POLY(VINYL ALCOHOL) MICROFIBRILLAR SHORT FIBER AND ITS PREPARATIVE METHOD

Abstract: This invention is a poly(vinyl alcohol) microfibrillar short fiber and its method of preparation, especially manufacturing the microfibrillar poly(vinyl alcohol) short fiber having high tensile strength, high tensile modulus, high fineness, and excellent alkali resistance using a special saponifying agent and through an advanced mechanical shearing operation in the course of saponification of poly(vinyl pivalate) to poly(vinyl alcohol) without requisite spinning, drawing, and heat treatment.

Description: POLY(VINYL ALCOHOL) MICROFIBRILLAR SHORT FIBER AND ITS PREPARATIVE METHOD HELD OF THE INVENTION This invention relates to poly(vinyl alcohol) microfibrillar short fibers , especially a microfibrillar poly(vinyl alcohol) short fiber having high tensile strength, high tensile modulus, high fineness, and excellent alkali resistance. The short fiber is prepared by a method using a special saponifying agent and an advanced mechanical shearing operation in the course of saponification of poly(vinyl pivalate) to poly(vinyl alcohol) without the spinning, drawing, and heat treatment required for conventional high strength and high modulus poly(vinyl alcohol). BACKGROUND OF THE INVENTION Poly(vinyl alcohol)(hereinafter PVA) fiber has been soptlighted as textile and industrial fibers for more than sixty years since it was first prepared by Herrmann in 1931 [German Patent No. 685,048]. There are two types of PVA used as a raw material of PVA fiber having high tensile strength and high tensile modulus. The first type is atactic PVA, with the following formula(a), and the other is syndiotactic PVA, represented by the following formula (b). Since the syndiotactic PVA has structural stability due to zigzag-type molecular structure, the syndiotactic PVA fiber has better mechanical property, thermal stability, chemical and weather resistance, when compared to the atactic PVA fiber. ( a ) OH OH OH —CH2-CH-CH 2 -CH-CH2-CH-CH2-CH-CH?-CH-CH2-CH— OH OH OH (b) In general, in the conventional preparative method of PVA fiber, the spinning , drawing, and heat treatment processes are included to give high orientation to the molecular chain. But the syndiotactic PVA has difficulty in drawing, due to strong intermolecular hydrogen bonding caused by the molecular structure compared to the atactic PVA. It is known that the syndiotactic PVA fiber developed up to now has higher tensile strength and modulus at a lower draw ratio than the atactic PVA fiber of the same molecular weight. Therefore, if the molecular orientation of the syndiotactic PVA having a compact structure is increased by increasing the draw ratio, the PVA fiber having higher tensile strength and modulus can be produced. To prepare a conventional PVA short fiber poly(vinyl ester), the precursor of PVA is synthesized and this precursor is saponified to produce PVA. After the synthesized PVA polymer had been solution-spun or gel-spun, the molecular chain of the PVA filament is oriented in parallel by the additional drawing and heat treatment. The PVA short fibers taple) is prepared by cutting the continuous PVA filament to a ® suitable length\. The high strength Vinylon fιber(Kuraray Co., Japan), now commercially available, is prepared by this method. The conventional PVA fiber may also be prepared according to Japanese Patent Laid Open Document 4-108, 109, the monomer having a side group giving steric hindrance is polymerized and a syndiotacticity-rich precursor is synthesized by the saponification of the polymer, followed by separating, washing, and drying. It is redissolved in the solvent, spun, drawn and dried. The PVA filament prepared by this process is cut by a special cutting-machine to obtain the short staple fiber. According to U. S. Patent No. 4,511,623, a short fiber can be prepared directly by polymerization with the help of the special action of pyridine/amide solvent, without spinning and drawing processes, in the course of preparing rigid rod poly(p- phenylene terephthalamide) known as aamid. However, this patent does not show preparing the short fiber accumulated with ultrafine microfibrils from the flexible chain polymer PVA in the course of saponification. According to U. S. Patent No. 5,238,995, the PVA polymer is prepared by the saponification of poly(vinyl pivalate) dissolved in tetrahydrofuran with the saponifying agent composed of potassium hydroxide/methanol solution, and then the PVA is separated, dried and redissolved in the solvent. After spinning, drawing, heat- treatment, washing, drying, and cutting, the PVA short fiber is produced. PVA prepared by this method has a degree of saponification of 99 mol%, syndiotactic diad content of over 60%, a high degree of orientation, and high crystallinity. According to Patent Laid Open Document 4-117,408 and 5-080,215, and Yamamoto [T. Yamamoto et al., Polymer Journal, 23, 185(1991)], poly(vinyl acetate) can be completely saponified by a general saponification method using sodium hydroxide/methanol solution. However, this syndiotacticity-rich high molecular weight polymer containing high molecular weight poly(vinyl pivalate) cannot be saponified effectively using sodium hydroxide. Hence, Yamamoto dissolved the syndiotacticity-rich poly(vinyl pivalate) polymer in tetrahydrofuran and synthesized the PVA with a hydroxyl group content of over 99 mol% by saponifying using potassium hydroxide/methanol solution. This saponification method has the advantage that the degree of saponification of over 99 mol% can be obtained without molecular chain scission. However, the syndiotactic PVA, which has a strong intermolecular hydrogen bonding as formula(c) indicates, is synthesized quickly, forming many hydroxyl groups in a very short time by a vigorous and speedy reaction of poly(vinyl pivalate) with the saponifying agent. ( c ) The hydrogen bonding force of the syndiotactic PVA causes gel or precipitate formation after the completion of saponification. Adding iodine compound to the PVA film prepared by film casting to improve the drawability of PVA has been developed [Y. S. Choi, et al., Polymer Journal, 22, 601(1990)]. This added iodine compound plays a role in weakening intermolecular hydrogen bonding by changing the crystal structure of PVA, thus improving the drawability of the polymer. As this compound is removed after the drawing, the original crystal sturcture of PVA is recovered and a highly oriented material is obtained. However, such a method should be applied in the course of or after spinning or film casting. The present inventors have conducted long term investigations and studies to develop a new method which can produce a PVA microfibrillar short fiber having high tensile strength and modulus, omitting procedures such as dissolving PVA synthesized after saponification, spinning the above PVA in the form of solution or gel, drawing more than ten times, and heating at a high temperature. The present inventors have realized that the high strength and high modulus PVA microfibrillar fiber which has different length, diameter, and elongation can be produced by adding a special alkali saponifying agent to the syndiotacticity-rich high molecular weight poly(vinyl pivalate)/tetrahydrofuran solution while being stirred with a special shearing device at a certain shear rate. The object of this invention is to simplify the complex preparinge process of PVA fiber and to provide a PVA microfibrillar fiber having high tensile strength and modulus, excellent alkali resistance, and good thermal stability. SUMMARY OF THE INVENTION This invention relates to the PVA microfibrillar short fiber which has a number- average degree of polymerization of 4,000-20,000, the syndiotactic diad content of 55-65%, the degree of saponification of 85.0-99.9%, a diameter of 1-50 μm, length of 0.5~300mm, irregular cross-sections, needle point-like ends, and an accumulated ultrafine microfibrillar structure. This invention prepares a PVA fiber only via saponification and mechanical stirring with a shear speed of over 500rpm, while omitting the later processes such as spinning, drawing and heat-treating which are required for manufacturing conventional high strength and high modulus PVA fibers. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 shows scanning electron micrographs for poly(vinyl alcohol) microfibrillar fibers of this invention. Figure 1 (a) is a photomicrograph for microfibrillar fiber magnified 4,000 times. Figure 1 (b) is a photomicrograph for microfibrillar fiber magnified 30,000 times. Figure 1 (c) is a photomicrograph for microfibrillar fiber magnified 50,000 times. Figure 2 shows a scanning electron micrograph for the commercial poly(vinyl alcohol) monofilament prepared via the conventional spinning method. DETAILED DESCRIPTION OF THE INVENTION This invention prepares high strength and high modulus PVA microfibrillar short fiber directly by dissolving syndiotacticity-rich high molecular weight poly(vinyl pivalate) in an organic solvent and adding a saponification agent while being stirred with an advanced mechanical stirrer. To prepare the PVA microfibrillar fiber having high tensile strength and modulus, excellent alkali resistance, high fineness, and good thermal resistance according to this invention, high content of syndiotactic group, high molecular weight, degree of saponification of over 85%, the good linearity of molecular chain, and absence of accompanying structure like 1,2-glycol, etc. should be kept. The most improtant factor which affects direct fiber formation during saponification and the physical properties of the PVA fiber is the syndiotacticity. For instance, the PVA fiber having a high molecular weight, but a syndiotactic diad content of 4-5% lower than other PVA fibers having a small molecular weight showed rather inferior mechanical and physical properties. PVA, which has a number- average molecular weight of about 400,000 and syndiotactic diad content of about 50% could not form fibril, but gel. In the process of preparing the PVA fiber of this invention, the time needed for completing fibrillation is only about 15 minutes due to the use of a new saponification agent which has not only a hydrogen bond forming ability, but also acts as a solvent. In the conventional method, after saponification had been completed, the produced PVA should be spun, drawn, and heat treated, whereas in this invention, the PVA microfibrillar fiber having high molecular orientation could be prepared successfully by the chemical reaction of the saponification agent. In addition, in this invention it is important to control the shear speed under appropriate conditions to prepare the microfibrillar short fiber. The saponification agent has a main role in this invention. Poly(vinyl pivalate) is first converted into the syndiotactic PVA by saponification using a special saponification agent, and the definite amount of hydroxyl groups formed during saponification are bound with the saponifying agent to develop the molecular orientation of PVA to fiber-axis direction. Then, after completing fibrillation, the saponification agent is separated from the microfibrillar fiber and the crystalline structure of PVA is formed. The saponification agent in this invention has a hydrogen bond forming ability with PVA and plays a role in providing high orientation to the PVA structure by mechanical shearing action, maintaining intramolecular hydrogen bonding, and forming a bridge between the intermolecular hydrogen bonding of PVA. A more detailed explanation for preparing the PVA microfibrillar short fiber with a high syndiotacticity in this invention follows. First, poly(vinyl pivalate) is dissolved in an organic solvent and oxygen in the reaction solution is removed while being stirred. After raising the reaction temperature to 50-60x3 , and an alkaline saponifying agent is mildly added, it is stirred at 10,000rpm. Thus, the viscosity of the reaction solution increases steeply in 6 minutes, and a gel is formed in the solution. The reason for the gel formation is that pivaloyl groups, the side group of poly (vinyl pivalate) are cleaved by the reaction with an alkali in the saponification agent and transformed into hydroxyl groups, the side group of PVA. Many hydroxyl groups of the resultant PVA form not only intermolecular hydrogen bonding, but also intramolecular hydrogen bonding, and PVA is solidified without orientation to a specific direction. However, as the stirring with 3,000rpm or more is continued, water in the saponification agent is regularly arranged among the molecular chains of PVA, laying bridges between the PVA molecules. Accordingly, the intramolecular hydrogen bonding is kept, while the direct intermolecular hydrogen bonding between PVA molecules is intercepted, keeping constant the distance between PVA chains. In time, the whole reaction solution becomes a gel and well arranged molecular chains are kept as they are. On the basis of the preparation described above, a solid-phase fibrous lump highly oriented to the fiber-axis direction is obtained. According to the said manufacturing method in this invention, the concentration of water contained in the saponification agent is important. If water does not exist, the intermolecular hydrogen bonding between the PVA molecules cannot be enfeebled. If the amount of water is about 3xl0 6 mole or more to 1 mole of poly(vinyl pivalate), logically the blocking of the intramolecular hydrogen bonding as well as the intermolecular hydrogen bonding of PVA is possible. In order to arrange the molecular chain of PVA along a certain direction, regardless of the type of stirring device, vigorous stirring with the speed of over lOOrpm, preferably over 500rpm, more preferably over 3,000rpm or more is necessary. For example, when the stirring speed was 500rpm or less, the PVA fiber having high tensile strength and modulus could be formed, but the degree of orientation to the fiber-axis direction decreased. The following formula(d) represents syndiotactic PVA forming intermolecular hydrogen bridges between PVA and water. ( ) Using a mixture of potassium hydroxide/methanol/water as the saponification agent is a prerequisite for the preparation of the PVA microfibrilla short fiber in this invention. This solution consists of Ixl0 "2 ~7xl0 '2 mole of potassium hydroxide, S lO^-SxlO 1 mole of methanol, and lxlO^-SxlO 1 mole of water to Ixl0- 7 ~7xl0 "7 mole of poly(vinyl pivalate). Organic solvents used are tetrahydrofuran, acetone, methylethylketone or dioxane, and tetrahydrofuran is especially the most effective solvent to form a strong fiber. Hence, it is possible to control the thickness and the length of the PVA microfibrillar fiber to any appreciable extent. The fibers prepared using a modified H-shape anchor type stirrer was finer and longer than those prepared using a simple anchor type stirrer probably owing to the more regular propagation of shear force to the inner part of the reaction mixture. In the case of relatively higher shear rate, finer and longer fibrils were obtained by setting a housing to the stiιτer in order to suppress the Weissenberg effect. After saponification, the saponification reaction mixture obtained through mechanical shearing operation is poured into methanol, followed by separation and washing. To obtain fibrillar fiber form, the solid fibrillar reaction mixture should be tapped mechanically or treated with an ultrasonic generator containing methanol solution. The PVA fiber having needle point-like ends in this invention can be widely used for many purposes, since its properties are like natural cotton, ramie, linen or jute, and are exceptionally superior to those of natural fibers. Because of excellent adiabatic property which resulted from a very fine microfibrillar structure, the PVA microfibrillar fibers, 1~5() μm in diameter and 0.5~300mm in length, can be used as a material replacing natural carcinogenic asbestos fiber. Furthermore, it is useful as a high performance composite material such as cement or concrete reinforcing fiber owing to the high tensile strength, high tensile modulus, excellent reinforcing fiber owing to the high tensile strength, high tensile modulus, excellent alkali resistance, and good affinity for the inorganic compound for building materials. The fiber in this invention can be used for a fishing net with the property of strong resistance to seawater and can be applied to the making of pulp for paper on the basis of its excellent physical properties. The details of this invention is demonstrated by the following examples. Example 1 In a 500ml 5-neck round bottom flask equipped with a thermometer, a nitrogen inlet, a reflux condenser, a dropping funnel, and an H-shape anchor-type stirrer, poly (vinyl pivalate)(lg : 2.88X10 "7 mol) having a number-average degree of polymerization of 27,100 was dissolved in tetrahydrofuran(100ml : 1.23 mol). After 10ml of the mixed solution of potassium hydroxide(2.5ml : 4.46X10 '2 mol), methanol(8.5ml : 2.09X10 "1 mol), and ateι( 1.5ml : 8.31Xiσ 2 mol) had been added slowly to the above poly(vinyl pivalate) solution at 60 , while being stirred at 500rpm for 4 minutes, the stirring speed of the reaction solution was raised to 10,000rpm for 5 minutes, and then reduced to 2,000rpm for 10 minutes. After the saponification reaction was complete, the solid fibrillar reaction mixture was tapped mechanically or treated in an ultrasonic generator containing methanol(3()0ml). The fibers thus produced were filtered, washed several times with methanol, and dried in a vaccum. Example 2 In a 500ml 5-neck round bottom flask equipped with a thermometer, a nitrogen inlet, a reflux condenser, a dropping funnel, and an H-shape anchor-type stirrer, poly (vinyl pivalate)(lg : 2.39X 10 "7 mol) having a number-average degree of polymerization of 32,600 was dissolved in tetrahydrofuran( 100ml : 1.23 mol). After 10ml of the mixed solution of potassium hydroxide(2.5ml : 4.46X10 '2 mol), methanol(8.5ml : 2.09X10 1 mole), and water(1.5ml : 8.31X10 "2 mol) had been added slowly to the above poly(vinyl pivalate) solution at 60x2 while being stirred at 500rpm for 4 minutes, the stirring speed of the reaction solution was raised to 10,000rpm for 5 minutes, and then reduced to 2,000rpm for 10 minutes. After the saponification reaction was complete, the solid fibrillar reaction mixture was tapped mechanically or treated in an ultrasonic generator containing methanol (300ml). The fibers thus produced were filtered, washed several times with methanol, and dried in a vacuum. Example 3 In a 500ml 5-neck round bottom flask equipped with a thermometer, a nitrogen inlet, a reflux condenser, a dropping funnel, and an H-shape anchor-type stirrer, poly (vinyl pivalate)(lg : 2.88X10 "7 mol) having a number-average degree of polymerization of 27,100 was dissolved in tetrahydroguran(100ml : 1.23 mol). After 10ml of the mixed solution of potassium hydroxide(2.5ml : 4.46X10 "2 mol), methanol(8.()ml : 1.97X10 "1 mole), and water(2ml : 1.16X10 "1 mol) had been added slowly to the above poly(vinyl pivalate) solution at 60x3 while being stirred at 500rpm for 3 minutes, the stirring speed of the reaction solution was raised to 10,00()rpm for 5 minutes, and then reduced to 2,000rpm for 10 minutes. After the saponification reaction was complete, the solid fibrillar reaction mixture was tapped mechanically or treated in an ultrasonic generator containing methanol(300ml). The fibers thus produced were filtered, washed several times with methanol, and dried in a vacuum. Example 4 In a 500ml 5-neck round bottom flask equipped with a thermometer, a nitrogen inlet, a reflux condenser, a dropping funnel, and an H-shape anchor-type stirrer, poly (vinyl pivalate)(lg : 2.88X10 *7 mol) having a number-average degree of polymerization of 27,100 was dissolved in tetrahydrofuran(100ml : 1.23 mol). After 10ml of the mixed solution of potassium hydroxide(2.5ml : 4.46X10 '2 mol), methanol(8.5ml : 2.09X10 '1 mole), and water(1.5ml : 8.31X10 "2 mol) had been added slowly to the above poly(vinyl pivalate) solution at 55 i while being stirred at 500rpm for 4 minutes, the stirring speed of the reaction solution was raised to 10,000rpm for 8 minutes, and then reduced to 2,000rpm for 10 minutes. After the saponification reaction was complete, the solid fibrillar reaction mixture was tapped mechanically or treated in an ultrasonic generator containing methanol(3()0ml). The fibers thus produced were filtered, washed several times with methanol, and dried in a vacuum. Comparative Example 1 In a 500ml 5-neck round bottom flask equipped with a thermometer, a nitrogen inlet, a reflux condenser, a dropping funnel, and an H-shape anchor-type stirrer, poly (vinyl pivalate)(lg : 1.47X10 "6 mol) having a number-average degree of polymerization of 7,900 was dissolved in tetrahydrofuran(100ml : 1.23 mol). After 10ml of the mixed solution of potassium hydroxide(2.5ml : 4.46X10 '2 mol), methanol(8.5ml : 2.09X 10 "1 mole), and water(1.5ml : 8.31xl0 "2 mol) had been added slowly to the above poly(vinyl pivalate) solution at 60x3 while being stirred at 500rpm for 4 minutes, the stirring speed of the reaction solution was raised to 10,000rpm for 5 minutes, and then reduced to 2,000rpm for 10 minutes. The reactant was solidified without the formation of the microfibrillar fiber. After the solid reaction mixture had been washed in methanol(300ml), gel and precipiatate-type (PVA)s were obtained. Comparative Example 2 In a 5()()ml 5-neck round bottom flask equipped with a thermometer, a nitrogen inlet, a reflux condenser, a dropping funnel, and an H-shape anchor-type stirrer, poly (vinyl pivalate)(lg : 2.88xl() "7 mol) having a number-average degree of polymerization of 27,100 was dissolved in tetrahydrofuran( 100ml : 1.23 mol). After 10ml of the mixed solution of potassium hydroxide(2.5ml : 4.46X10 '2 mol) and methanol(10ml : 2.46X10 "4 mol) had been added slowly to the above poly (vinyl pivalate) solution at 60X3 while being stirred at 500rpm for 4 minutes, the stirring speed of the reaction solution was raised to 10,000rpm for 5 minutes, and then reduced to 2,000rpmfor 10 minutes. The reaction mixture became solidified without fibril formation. After the reaction mixture solidified had been transferred to the other flask, the needle-like precipitate was obtained by mechanical crushing with a high speed mixer. The characteristics of the PVA microfibrillar fiber prepared by the methods demonstrated in examples 1-4 are shown in the following table. Example Comparative Example 1 2 3 4 1 2 Syndiotactic diad 64 59 64 64 52 64 content (mol%) Degree of 99.4 99.6 99.0 96.1 99.7 99.1 saponification (mol% Crystal melting 260 247 258 253 231 248 temperature Tensile strength >15 >9 >12 >10 - - (g/den) Number-average degree of 16,700 15,400 16,800 5,400 16,100 polymerization In this invention, poly(vinyl pivalate), which has very good structural regularity is used as a starting material. To prepare a PVA microfibrillar short fiber having high tensile strength and modulus in this invention, structural regularity and the degree of saponification of PVA are important. Adequate degree of saponification, i.e., appropriate concentration of hydroxyl groups, plays an improtant role in preparing the PVA fiber having high tensile strength and modulus since this makes the PVA molecular chains effectively oriented and the size of crystal formed properly controlled. In this invention, the tensile strength was over 15g/den at the degree of saponification of 99.4 mol%, and the crystal melting temperature of the PVA microfibrillar fiber prepared according to example 1 in this invention was over 260x3 by differential scanning calorimetry. The crystal melting temperature of the microfibrillar fiber in this invention is comparable to that of a fiber prepared by spinning PVA having a similar syndiotactic diad content and molecular weight in dimethylsulfoxide, drawing over 10 times, and heat-treating at over 200X3. According to this invention, the PVA microfibrillar fiber, being a match for the high strength PVA spun fiber, can be prepared even though the conventional processes, spinning, high drawing, and heat-treating at a high temperature are ommitted. The tensile strength of the PVA microfibrillar fiber prepared by the method given in example 1 in this invention surprisingly indicated over 15g/den on an instron tensile tester. To prepare a fiber having the tensile strength of over 15g/den by a conventional method, PVA with a very high molecular weight should be synthesized, and making a stable solution is very difficult owing to its high molecular weight. After the solution or gel had been made, the spinning, drawing over 10 times, and heat-treating at a high temperature must be conducted. However, in this invention, all the above processes are omitted and the high strength PVA fiber can be obtained only by the saponification of poly(vinyl pivalate). Moreover, the degree of solubility of the PVA microfibrillar fiber in this invention in hot water at 105x3 for 3 hours was nil and the degree of swelling in water at 30X3 for 50 hours was below 0.2. These values are lower than those of a PVA fiber prepared via the spinning, drawing and heat-treating in the conventional method. It was known that these values cannot be obtained, if the additional acetalization procedure for the reduction of the degrees of solubility and swelling to boiling water does not proceed. Accordingly, the PVA microfibrillar fiber prepared by the method described in this invention has low degrees of solubility and swelling to boiling water despite the omission of the conventional spinning, drawing, heat- treatment, and acetalization. The PVA fiber in this invention has a very high resistance to strong alkaline aqueous solutions of over pH 13.5. Figure 1 shows the scanning electron micrographs for the PVA microfibrillar short fiber in this invention. It shows that the PVA microfibrillar short fiber has an accumulated ultrafine microfibril stmcture unlike the conventional PVA spun fiber and the fibrils are highly oriented. Additionally, the degree of crystallinity of the fiber in this invention was determined using a density gradient tube and a value of more than 40% was obtained. This value cannot be obtained if the conventional PVA fiber is not heat-treated at over 150X3 and not drawn over several times. The apparent crystallite size obtained by the wide-angle X-ray diffraction analysis of the PVA fiber in this invention was over 45 A .

Claims: WHAT IS CLAIMED IS : 1. A PVA microfibrillar short fiber including a dimension of l ~50μm in diameter and 0.5~30()mm in length, a syndiotactic diad content of 55-64%, a degree of saponification of 85.0-99.9%), a number-average degree of polymerization of 4,000-20,000, needle point-like ends, and an accumulated ultrafine microfibril sutructure. 2. A method of preparing high strength and high modulus PVA microfibrillar short fiber comprising saponifying poly(vinyl pivalate) solution while being stirred at a stirring speed of over 500rpm, without the dissolving, spinning, drawing, and heat-treatment of PVA. 3. The method of claim 2, wherein the organic solvent for poly(vinyl pivalate) is tetrahydrofuran, acetone or methylethylketone. 4. The method of claim 2, wherein the saponification agent comprises Ixl0 "2 -7xl0 "2 mole of potassium hydroxide, SxlO^-SxlO "1 mole of methanol, and lxlO^-SxlO "1 mole of water to Ixl0 "7 ~7xl0 "7 mole of poly(vinyl pivalate).

Inventors: CHOI YOUNG KEUN, HA WAN SHIK, LYOO WON SEOK, CHOI, YOUNG, KEUN, HA, WAN, SHIK, LYOO, WON, SEOK
Applicants: HA WAN SHIK, LYOO WON SEOK, SUNKYONG IND LTD, HA, WAN, SHIK, LYOO, WON, SEOK, SUNKYONG INDUSTRIES CO., LTD.
Application year: 1995
Main classification: D01F6
IPC codes: D01F6