KR20170050909A - Manufacturing method for a nonwoven fabric containing natural functional fibers with excellent water absorption - Google Patents
Manufacturing method for a nonwoven fabric containing natural functional fibers with excellent water absorption Download PDFInfo
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- KR20170050909A KR20170050909A KR1020150153035A KR20150153035A KR20170050909A KR 20170050909 A KR20170050909 A KR 20170050909A KR 1020150153035 A KR1020150153035 A KR 1020150153035A KR 20150153035 A KR20150153035 A KR 20150153035A KR 20170050909 A KR20170050909 A KR 20170050909A
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4266—Natural fibres not provided for in group D04H1/425
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01G—PRELIMINARY TREATMENT OF FIBRES, e.g. FOR SPINNING
- D01G15/00—Carding machines or accessories; Card clothing; Burr-crushing or removing arrangements associated with carding or other preliminary-treatment machines
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/425—Cellulose series
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/44—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties the fleeces or layers being consolidated by mechanical means, e.g. by rolling
- D04H1/46—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties the fleeces or layers being consolidated by mechanical means, e.g. by rolling by needling or like operations to cause entanglement of fibres
- D04H1/48—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties the fleeces or layers being consolidated by mechanical means, e.g. by rolling by needling or like operations to cause entanglement of fibres in combination with at least one other method of consolidation
- D04H1/49—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties the fleeces or layers being consolidated by mechanical means, e.g. by rolling by needling or like operations to cause entanglement of fibres in combination with at least one other method of consolidation entanglement by fluid jet in combination with another consolidation means
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06C—FINISHING, DRESSING, TENTERING OR STRETCHING TEXTILE FABRICS
- D06C3/00—Stretching, tentering or spreading textile fabrics; Producing elasticity in textile fabrics
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06C—FINISHING, DRESSING, TENTERING OR STRETCHING TEXTILE FABRICS
- D06C7/00—Heating or cooling textile fabrics
Abstract
Description
The present invention relates to a method for producing a nonwoven fabric comprising a natural functional fiber having excellent water absorbency by pretreating natural functional fibers and mixing them with cellulose fibers to produce a nonwoven fabric.
The nonwoven fabric is formed by forming a sheet-shaped web that tangles various fibers such as natural fibers, chemical fibers, glass fibers, and metal fibers according to their mutual characteristics, and combines them in a mechanical or physical manner. As a structure, various nonwoven fabrics have been extensively used in various industrial fields depending on nonwoven fabric use, characteristics, and functions. Further, studies on various nonwoven fabrics have been conducted by mixing secondary woven fabrics or components capable of adding various functionalities.
Particularly, it is possible to produce a nonwoven fabric to which the function of the natural polymer is added by converting natural polymers such as collagen, gelatin, chitin, chitosan, alginic acid, sericin, florane and the like into fibers and mixing them with cellulosic fibers to produce nonwoven fabrics.
Alginate fibers produced by using alginic acid have attracted attention as biodegradable fiber materials both domestically and internationally as a raw material of seaweed as a raw material, and alginate has a carboxyl group of uronic acid in the molecule, , Usually in the form of the sodium salt. Alginic acid can be easily made into fibers by using a calcium chloride solution as a coagulating bath to produce alginate fibers.
Since alginic acid, which is a raw material of alginate fiber, is not toxic to the human body and is easy to be processed and dissolved in water and exhibits high viscosity, it is widely used in foods, medicines and textile industries and forms gels by forming crosslinks with metal salts. In recent years, chitin and chitosan have attracted attention as natural polymer materials as wound dressing agents.
Chitosan obtained by deacetylation of chitin extracted from shells of crustaceans (crabs, shrimp, gauze, squid bones, etc.) is easy to absorb in the human body. Chitosan is a type of aminopolysaccharide. Its unique chemical structure, As a natural polymer present, it is non-toxic, biodegradable, and biocompatible by its unique cationic nature. Therefore, it has biochemical characteristics such as cell binding and biotissue culture, antibacterial and hemostatic action, cholesterol lowering action, intestinal Metabolism, antitumor activity by immunity enhancement, improvement of liver function and hypoglycemia, and detoxification of heavy metals.
In order to add useful functions such as antibacterial, deodorant, warmth and moisturizing properties of the above-mentioned chitosan to the nonwoven fabric, a chitosan solution in which high purity natural chitosan is generally dissolved is extruded through a spinning nozzle and spun out, and then sodium hydroxide, sodium sulfate, Sodium chloride in an aqueous solution containing an alkali metal salt selected from the group consisting of sodium chloride and sodium chloride.
The alginate fiber and chitosan fiber are excellent in antibacterial and moisturizing properties and can be applied to deep wounds in which a large number of exudates are generated, and have advantages such as fast absorption rate, stability that the edges are not bent when the exudates are absorbed, .
In Published Patent Application No. 2001-0097226 (published on November 11, 2001), chitosan fiber prepared by shaking solution of chitosan prepared from shrimp and crab was prepared, and the obtained fiber was softly and flexibly processed by needle punching or chemical bonding A method of producing a chitosan nonwoven fabric having sufficient strength is proposed.
Japanese Patent Application Laid-Open No. 2004-176230 (published on June 26, 2004) discloses a hygroscopic fiber structure which improves hygroscopicity of fibers by attaching multivalent metal salt of alginic acid to the surface of the fiber structure and improves the feel without sticking even when wet, A manufacturing method is proposed.
However, in the case of the nonwoven fabric and the fiber structure including the functional natural materials such as chitosan and alginate of the above-mentioned prior art, the absorbency of the nonwoven fabric and the fiber structure is lowered due to the flexibility of the surface of the functional natural fiber, There is a problem in that the transfer of the components is deteriorated.
In the present invention, in order to prevent the lowering of the water absorbency of the nonwoven fabric containing the natural functional fiber, the natural functional fiber is pretreated by adding a fiber finishing agent to remove the flexible component of the fiber surface formed during synthesis and spinning of the natural functional fiber To provide a method for producing a nonwoven fabric containing natural functional fibers having excellent water absorbency.
According to an aspect of the present invention, there is provided a method for manufacturing a natural functional fiber, comprising the steps of: heating a natural functional fiber by adding textile auxiliaries to the natural functional fiber; A mixing step of mixing the natural functional fiber and the cellulose fiber through the temperature-lowering step, and a step of preparing a non-woven fabric by carding and water-punching the mixed natural functional fiber and the cellulose fiber, It is a nonwoven fabric included.
The natural functional fiber may be chitosan and / or alginate fiber, and the fiber preparation may preferably contain a surfactant.
In the heating step, 0.1 to 1 part by weight of the fiber auxiliary is preferably contained in 100 parts by weight of the natural functional fiber. It is more preferable that the heating step is performed at 90 to 100 ° C for 5 to 15 minutes.
In the temperature-lowering step, it is preferable that the heated natural functional fiber is heated to 35 to 45 ° C or the heated natural functional fiber is thermally reduced at a rate of 5 to 11 ° C / min.
In the mixing step, 70 to 97 wt% of the cellulose fibers and 3 to 30 wt% of the natural functional fibers may be mixed.
Another embodiment of the present invention is a nonwoven fabric comprising the natural functional fibers excellent in absorbency produced by the above production method.
The present invention relates to a method for producing a nonwoven fabric containing natural functional fibers having excellent water absorbency, wherein the natural functional fibers are pretreated by adding a fiber finishing agent to the natural functional fibers, It is possible to obtain an effect of increasing the absorbency.
Also, since the surface of the nonwoven fabric of the present invention is not smooth due to the removal of the softening component, the functional component of the natural functional fiber can be transferred to the contact surface more quickly than the nonwoven fabric containing the natural functional fiber.
BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a flowchart showing a method for producing a nonwoven fabric containing natural functional fibers excellent in absorbency of the present invention.
FIG. 2 is a photograph showing fibers stained with a Bokenstain fiber discriminating reagent according to presence or absence of pretreatment of chitosan fiber. FIG.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The preferred embodiments of the present invention will now be described in detail with reference to the accompanying drawings. Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. As well as the fact that
Throughout this specification, when a member is located "above " another member, this includes not only when a member is in contact with another member, but also when another member is present between the two members.
Throughout this specification, when an element is referred to as "including" an element, it is understood that it may include other elements as well, without departing from the other elements unless specifically stated otherwise.
Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings.
First, FIG. 1 illustrates a method of manufacturing a nonwoven fabric including a natural functional fiber having excellent water absorbability according to an embodiment of the present invention. The method includes heating a natural functional fiber by containing textile auxiliaries, A temperature-lowering step of cooling the functional fiber to a temperature, a mixing step of mixing the natural functional fiber and the cellulose fiber through the temperature-lowering step, and a step of producing the nonwoven fabric by carding and water-punching the mixed natural functional fiber and the cellulose fiber have.
The natural functional fiber is a fibrous natural polymer selected from the group consisting of collagen, gelatin, chitin, chitosan, alginic acid, sericin and florane. Preferably, the natural functional fiber is composed of chitosan fiber and / or alginate fiber Can be used.
Particularly, chitosan fiber and alginate fiber are excellent in antibacterial property and moisturizing property and are widely used for medical applications. It is applicable to deep wounds in which a large amount of exudate is generated due to high absorption rate, and stability and wounds And it does not stick to the site.
However, in the case of the above-mentioned natural functional fibers, due to the flexible component of the fiber surface formed during the synthesis and spinning process, the absorbency of the non-woven fabric is lowered when mixed with the cellulose fibers, and the transfer of the components of the natural functional fibers is also lowered There was a problem.
Therefore, in order to remove the softening component of the surface of the natural functional fiber, it is preferable to prepare the nonwoven fabric by mixing with the cellulose fiber after the heating step and the warming step.
The heating step includes heating the natural functional fiber with textile auxiliaries and preferably 0.1 to 1 part by weight of the fiber auxiliary to 100 parts by weight of the natural functional fiber at 90 to 100 캜 It is preferable to heat for 5 to 15 minutes.
The surfactant may be a surfactant. The surfactant may be a commercially available anion, a nonionic surfactant, a surfactant, a cationic surfactant, Ionic, cationic or amphoteric surfactant can be used, but most preferably nonionic surfactant having no ionic property can be used.
In particular, since alginate fibers have a large number of carboxyl groups and hydroxyl groups in the molecular structure, when cationic surfactants are used, they can aggregate with the components contained in the alginate fibers and be adsorbed into the fibers without being removed, and use anionic surfactants It is most preferable to use a nonionic surfactant since it is difficult to remove the flexible component on the surface of the fiber since it has the same ionic property. Specifically, polyoxyethylene compound and / or ethoxylate compound Can be used.
More specifically, polyoxyethylene tridecyl ether and / or alkyl alcohol ethoxylates (C8 to C16) can be used.
In the heating step, 0.1 to 1 part by weight of a surfactant-containing fiber preparation is preferably contained in 100 parts by weight of the natural functional fiber. If the amount is less than 0.1 part by weight, the flexible component is not sufficiently removed The absorbability and the effect of increasing drug transfer can not be sufficiently exerted, and when the amount is larger than 1 part by weight, the inside of the functional fiber may be damaged and the functionality may be deteriorated.
It is preferable that the heating step is carried out at 90 to 100 ° C for 5 to 15 minutes. If the temperature and the time are out of the above range, the flexible component of the natural functional fiber is not sufficiently removed, or the cellulose component is mixed with the cellulose fiber, The physical properties of the chitosan may change to cause a change in hue or yellowing, and the inside of the chitosan fiber may be damaged to weaken the binding force between the fibers during the production of the nonwoven fabric.
The temperature-lowering step of lowering the temperature of the natural functional fiber heated through the heating step may be preferably carried out at a temperature of 35 to 45 ° C at a rate of 5 to 11 ° C / min. More preferably, the temperature can be lowered by 40 占 폚.
It is preferable that the activation of the fiber preparation is lowered through the temperature-lowering step to prevent excessive deodorization of the flexible component of the natural functional fiber, and the temperature of the untreated fiber preparation is gradually lowered to effectively wash off the fabric preparation.
In the mixing step of mixing the pretreated natural functional fiber and the cellulose fiber through the heating step and the warming step, the cellulose fiber may be mixed with 70 to 97 wt%, and the natural functional fiber may be mixed with 3 to 30 wt%. When the natural functional fiber is contained in an amount of less than 3 wt%, the functionality of the natural functional fiber tends to be insignificant as in the case of the conventional nonwoven fabric. When the natural functional fiber is more than 30 wt% The cost competitiveness is deteriorated and the content of cellulosic fibers is decreased, so that it is difficult to maintain the shape of the nonwoven fabric.
The natural functional fibers of the present invention are preferably natural functional fibers produced from natural products, but more preferably chitosan fibers and / or alginate fibers can be used, And can be used without limiting its kind.
When the fibers are mixed as described above, the nonwoven fabric containing the natural functional fibers of the present invention having excellent water absorbency can be produced through the steps of carding and rawter punching the mixed natural functional fibers and cellulose fibers.
The carding is a step of arranging the raw material state as a preparation step for forming a raw material (nonwoven fabric), and water punching is a step of forming high-pressure water into fibers to entangle the fibers to form a nonwoven fabric. The carding and water punching are well known in the field of producing a nonwoven fabric, and thus a detailed description thereof will be omitted herein.
When the nonwoven fabric is manufactured through the steps of manufacturing the nonwoven fabric as described above, the nonwoven fabric may be further processed by rolling, slitting according to the standard, and punching or folding.
Hereinafter, embodiments relating to a method for producing a nonwoven fabric including natural functional fibers excellent in absorbency of the present invention will be described. However, the scope of the present invention is not limited to the following preferred embodiments, and a person skilled in the art can carry out various modifications of the contents described in the present invention within the scope of the present invention.
[Manufacturing Example]
Fabrication of non-woven fabric containing natural functional fibers excellent in absorbency
After 600 kg of chitosan fiber was added to the fiber preparation, it was heated at 95 ° C for 10 minutes. Thereafter, the pre-treated chitosan fiber was prepared by slowly warming it to 40 ° C at a rate of 7.8 ° C / min with over-flow (cold water).
After 20 kg of the pretreated chitosan fiber was mixed with 80 kg of each cellulose fiber, the web was processed by a carding machine to uniformly group the cellulose fibers and the pretreated chitosan fiber web, and then the nonwoven fabric .
[Experimental Example 1]
Evaluation of properties of chitosan fiber with and without pretreatment
Commercially available chitosan fibers and chitosan fibers pretreated by the methods described in the above preparation examples were respectively measured by Bokenstain fiber discrimination reagent method.
The reactivity of the dye is different depending on the degree of the constituent of the flexible material formed on the surface of the fiber. The more the flexible component is, the lower the reactivity of dyeing is, and the dyeing is not performed well.
As shown in FIG. 2, it was confirmed that chitosan fibers pretreated as compared to chitosan fibers not pretreated showed deep blue color similar to that of natural cotton fibers.
This shows that the reactivity of dyeing is different depending on the amount of the flexible component formed on the surface of the fiber. The smaller the amount of the flexible component is, the better the reactivity of dyeing is, and the color of dyeing is clear.
Thus, it was confirmed that the pretreatment process of adding the fiber preparation to the chitosan fiber and heating the fabric after heating to remove the softening agent on the surface of the chitosan fiber resulted in a clear dyeing.
[Experimental Example 2]
Evaluation of absorbency according to amount of fiber additive
According to the preparation method of the above Preparation Example, 600 kg of chitosan fiber was pretreated by varying the content of the fiber preparation to prepare a nonwoven fabric, and the absorbency was evaluated.
A nonionic surfactant containing polyoxyethylene tridecyl ether and alkyl alcohol ethoxylates in a weight ratio of 6: 5 was used as the fiber preparation.
5 g of the produced nonwoven fabric was immersed in water at 25 캜 for 3 minutes, then taken out from the water in a gentle manner and taken out from the water side to the side of a 10-mesh wire net for 1 minute. The water was dropped into the beaker, Respectively.
As shown in Table 1, the water absorption amount of the nonwoven fabric prepared without addition of the fiber preparation was the lowest at 30.26 g, and 3.0 kg of the fiber preparation was pretreated, and the prepared nonwoven fabric was 38.91 g And showed a high absorption amount.
[Experimental Example 3]
Evaluation of Properties of Fiber Preparations according to Heating Temperature
According to the preparation method of the above-mentioned preparation example, 3.0 kg of fiber preparation was added to 600 kg of chitosan fiber, and the fiber was pretreated while changing the heating temperature. Followed by mixing to prepare a nonwoven fabric.
The breaking strength was measured by cutting the nonwoven fabric to a width of 10 mm × 150 mm, and measuring the breaking strength of the nonwoven fabric through a tensile tester (measured by grappling method based on Fafegraph-M, Textecho Co., Germany, KSK 0520).
The absorbency was evaluated according to the experimental method of Experimental Example 2 above.
As can be seen from Table 2, when the heating temperature was 105 ° C, the inside of the chitosan fiber was damaged due to excessive deodorization of the flexible component, and it was confirmed that the breaking strength of the nonwoven fabric was as low as 0.44 Kg / ° C., it was confirmed that the water-absorbing property was inferior in comparison with the result of Experimental Example 2, and that when the heating temperature was 105 ° C., the water-absorbing amount was rather reduced due to excessive deodorization of the flexible component .
Therefore, when preparing the nonwoven fabric using the chitosan fiber as the natural functional fiber, 0.1 to 1 part by weight of the fiber preparation is added to 100 parts by weight of the chitosan fiber, and the resultant is pretreated at 90 to 100 ° C to remove the softening component of the chitosan fiber surface It was confirmed that the water absorption was increased.
Claims (9)
A temperature-lowering step of lowering the temperature of the heated natural functional fiber;
A mixing step of mixing the natural functional fiber and the cellulose fiber through the temperature-lowering step; And
Preparing a nonwoven fabric by carding and water-punching the mixed natural functional fiber and the cellulose fiber; Wherein the nonwoven fabric comprises a natural functional fiber excellent in absorbency.
The natural functional fiber may include,
A method for producing a nonwoven fabric comprising a natural functional fiber excellent in absorbency, which is chitosan and / or alginate fiber.
The method for producing a nonwoven fabric according to any one of claims 1 to 3, wherein the preparation for fibers comprises a surfactant.
In the heating step,
Wherein the natural functional fiber is contained in an amount of 0.1 to 1 part by weight based on 100 parts by weight of the natural functional fiber.
The heating step
Wherein the nonwoven fabric is heated at 90 to 100 占 폚 for 5 to 15 minutes.
In the temperature-lowering step,
Wherein the heated natural functional fiber is heated to 35 to 45 ° C.
Preferably,
Wherein the heated natural functional fiber is heated at a rate of 5 to 11 占 폚 / min.
In the mixing step,
Characterized in that 70 to 97 wt% of the cellulose fibers and 3 to 30 wt% of the natural functional fibers are mixed together.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102265286B1 (en) * | 2020-10-06 | 2021-06-14 | 최광일 | Method for manufacturing cordyceps scorched rice using grain products |
| KR20220107385A (en) * | 2021-01-25 | 2022-08-02 | 경북대학교 산학협력단 | Method of manufacturing water soluble film and water soluble film thereby |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004141255A (en) | 2002-10-22 | 2004-05-20 | Asahi Kasei Fibers Corp | Wet wiper |
| KR100912644B1 (en) | 2009-02-13 | 2009-08-17 | 김덕례 | The preparing method of chemically transformed chitosan fiber |
| KR101149061B1 (en) | 2010-11-16 | 2012-05-24 | 이수복 | Chitosan non-woven fabric for mask pack material, and method for manufacturing the non-woven fabric |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102265286B1 (en) * | 2020-10-06 | 2021-06-14 | 최광일 | Method for manufacturing cordyceps scorched rice using grain products |
| KR20220107385A (en) * | 2021-01-25 | 2022-08-02 | 경북대학교 산학협력단 | Method of manufacturing water soluble film and water soluble film thereby |
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