manufacturing speed and reducing labor costs. As well as there is an effect of reducing the amount of ethanol used for dehydration, there is an effect that can manufacture SAP fibers at an economical cost through this.

In addition, in the method for producing a superabsorbent polymer fiber yarn made of natural ingredients according to the present invention, it is possible to manufacture SAP fiber yarn using not only the finished product of kappa carrageenan, but also the raw material, Cotony, before processing, so it is not necessary to use the expensive finished product of carrageenan, thereby reducing the manufacturing cost. It has the effect of drastic savings.

1 is a block diagram of an SAP yarn manufacturing apparatus 100 for producing a superabsorbent polymer fiber yarn of a natural component according to the present invention.
2 is a flowchart schematically illustrating a preferred embodiment of a method for producing a superabsorbent polymer fiber yarn of a natural component according to the present invention.
3 is a flowchart schematically showing another embodiment of the preferred embodiment of the method for manufacturing the natural component superabsorbent polymer fiber yarn according to the present invention.
4 is a water absorption test result in the case of manufacturing SAP by inducing gelation of KC without adding a crosslinking agent.
5 is a water absorption test result according to the size of the SAP particles prepared with KC.
6 is a water absorption test result according to the grinding method of SAP prepared with KC.
7 is a test result of water absorption capacity according to particle size when SAP prepared from KC is generally pulverized.
8 is a water absorption test result according to the particle size when the SAP prepared from KC is pulverized under liquid nitrogen.
9 is a schematic diagram of the equipment for measuring the absorbency under pressure for SAP.
10 is a test result of the water absorption capacity of the SAP yarn according to the concentration of the KC solution.
11 is a test result of water absorption capacity and absorbency under pressure according to the change in molar concentration of KCl solution when the raw material is a KC finished product and the concentration of the KC solution is 5 wt%.
12 is a test result of water absorption capacity and absorbency under pressure according to the change in molar concentration of KCl solution when the raw material is cotony and the concentration of the KC solution is 5 wt%.

Various embodiments will be described in more detail with reference to the accompanying drawings so that the above-described objects and features become clear. Accordingly, those skilled in the art to which the present invention pertains will be able to easily implement the technical idea of the present invention. In the description of the present invention, if it is determined that it is already well known in the technical field as a known technology related to the present invention, and a detailed description of the known technology may unnecessarily obscure the gist of the present invention, the detailed description thereof will be omitted. decide to do

Unless defined otherwise, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which various embodiments belong. As for the terms used in the present invention, general terms that are currently widely used are selected as much as possible, but in certain cases, there are also terms arbitrarily selected by the applicant, and in this case, the meaning is described in detail in the description of the corresponding invention, so the name of a simple term It is intended to clarify that the present invention should be understood as the meaning of a term other than this.

In the description of various embodiments, expressions such as “first”, “second”, “primary”, “secondary”, “first” or “second” may modify various components of the embodiments, The components are not limited. For example, the expressions do not limit the order and/or importance of corresponding elements. The above expressions may be used to distinguish one component from another component.

Hereinafter, with reference to the drawings, the superabsorbent polymer fiber yarn of the present invention and its manufacturing method will be mainly described with respect to the manufacturing method. First, FIG. 1 is a block diagram of an SAP yarn manufacturing apparatus 100 for producing a superabsorbent polymer fiber yarn of a natural component according to the present invention. As shown in FIG. 1 , the SAP yarn manufacturing apparatus 100 includes a spinning dope production furnace 110 , a spinning pump 120 , a coagulation tank 130 , a spinneret 131 , an ethanol impregnation tank 140 , and a drying furnace. It is preferable to configure it to include 150 and the fiber yarn recovery device 160 .

Meanwhile, FIG. 2 is a flowchart schematically showing one of the preferred embodiments of the method for producing a superabsorbent polymer fiber yarn of a natural component according to the present invention. According to this embodiment, it is possible to manufacture SAP (Super Absorbent Polymer) fiber yarn using the finished product of kappa carrageenan powder manufactured by processing red algae such as cottonii. It is preferable to prepare it including the spinning dope preparation step (s110), the spinning step (s120), the dehydration step (s130), and the drying step (s140).

In the spinning dope preparation step (s110), distilled water is added to the raw material containing the kappa carrageenan component to make a mixed solution, and then the mixed solution is stirred and heated to obtain a spinning dope having a concentration of 4 wt% to 6 wt% of the raw material. It is preferable to make Here, the raw material is preferably a finished product of kappa carrageenan powder manufactured by processing cotony, and the heating of the mixed solution is most preferably heated to maintain 90° C. or higher for 18 to 22 minutes.

In the spinning step (s120), the spinning dope prepared in the spinning dope preparation step (s110) is cross-linked while wet spinning in a coagulation tank containing a KCl solution having a molar concentration of 0.05M to 0.5M to cross-link SAP (Super Absorbent Polymer) yarn is obtained. Here, the most preferable molar concentration of the KCl solution is 0.1M, which will be explained in the experimental examples and related results to be described later. In addition, in the spinning step (s120), it is preferable to spin while maintaining the temperature of the spinning dope solution at 80° C. or higher, because kappa carrageenan gels when cooled below a certain temperature, and for smooth spinning, the spinning Until the undiluted solution is spun into the KCl solution through the spinneret 131, it is most preferable to maintain the temperature of the spinning undiluted solution at 80° C. or higher. Therefore, it is also preferable to heat-insulating from the spinning dope production furnace 110 through the spinning pump 120 to the spinneret 131 . In addition, in the case of the KCl solution, it is preferable to maintain it at 15° C. to 25° C. in order to ensure proper strength for the yarn and ensure cross-linking density.

And it is preferable that the diameter of the SAP yarn spun through the spinnerette 131 is 500 μm to 800 μm, which is a thickness that enables the production of SAP yarn having appropriate strength and absorption capacity in a continuous process. falls within the range. If it is less than 500㎛, the strength is too weak to make a continuous process difficult, and if it is 800㎛ or more, the absorption capacity is lowered, and the quality as a SAP yarn is deteriorated.

In addition, the dehydration step (s130) is a process of removing the moisture contained in the SAP yarn obtained in the spinning step (s120), for this purpose, a 93% to 97% ethanol solution, most preferably a 95% ethanol solution It is preferable to impregnate the contained ethanol treatment tank 150 to remove moisture while transporting it.

Finally, the SAP yarn that has undergone the dehydration step (s130) is preferably transferred in the drying furnace 150 and subjected to a drying step (s150) of stretching and drying.

And Figure 3 is a flow chart schematically showing another one of the preferred embodiments of the method for manufacturing the superabsorbent polymer fiber yarn of natural ingredients according to the present invention, according to this embodiment, the kappa carrageenan powder is not a finished product It becomes possible to manufacture SAP yarn using raw materials. As a manufacturing method for this, it is preferable to include a raw material processing step (s200), a spinning dope preparation step (s210), a spinning step (s220), a dehydration step (s230) and a drying step (s240) as shown in FIG. 3 . Do.

The raw material processing step (s200) is a process of washing red algae raw material (Kappaphycus alvarezii or Kappaphycus cottonii), which is a raw material of red algae capable of producing kappa carrageenan, with distilled water to remove salt, and then drying. According to this embodiment, when the raw material is used rather than the finished product of kappa carrageenan, since raw materials are used instead of the expensive finished product, the cost can be greatly saved, and the shape of the SAP yarn due to the fiber and protein present in the raw material is maintained and You get an effect that can enhance the strength.

In this embodiment, the remaining steps after the raw material processing step (s200), that is, the spinning dope preparation step (s210), the spinning step (s220), the dehydration step (s230), and the drying step (s240) are in the embodiment described with reference to FIG. The spinning dope preparation step (s110), spinning step (s120), dehydration step (s130) and drying step (s140) of the spinning undiluted solution are the same as each, but the molar concentration of the KCl solution in the spinning step (s220) is 0.1M to 0.5M Preferably, the most preferred molar concentration is 0.1M. This will be described through Examples and Experimental Examples to be described later.

Hereinafter, various examples, comparative examples, and experimental examples up to deriving the preferred embodiments described above will be described with reference to the drawings.

<Selection of biomass raw material and crosslinking agent>

Research on various biomass raw materials was conducted until preferred embodiments of the method for producing a superabsorbent polymer fiber yarn made of natural ingredients according to the present invention were derived. Raw materials for biodegradable SAP using biomass-based polymers should be non-toxic and biodegradable at the same time to form an appropriate market price. Among them, k-Carrageenan obtained by processing seaweed (red algae) is a material used as a food raw material and is a safe and easily obtainable material, but has a relatively high market price. On the other hand, it is concluded that cotony, a natural raw material used in the production of k-Carrageenan, contains about 46% of kappa carrageenan and can be used directly, considering that there is no special purification process in the production process of kappa carrageenan. It is possible to effectively reduce the manufacturing cost by using it directly. Therefore, along with the finished product, kappa carrageenan, cotony, the raw material of kappa carrageenan, was selected as the raw material.

_{In addition, as a result of research on KCl, KSCN, and BaCl 2} as suitable crosslinking agents for raw materials, that is, kappa carrageenan and raw material (cottony), kappa carrageenan meets metal ions such as K+ and Ba2+ to form a physical cross-link. On the other hand, BaCl ₂ and KSCN were investigated to be harmful to the human body. Therefore, it was concluded that KCl is the most appropriate crosslinking agent having an appropriate degree of crosslinking and safety.

<Example 1> SAP production by inducing gelation without adding a crosslinking agent

To 3 kg of kappa carrageenan, 200 liters of water was added to prepare a mixed solution, put in a stirrer, stirred at room temperature to disperse, and then stirred to dissolve it while heating to 90°C. While stirring and heating were continued, 200 kg of 95% ethanol was slowly added, and then cooling water was added to the jacket of the stirrer and stirring was continued for 1 hour. After that, about 3 kg of crystals were recovered using a 1 micro bag filter and a press. The temperature of the jacket was 65° C., and the crystals were recovered with a moisture content of 3% and a total weight of 3 kg by vacuum drying for 4 hours, and the particles were pulverized to 500 μm to 1,000 μm to obtain SAP particles.

<Comparative Example 1>

SAP particles were obtained by pulverizing the crystals recovered in the process of pulverizing the crystals in the process of Example 1 to less than 500 μm.

<Experimental Example 1>

Water absorption capacity of the SAP particles obtained in Example 1 and Comparative Example 1 was measured. For the water absorption capacity measurement method, the Tea Bag Test was used with reference to the official absorption capacity test method (KS P ISO 17190-5). For the Tea Bag Test, an appropriate amount of SAP (0.1g±0.001g) is placed in a 40-60 mesh size tea bag and immersed in 100ml of water for a certain period of time (10 seconds to 1 hour). After a certain time, the tea bag is removed from the water. Measure the weight. After measuring the weight of the tea bag without SAP in the same manner as above, the amount of water absorbed by the SAP for a certain period of time and the water absorption rate accordingly are calculated as follows.

- Amount of water absorbed by SAP (g) = Wt - (Ww + Wd)

- Absorption capacity (g/g) = (Wt - (Ww + Wd)) / Wd

- Wt : Weight of tea bag including SAP after soaking in water for a certain period of time

- Ww : Weight of empty tea bag after soaking in water for a certain period of time

- Wd : Weight of SAP used in the experiment

In addition, a vial test was conducted to determine the first, second, and third absorption times.

<Result 1>

As a result of the absorption capacity experiment, as shown in FIG. 4, the maximum absorption capacity was 3,850% after 1 hour in SAP having a particle size of 500 μm to 1,000 μm, and in the vial test result, particles smaller than 500 μm as well as particles of 500 μm to 1,000 μm were obtained. In both figures, secondary and tertiary absorption tended to be slow due to agglomeration, and agglomeration was found to be very severe in SAP having a particle size of less than 500 μm.

Less than 500μm: over 5 minutes of primary absorption

*500μm ~ 1000μm: 1st absorption 5 seconds, 2nd absorption 30 seconds, 3rd absorption 50 seconds, 4th absorption 5 minutes or more

In addition, it was also found that it was difficult to make a uniform dispersion solution by agglomeration of kappa carrageenan powders even in the process of dissolving kappa carrageenan by heating.

<Example 2> Preparation of SAP without crosslinking agent after acid treatment on kappa carrageenan

After mixing 12 kg of kappa carrageenan with 200 liters of water to make a mixed solution, it was poured into a stirrer together with 300 liters of an aqueous HCl solution (pH 2.7) at room temperature, stirred at room temperature to disperse, and then dissolved while heating and stirring to 90°C. While stirring and heating were continued, 800 kg of 90% ethanol was slowly added, and cooling water was added to the jacket, followed by stirring continuously for 1 hour to crystallize. After crystal recovery using 1 micro bag filter and a press, the SAP crystals having a moisture content of 3% and a total weight of 12 kg were recovered by vacuum drying at a jacket temperature of 65° C. for 4 hours, and pulverizing them to a size of 500 μm to 1,000 μm. did.

<Comparative Example 2>

In the process of pulverizing the crystals recovered in Example 2, SAP particles pulverized to less than 500 μm and more than 1,000 μm were obtained, respectively.

<Experimental Example 2>

Water absorption capacity was measured for the SAP particles obtained in Example 2 and Comparative Example 2. The same method as the method applied in Experimental Example 1 was used as a method for measuring water absorption capacity.

<Result 2>

As shown in FIG. 5 , water absorption capacity of 2,000% before/after was exhibited in all three particle sizes of less than 500 μm, 500 μm to 1000 μm, and more than 1000 μm. In addition, it appears that some damage was done to the structure of the biomass by the acid treatment, which resulted in a decrease in strength and a decrease in absorption capacity. The reason why the water absorption capacity of both Examples 1 and 2 was somewhat insufficient was presumed to be because the strength was lowered because no crosslinking agent was added, and it was concluded that crosslinking agent treatment was necessary.

<Example 3> SAP preparation using KCl as a crosslinking agent in kappa carrageenan

In a stirrer, 1.2 kg of kappa carrageenan powder was added to 60 liters of an aqueous KCl solution (0.2 mol) at room temperature, stirred and dispersed at room temperature, and then stirred and dissolved while heating to 90° C. to prepare a KC (kappa carrageenan) aqueous solution. 60 liters of 95% ethanol was slowly added to the KC aqueous solution while heating and stirring were continued. After completion of the ethanol input, cooling water was added to the jacket, and the mixture was stirred for 1 hour while cooling, and then about 20 kg of crystals were recovered using a 1 micro bag filter and a press. The recovered crystals were vacuum dried for 4 hours while maintaining the jacket temperature at 65° C. to recover SAP having a moisture content of 3% and a total weight of 1.2 kg.

<Comparative Example 3a>

After adding 30 liters of an aqueous KCl solution (0.2 mol) at room temperature and 1.2 kg of kappa carrageenan powder at room temperature to a stirrer, the mixture was dispersed by stirring at room temperature, and then dissolved by stirring while heating to 90° C. to prepare a KC aqueous solution. When an aqueous KC solution was slowly poured into an ethanol bath under high-speed stirring, SAP in the form of large and thick ropes or lumps was produced. In the process of vacuum drying at a jacket temperature of 65° C. for 4 hours, the rope-type SAP was wound around the impeller of the stirrer, and the drying was stopped because little progress was made.

<Comparative Example 3b>

In Example 3, as the impeller was crystallized by slowly pouring 95% ethanol in a stirring environment, the SAP was recovered in the form of fine powder, which caused a problem with low absorption performance. In order to solve this problem, in Comparative Example 3b, ① Cut off the heat source immediately after dissolution is complete (drain all the hot water inside the jacket) ② Stop stirring ③ Add 95% ethanol at once to get a big decision. As it showed coarse particles as shown in Fig., a grinding process of general grinding or grinding under liquid nitrogen was added.

Therefore, 60 liters of KCl aqueous solution (0.2 mol) at room temperature and 1.2 kg of carrageenan powder were put into a stirrer, dispersed by stirring at room temperature, and then dissolved by stirring while heating to 90° C. to make a KC aqueous solution. Immediately after the dissolution was completed, all the hot water in the jacket was drained and stirring was stopped, and then 60 liters of 95% ethanol was added at once. The surface of the KC aqueous solution crystallized rapidly in the unagitated state, and the KC aqueous solution and the ethanol layer were clearly separated. Immediately after ethanol was added, cold water was supplied to the jacket while operating the stirrer, and after stirring and cooling for 1 hour, crystals were recovered using a 1 micro bag filter and a press. About 20 kg of the recovered crystals were re-immersed in 30 liters of 95% ethanol, overnight, and then the crystals were recovered using a bag filter and a press, but the degree of compression was weakened. The jacket temperature was 65° C. and vacuum dried for 5 hours to recover SAP with a moisture content of 8% and a total weight of 1.2 kg.

<Experimental Example 3>

Water absorption capacity was measured for the SAP particles obtained in Example 3 and Comparative Example 3b. The same method as the method applied in Experimental Example 1 was used as a method for measuring water absorption capacity. For the particles pulverized in Comparative Example 3b, water absorption capacity was measured by classifying them into particles of less than 200 μm, 200 μm to 500 μm, 500 μm to 710 μm, 710 μm to 1000 μm, and 1000 μm to 1700 μm.

<Result 3>

In Example 3, Comparative Example 3a, and Comparative Example 3b, when KC was dispersed in an aqueous KCl solution, it was more easily dispersed than when dispersed in distilled water, and thus, it was easy to prepare a uniform KC aqueous solution. However, in Example 3, the fine powder of SAP was recovered and showed a low absorption capacity, and severe agglomeration was found, which is believed to be because the SAP had a fine powder form, which was found to be the cause of the low absorption capacity. Also, as the scale increased, a decrease in the cooling rate was observed. Accordingly, SAP crystals were gradually formed, and while stirring was continued, the SAP crystals were made small. Therefore, it was determined that a change in the SAP manufacturing process was necessary to manufacture SAP of larger particles.

In Comparative Example 3a, the particle size was controlled by controlling the cooling rate of the SAP. Therefore, an attempt was made to manufacture SAP using a method of rapidly dropping the temperature of the KC solution by slowly pouring the KC solution into an ethanol bath under high-speed stirring, but SAP in the form of a thick rope or a large lump was produced, and the low specific surface area Because of this, a long ethanol treatment time was required. And during the drying process, the rope-type SAP was entangled in the impeller and failed to dry.

In Comparative Example 3b, the crystal properties were similar to those of thin fibers, and thus the drying time was increased by about 1 hour compared to the fine powder form. was found in small quantities. It was observed that these lumps had to be re-dried or discarded after shredding after separating by sieving because drying to the inside was impossible due to the formation of a film on the surface. 6 to 8 are results of comparing the absorption capacity according to the grinding method and the crushed particle size in Comparative Example 3b. FIG. 6 is the water absorption capacity test result according to the grinding method of SAP, and FIG. 7 is the particle size when the SAP is generally crushed. It is the test result of water absorption capacity according to the size, and FIG. 8 is the water absorption capacity test result according to the particle size when the SAP is pulverized under liquid nitrogen. As shown in FIGS. 6 to 8 , the absorption capacity was about 5,000%. The properties of the manufactured SAP are in the form of thin and short fibers, and for the manufacture of application products, SAP must be manufactured as particles in a form that can be sprayed. Therefore, it was necessary to undergo a process of pulverizing to an appropriate size, and pulverization was carried out using two methods: pulverization using a general pulverizer or cooling with liquid nitrogen and pulverization. The moisture absorption rate was measured according to each pulverization method. As a result of the water absorption capacity test, the SAP recovered by normal grinding showed a water absorption rate of about 5,000%, and the water absorption rate of the SAP recovered by grinding under liquid nitrogen was about 5,600%, which showed a water absorption performance that was improved by about 600% compared to the general grinding. About 90L of ethanol should be used to recover 1.2 kg of SAP by the above method, and the production cost was too high because of the liquid nitrogen and liquid nitrogen pulverization equipment used during pulverization.

<Necessity of manufacturing SAP in the form of fibers>

In order to make an application using SAP, absorbency is also important, but Absorbency Under Load (AUL) must be sufficiently secured. Therefore, in order to increase the absorbency under pressure, it was necessary to change the form of SAP to the form of fibers. In addition, since a large amount of ethanol is consumed in the process according to the above embodiments, this results in an increase in the unit price of the product, so it was necessary to find a solution for cost reduction.

For example, when spinning fibers with a thin thickness of about 500-800 μm, ethanol treatment is easy, and due to the continuous process, it is possible to manufacture a large amount of SAP even with a small amount of ethanol. In addition, in the case of a fiber type, water holes are created due to the shape of the fibers while absorbing and expanding, and agglomeration does not occur, and excellent water absorption ability is shown not only in the initial absorption but also in the secondary and tertiary absorption. Therefore, an embodiment of manufacturing the SAP yarn by spinning the fiber to a thin thickness was experimented. The reason why it is preferable to set the thickness of the fiber to 500-800 μm is that when the thickness of the fiber is less than 500 μm, the strength of the fiber is too low to apply the continuous process, and the experimental results for Comparative Example 3b (Fig. 7) and FIG. 8), when the particle size of the SAP is large, the water absorption capacity is lowered, so it is preferable to keep the thickness of the spun fiber at least 800 μm or less.

Methods for spinning polymer fibers are largely melt spinning, dry spinning, and wet spinning. Melt spinning is a method in which a polymer is melted, spun through a nozzle, and cooled at the same time to recover fibers. Dry spinning is a method in which a polymer is dissolved in an organic solvent and spun through a nozzle, while simultaneously drying the solvent to recover fibers, and wet spinning Spinning is a method of recovering fibers by dissolving a polymer in a solvent and then spinning it in a non-solvent coagulation tank. In the present invention, since crosslinking using KCl aqueous solution is required for kappa carrageenan, it is preferable to apply a wet spinning method of spinning in KCl aqueous solution.

<Example 4> SAP yarn production by crosslinking kappa carrageenan powder in KCL solution

Kappa carrageenan powder was added to distilled water to make a mixed solution, stirred and heated to 90° C. or higher, and then heated for 20 minutes to prepare a spinning dope having a kappa carrageenan concentration of 5 wt%. And while maintaining the spinning stock solution at 80°C or higher, the molar concentration was 0.5M and cross-linking was performed while wet spinning in a coagulation bath containing KCl solution at 20°C to obtain SAP yarn. The SAP yarn was impregnated in an ethanol treatment tank containing 95% ethanol solution to remove moisture while transported, and then stretched and dried while transported in a drying furnace.

<Comparative Example 4a>

In Example 4, the spinning stock solution was prepared as a spinning stock solution having a concentration of kappa carrageenan of 6 wt%, and the rest was carried out in the same manner as in Example 4.

<Comparative Example 4b>

In Example 4, the molar concentrations of KCl were changed to 0.05M, 0.1M, and 0.2M, respectively, and the rest were carried out in the same manner as in Example 4.

<Experimental Example 4>

Water absorption capacity and absorbency under pressure (AUL) were measured for the SAP yarns obtained in Example 4, Comparative Example 4a, and Comparative Example 4b. The water absorption capacity measurement method was the same as the method applied in Experimental Example 1, and the water absorption capacity under load (AUL) measurement method was Korean Industrial Standard KS P ISO 17190-7 (Characterization of polymer-based absorbent materials). Test method: Measurement of weight absorbed during pressure) was carried out referring to the test method. A conceptual diagram of the equipment for measuring the absorbency under pressure is shown in FIG. 9 . As shown in FIG. 9, an appropriate amount of SAP (0.9 g ± 0.005 g) is distributed on the lower screen of the glass cylinder (inner diameter = 60 ± 0.2 mm, height = 50 ± 0.5 mm). Place a plastic piston (diameter = 60±0.2mm) on the glass cylinder containing the test sample and measure the weight of the cylinder mechanism (W1). After that, place a porous glass filter (Porosity = 0) in a Petri dish and fill each Petri dish with water. After placing the complete cylinder mechanism on the porous glass filter of the Petri dish containing the water, the weight of the piston (574±5 g) is adjusted so that the pressure becomes 0.3 psi by raising the cylindrical weight. After allowing the test sample to absorb water and blood for a certain period of time (60±1 minutes), measure the weight of the cylinder device (W2). The absorbency under pressure (AUL) for the amount of water absorbed by the SAP under pressure for a certain period of time was calculated as follows.

- AUL(g/g) = (W2(g)-W1(g))/SAP weight(g)

<Result 4>

As shown in FIG. 10, SAP prepared by spinning in 0.5 Mol of KCl has an absorption capacity of about 5,600% when the concentration of kappa carrageenan in the spinning dope is 5 wt% (Example 4), and the absorption capacity when the concentration of the spinning dope is 6 wt% As 3,900% (Comparative Example 4a), higher absorption performance was exhibited when the concentration of the spinning dope was 5%. When the concentration was 4wt%, it came out similar to the case of 6wt%. Therefore, in Comparative Example 4b, the concentration of the spinning dope was fixed to 5 wt%.

As shown in FIG. 11, when the concentration of the spinning stock solution is 5 wt%, the absorption capacity of the SAP yarn was compared by changing the Mol concentration of the KCl solution in the coagulation tank. As a result, the general absorption capacity according to the Mol concentration of the KCl solution was around 4,000%. Although there was no significant difference, as a result of the AUL test, the maximum absorbency under pressure for the SAP yarn crosslinked with 0.1 Mol of KCl solution was 2,000%. In the case of the SAP yarn crosslinked with 0.05 Mol of KCl solution, the absorbency under pressure was reduced due to the low crosslinking density, and agglomeration was observed.

Through this, in the case of manufacturing SAP yarn using the finished product of kappa carrageenan powder, it was found that it is most preferable to cross-link with the kappa carrageenan concentration of the spinning dope at 5 wt% and the concentration of the KCl solution at 0.1 Mol. Therefore, when it is desired to spin a SAP fiber yarn by making a spinning dope with a finished product of kappa carrageenan powder, it is preferable that the concentration of the spinning dope is 4 wt% to 6 wt%, and the molar concentration range of the KCl solution as a crosslinking agent is 0.05Mol to 0.5Mol. Do. And ethanol suitable for dehydrating the spun SAP fiber yarn is preferably an ethanol solution of 93% to 97%.

<Example 5> Preparation of SAP yarn by crosslinking the raw material, Cotony, with KCL solution

Cotony, the raw material of kappa carrageenan, was added to distilled water to make a mixed solution, stirred and heated to 90° C. or higher, and then heated for 20 minutes to make a spinning dope having a raw material concentration of 5 wt%. And while maintaining the spinning dope solution at 80°C or higher, the molar concentration was 0.2M and cross-linking was performed while wet spinning in a coagulation bath containing a KCl solution at 20°C to obtain SAP yarn. The SAP yarn was impregnated in an ethanol treatment tank containing 95% ethanol solution to remove moisture while transported, and then stretched and dried while transported in a drying furnace.

<Comparative Example 5>

In Example 5, the molar concentration of KCl was changed to 0.1M and 0.5M, respectively, and the rest was carried out in the same manner as in Example 5, respectively.

<Experimental Example 5>

Water absorption capacity and absorbency under pressure (AUL) were measured for the SAP yarns obtained in Example 5 and Comparative Example 5. The same method as the method applied in Experimental Example 1 was used for measuring the water absorption capacity, and the same method as the method used in Experimental Example 4 was used for the water absorption capacity under pressure (AUL) measurement method.

<Result 5>

As shown in FIG. 12, when a SAP yarn is prepared by crosslinking with a spinning dope of 5 wt% of the raw material and a 0.2 Mol KCl solution (Example 5), the maximum absorption capacity of the SAP yarn is about 4,000%, and cross-linking with a 0.1 Mol KCl solution Although it was slightly lower than the case of manufacturing, the AUL value was about 1,950%, showing the highest value. In the case of manufacturing SAP yarn by crosslinking with 5wt% of raw material spinning dope solution and 0.1Mol KCl solution, agglomeration was observed and showed an AUL value of about 1,500%. Therefore, when manufacturing SAP yarn by crosslinking raw material Cotony with KCL solution, it is most preferable to crosslink with the raw material concentration of the spinning dope solution as 5 wt% and the Mol concentration of the KCl solution as 0.2 Mol. Therefore, when it is desired to spin the SAP fiber yarn by making a spinning dope with the raw material of Cotony, the concentration of the spinning dope is 4 wt% to 6 wt%, and the molar concentration range of the KCl solution as a crosslinking agent is preferably 0.1 Mol to 0.5 Mol. . And ethanol suitable for dehydrating the spun SAP fiber yarn is preferably an ethanol solution of 93% to 97%.

Although the present invention has been described with the various examples described above, the present invention is not necessarily limited to these examples, and various modifications may be made within the scope without departing from the technical spirit of the present invention. Therefore, the examples disclosed in the present invention are not intended to limit the technical spirit of the present invention, but to explain, and the scope of the technical spirit of the present invention is not limited by these examples. The protection scope of the present invention should be construed by the following claims, and all technical ideas within the equivalent range should be construed as being included in the scope of the present invention.

Claims (11)

By stirring and heating a mixed solution in which distilled water is added to a raw material made of a raw material of Kappaphycus alvarezii having a kappa carrageenan component, the concentration of the raw material in the mixed solution is made into a spinning dope having 4 wt% to 6 wt%, After crosslinking the spinning stock solution by spinning it in a KCl solution having a molar concentration of 0.05M to 0.5M, it is impregnated in 93% to 97% ethanol solution, dehydrated and dried. delete delete delete Raw material processing step of washing a raw material made of a raw material of Kappaphycus alvarezii having a kappa carrageenan component in distilled water to remove salt and drying;
A spinning dope preparation step of adding distilled water to the raw material to make a mixed solution, and then heating the mixed solution with stirring to prepare a spinning dope having a concentration of the raw material in the mixed solution of 4 wt% to 5 wt%;
A spinning step of obtaining a SAP (Super Absorbent Polymer) yarn by crosslinking while wet spinning the spinning dope in a coagulation tank containing a KCl solution having a molar concentration of 0.05M to 0.5M;
a dehydration step of removing moisture while transferring the SAP yarn by impregnating it in an ethanol treatment tank containing 93% to 97% ethanol solution; and
a drying step of stretching and drying the SAP yarn that has undergone the dehydration step while transferring it in a drying furnace; A method for producing a natural component superabsorbent polymer fiber yarn comprising: delete delete The method of claim 5,
In the spinning dope preparation step, the heating of the mixed solution is a method for producing a natural superabsorbent polymer fiber yarn, characterized in that heating is maintained at 90° C. or higher for 18 to 22 minutes. The method of claim 8,
In the spinning step, spinning while maintaining the temperature of the spinning dope solution at 80° C. or higher, and maintaining the KCl solution at 15° C. to 25° C. The method of claim 5,
In the spinning step, the method for producing a superabsorbent polymer fiber yarn of natural ingredients, characterized in that the SAP yarn is spun so that the diameter is 500㎛ to 800㎛
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