WO2008153239A1

WO2008153239A1 - Manufacture method of wet-tissue with antimicrobial and anti-fungus function

Info

Publication number: WO2008153239A1
Application number: PCT/KR2007/003445
Authority: WO
Inventors: Gu-Wan Jeong
Original assignee: Nanopoly Co., Ltd
Priority date: 2007-06-11
Filing date: 2007-07-16
Publication date: 2008-12-18
Also published as: JP2011501977A; US20100180413A1; KR100887768B1; JP5179576B2; CN101960070A; KR20080108714A

Abstract

This invention is on manufacturing method of antimicrobial and anti- fungus wet tissues with antimicrobial and anti-fungus whole cloth for wet tissue(i.e. non-woven fabrics, cottons and papers) manufactured with nano metal particles soak in tissue manufacturing water with nano sized metal particles which have antimicrobial and anti-fungus function to have multiple effects. According to this invention, woven fabrics, cottons and papers soak in the tissue manufacturing water that one or more than one of selected nano metal particles from gold, platinum, silver, germanium, selenium, zinc, copper and tungsten are mixed in the tissue manufacturing water and then they have antimicrobial and anti-fungus function. The antimicrobial and anti-fungus whole cloth for wet tissue is formed into antimicrobial and anti-fungus non-woven fabric whole cloth by mixing and blending selected one or mixtures more than one of the fabric materials of viscose rayon, polyester, polyethylene, polypropylene, cotton and pulp with selected one or mixtures more than one of nano metal particles of platinum, gold, silver, germanium, selenium, zinc, copper and tungsten.

Description

[DESCRIPTION] [Invention Title]

MANUFACTURE METHOD OF WET-TISSUE WITH ANTIMICROBIAL AND ANTI-FUNGUS FUNCTION [Technical Field]

<i> This invention relates to a manufacture method of wet-tissue with antimicrobial and anti-fungus function with Non-woven fabrics, Cotton fabrics and other tissue papers or nano particle treated on-woven fabrics which already have antimicrobial and anti-fungus function, more particulary to the technology how to make those materials to have antimicrobial and anti-fungus functions by adding nano particles. [Background Art]

<2> In general, the disposable wet tissues are used at various commercial and public places such as restaurants, public transportation and hospitals by unspecified persons to clean themselves and take care of excrements of kids.

<3> As they clean up by scrubbing the skin with the wet tissue, it is required to have stability with skin and strong function to remove foreign materials from the skin of users.

<4> Therefore, the wet tissues are being manufactured with paper or fabrics of soft materials such as non-woven fabrics, and it is cut to specific sizes and add distilled water before they are sealed and packed in synthetic resin packing material.

<5> The non-woven fabrics as the major raw materials for wet tissue are manufactures by put the fabrics parallel or unfixed direction and combine to make it felt shape. There are Viscose rayon, Polyester (PE), and Polypropylene (PP) as synthetic fibers, and cotton as well as natural pulp as raw materials for wet tissues.

<6> There are basically two ways to manufacture the non-woven fabrics; they are immersion method and dry method. The immersion method is same as sheet forming method to making paper product that spread synthetic resin binder on the fabrics and drying and heating. The dry method is erupt synthetic resin on the fabrics like a cotton sheet and heat and drying.

<7> There are Non-woven fabrics of Chemical bonding type, Thermal bonding type, dry/ wet type including Air Ray non-woven fabrics , Needle punching type, Melt Blown type and Stitch type depending on manufacturing process. <8> The chemical Bonding type of Non-woven fabric is being manufactured through drying process by having adhesives penetrate into fabrics while web bonding.

<9> And there are two ways to manufacture non-woven fabrics depending on how to make the adhesives penetrate into fabrics: one is sediment adhesion method which is to penetrate by dipping, and the other one is Spray method which is to spray the adhesives on to fabrics. The non-woven fabrics using sediment adhesion method are OB type, CB type and MB type.

<io> The proper fibers to do Chemical bonding are Viscose Rayon, Polyester and blended fibers of Viscose Rayon and polyester. According to the manufacturing method of chemical bonding, the shapes and features of the non- woven fabrics can be differ per the adhesives used for web formulation. The adhesives include soluble types and non-soluble, soft types and hard types.

<π> Non-woven fabrics with the chemical Bonding method can be manufactured in many different ways per its production process, fabrics and adhesives, and it has variety and wide applications such as for automobile, Electronics, internal use for Electronics products, Filters, Adhesive tapes, Civil engineering and cleaner as industrial application and artificial flowers, general pacing materials, medical adhesive tape and cosmetics mask pack as general applications.

<i2> Non-woven fabrics of the thermal bonding method is being manufactured by mixing raw materials of PolypropyleneCP.P.) which is flammable at low temperature, and melt it by heat or pressure and combine fibrous tissue and form the Web. This method is being used to produce lower weight non-woven fabrics.

<i3> There are Polypropylene (PP), Blended Yarn (Polyester +PE, PP+PE, Polyester+PP) , Viscose Rayon and Polyester as fabric raw materials for Thermal Boding type of Non-woven Fabrics. As the Viscose Rayon itself is impossible to form the Web, Mix with Polypropylene or Blended fibers.

<i4> Such Thermal Bonding type Non-woven fabrics are lower in tensile strength but has soft touch-feeling, superior absorptiveness, adhesive is not required, form the Web by heat which does not generate harmful materials. When the blended fiber is used, it has superior adhesive property by heat, and therefore, it is being widely used for baby diapers, sanitary diapers, sanitary masks, Wet tissues and Wipers.

<15> Span bond type non-woven fabric is being manufactured by for the Web with pressure after melting and spraying the fabric chips. Mainly Polyester and Polypropylene are being used as material chips and sometimes Nylon is also used.

<i6> Span bond has the advantage of tensile strength is higher and superior in durability and chemical resistance while it has lower tensile strength because it is filament that does not stop from the starting point to the end in production without cut. It is being used for industrial applications such as interior material for automobiles, Filter, Cable protector, Civil Engineering, Agricultural and Coating, and packing material for flowers, basic wall papers, packing materials, Beds and furniture and printing materials as general industrial applications.

<i7> As Air-ray type of Non-woven fabric is being manufactured with Compressed air and adhesives, there is no difference in tensile strength of parallel and horizontal direction.

<i8> It is being used as Filter, wick, carpet, forming agent, Wipers (rug, dishcloth, towel) and insulation materials.

<i9> Wet Non-woven fabrics use the same manufacturing process as paper manufacturing which is sheet forming method. The difference is that it does not use pulps as materials but uses other fabrics which allow free control of its specification, and being used for Wipers, Towel, Filter bag and cover of Diapers.

<20> Needle-punching type non-woven fabrics are manufactured with special needles to form the web which enables to vary its thickness of the products with number of punching and density of needles. It is applied to Carpet, Blanket, Filter, wick coating agent.

<2i> Span-ray non-woven fabrics are manufactured by spraying high pressure water to the fabrics to form the web. Viscose Rayon, Polyester, Polypropylene as itself or blended are used as raw materials. As the products is good in flexibility, breath-ability and hygienic, it is used for Medical wick, household items, Coating agent, roofing materials, wiper and sanitary products.

<22> Specially, as the Span-ray non-woven fabrics have soft-touch feeling, superior absorptiveness of water, superior cleaning function and form web with water, its manufacturing process is hygienic, and therefore it is used mainly for sanitary products such as Wet Tissue, Wiper and cosmetic mask pack.

<23> Melt blown type non-woven fabrics are manufactured by weaving blended high molecule to get ultra thin yarn with high compressed heat and form the web. With its superiority of flexibility, permeability and insulation, it is used for Filter, Insulation materials, Wipers, Oil absorbing sheet and sanitary napkins.

<24> And as the Starch bond type non-woven fabrics do not use adhesives but quilting method, it is thin but high tensile strength and it is used mainly for wick and interior materials for automobile.

<25> The other hands, the general wet tissues are manufactured to clean the body partially by adding specially prepared water to cottons or pulps or some of above-mentioned non-woven fabrics (i.e. thermal bonding type non-woven fabrics and etc.).

<2β> Moisturizer and surfactant are generally added to specially prepared water for wet tissue to produce wet tissues. And those wet tissues use chemical preservatives, alcohol and perfumeries to protect contamination of the wet tissues, possible changes of the characters of the materials added and to lessen the bad smells. <27> The chemical preservatives are Benzoic acid, Sorbic acid, Methylparaben, Ethylparaben, Propylparaben, Butylparaben, 3-iodo-2-propynyl butyl carbonate, 4-thiazolyl-benzimidazole, 2-(4- thiazolyl)- benzimidazole, benzalkonium chloride, polyvinyl Butyral, deiodinemethyl , p- tolyulfanilatnide,2.4.5.6-tetrachliro-iso-butyno-nitryl, p-hydroxybenzoate.

<28> All of those materials are skin irritator and may generate skin problems, and it has high possibility to be accumulated to the body of kids who are weak in resistance and it can be the reason for atopic skin problems.

<29> Again, those types of additives which are chemical preservatives contained in wet tissue can generate irritation to the skin or harmful to human body.

<30> Further, antimicrobial materials and alcohol generate bad smell that gives bad feeling.

<3i> Even though the antimicrobial materials and alcohol are added to wet tissues, there is still high possibility for the bacteria and fungus to be increased in the closed containers because the moisturizer, plasticizer, antioxidant, adhesive agents which are the additive materials for non-woven fabrics (PET, PP, PE, Nylon, Viscose rayon, Pulp, Cotton) become nutritive elements to microorganism in the container where the proper temperature is maintained and Ultraviolet rays is blocked.

<32> Further, there is high possibility for the bacteria to be increased and fungus is generated during the manufacturing and distribution process if the non-woven fabrics as raw material for wet tissues are contaminated, and therefore, the chemical preservatives are used. However, as a specific chemical preservatives is not able to cover all different bacteria, it is fact that at least 2-3 different kind of chemical preservatives of large quantity need to be used, total 3,000-6,000ppm in general.

<33> Accordingly, considering that the chemical preservatives has strong possibility to raise skin problem if it is added to the specially prepared water for wet tissue to kill fungus, using nano silver as a replacement to chemical preservatives to kill fungus are being seriously considered. <34> For an example, Korean Laid-Open Patent No. 10-2006-1758 shows that Silver colloid as antimicrobial material solved color change problem to yellowish and black and it has antimicrobial effect. It also described on the technology to apply it for Wet Tissues with Silver Colloid of smell-less and harmless to human body.

<35> According to the technology of the above-mentioned Korean Laid-Open Patent No. 10-2006-1758, after forming lOOppm of nano silver Colloid in the first process, mix about 1 ppm of sodium hypochlorite into this colloid as catalyst in the second process, 150ppm of nano silver colloid in the first process, mix calcium carbonate as catalyst into the out-put of the second process to get silver colloid of pH8.5 by melting the calcium carbonate in the third process, mix sodium acetate into the out-put of the third process to control to get pH7.5 in the fourth process, produce antimicrobial silver colloid of unchangeable color by filtering silver compound and then, produce wet tissue of unchangeable color to yellow by dip the wet tissue materials into the silver colloid in the last process.

<36> The above-mentioned process shows that it solved the problems of color changes caused by halogen compound and mineral ingredients or lye and other toxic materials to use it as antimicrobial materials to white wet tissues. In the first process, put chlorine (halogen material) into silver colloid and have it react, and compounding calcium carbonate to yellowish color to make the pH weak alkali.

<37> Further, it describes that transparent silver colloid can be made through filtering the floating particles of transparent white color which are formed by neutralization with nitric acid soda.

<38> However, regardless of its reality, it concentrates on protecting against color changes to yellowish to produce wet tissue. It does not contain enough technical information on the optimistic size of solid silver to control and get rid of fungus.

<39> The technical explanation to produce wet tissue with specific silver colloid produced through the 1st -5th process is rather limited, and there is n definition if such silver colloid is ion or metal which gives us doubts antimicrobial efficacy, effects against fungus and its durability. If that is ion, it can be easily combined to other materials which may be remained in the raw fabric and treated water of wet tissue, and it is hard to expect its durability.

<40> The above-mentioned manufacturing method of wet tissue is the technology which make difficult to estimate the durability after open the pack and overall validity of the products but simply considers how to provide antimicrobial function to treated water for wet tissues.

<4i> As an another example, Korean Laid-Open Patent No. 10-2006-95685 provides the method of protecting the propagation of microbes by wetting the wet-tissues into nano silver contained water in the manufacturing process of wet tissue and the method how to eliminate the microbes effectively by transferring the harmless nano silver materials to the hands of customers.

<42> According to the method, it is required to mix nano silver treated water of 25-150ppm to wet-tissue which is formed with compound of nano silver treated water, surfactants, anti-fungus materials and preservatives to papers and fabrics.

<43> However, the above-mentioned Korean Laid-Open Patent No. 10-2006-95685 describes that anti-fungus materials need to be added besides nano silver treated water used for antimicrobial function. But it has no definition on the size of nano silver particles of the nano silver treated water used but only concentration level only. This can be the case only when the nano silver is added as supplements for antimicrobial function while anti-fungus materials and preservatives are also used.

<44> As notices, the nano-sized silver particles shows its antimicrobial and anti-fungus functions by energy of the surfaces with increased surface area, the technology is rather unclear and has practical problem to apply with only limited concentration level unless it explains clearly about the particle sizes. It emphasizes only on adding antimicrobial function instead of anti- fungus function limited to manufacturing water in the wet tissue manufacturing process.

<45> As an another example, Korean Laid-Open Patent No. 10-2006-110952 suggests functional wet tissue that eliminates accumulated heavy metals from the skin, activate cells and have the functions of smoothing blood circulation, hygienic, superior safety to the skin and antimicrobial and antifungal functions against microbes stays on the skin by adding polyglucosamine, ceramic liquid, lotion, aloe and vitamin to nano silver material treated Span lace which is natural pulp.

<46> According to the above-mentioned Korean Laid-Open Patent No. 10-2006- 110952, it is to mix 30-35 weight(wt)% of Span lace, nature pulp material to mixed water of 63-69 wt% with nano silver powder of 1-2 wt%. This nano silver power must be either 10-lOOppm in concentration with 1-lOnm in size or nano silver coating powder (capsule type) of 10-lOOppm in concentration with 100-200nm in size. And mix 0.2-0.4 wt% of polyglucosamine and 0.6-0.8 wt% of liquid ceramic into above liquid and add 1-2 wt % of at least two kinds of mixture of lotion, aloe and vitamin or one of them.

<47> However, the technology is limited to apply nano silver powder or nano silver coated capsule and it has some difficulties to execute and apply it to keep anti-fungus function with 1-lOOppm concentration of nano silver itself alone a the concentration level is not sufficient.

<48> In fact, the most serious problem of contamination during the manufacturing process and usual contamination of the fabrics for wet tissue is Aspergillus Niger. It has been already proved through a few experiments that it is not possible to protect or eliminate the Aspergillus Niger by silver alone under the circumstances in the wet tissue pack with nano particle of 1-lOnm with lOOppm concentration.

<49> An early experiment has been carried out and proved that 150-200ppm concentration is required to use nano silver alone for tissue manufacturing water.

<50> Further, it still has possibility to have color change into yellow by reacting with UV or form precipitates by reacting with remaining sulfides in the fabrics.

<5i> And, it has been confirmed a few times through experiments that 2-4 times of concentration level of 200ppm are required to keep anti-fungus function as the energy value is decreased per surface size with nano silver of 10-lOOnm size.

<52> As the technology to use it after coating the nano silver particles to the surface of the particles or put the particles into the capsule, it has high possibility to offset its surface energy which reacts on the surface of nano silver particles.

<53> This is the basic difference technology in antimicrobial and anti- fungus efficiency from the technology which utilizes the technology of surface energy itself of uncoated nano particles of metals of not only silver but also platinum, gold, copper, zinc and selenium.

<54> And, even though we assume that all the contents of technology in the above-mentioned Korean Laid^~0pen Patent No.10-2006-110952 are proper, it uses powder or capsule type of silver only, it has high possibility of color changes and color contamination. It is limited to only to use for manufacturing water for wet tissues, not considering antimicrobial and anti- fungus treatment to non-woven fabrics and pulps.

<55> According to Korean Patent No.10-0693293 suggested by the inventor, it is featured to use below IOnm particle size to produce preservatives-free cleaning wet tissue which has antimicrobial and deodorizer functions using nano particles of metals or to use l-2nm nano silver particles to minimize the quantity to be used. The quantity to use is 50-100ppm concentration when the particle size of below IOnm is used, and 0.4-lppm concentration is used with l-2nm particle size.

<56> In the above-mentioned patent, Nano silver is used for manufacturing water of tissues only. However, the reject rate (fungus incidence) came to 1- 5% in practical repeated mass production.

<57> 10,000packs each were produced 3 times in year of 2006, the Aspergillus Niger were found and confirmed from average min. 100 packs to max 500 packs out of each lot in 7-30 days during storage and distribution period. It is confirmed that the Aspergillus Niger were grown 50% by contamination of non- woven fabrics, 30% by contaminated manufacturing process, and 20% by other factors.

<58> This indicates that there are different levels of sanitary environmental conditions contamination levels between the manufacturers and there are limitations to maintain sanitary manufacturing process which is required to manufacture wet tissues with non-woven fabrics.

<59> It is difficult to produce good antimicrobial and antifungal wet Tissue with the above-mentioned patente technology by mixing nano silver into tissue manufacturing water to provide antimicrobial and anti-fungus functions to the wet issue because the non-woven fabrics itself as raw materials can be contaminated during its manufacturing, distribution and handling process or possibility of spores in the air stick to the non-woven fabrics which can be the factor for bacteria or fungus to increase.

<60> Considering this contamination problem of non-woven fabrics, the technology to provide antimicrobial and deodorizer functions to the non-woven fabric itself has been suggested.

<6i> As examples, Korean patent No. 10-643515 introduces polypropylene span- bond type non-woven fabrics and its manufacturing technology which solves the problems of human beings and environment caused by using improper antimicrobial and deodorizer chemicals, increases economical efficiency for the necessity of drying process against moisture absorption and work efficiency against increased pressure raised by uneven dispersion in the polymer and problems of cut-thread and provide antimicrobial and deodorizer functions not to allow the virus, bacteria and fungus to inhabit.

<62> According to the Patent, it is produced with pure metallic nano silver particles of l-3nm level combined with silica particles of below lnm and polypropylene and the added quantity of nano silver is to be 10-l,000ppm of total polypropylene resin of Polypropylene span bond non-woven fabric, Melt blown span bond multilayer non-woven fabric, using the prefabricated master batch chip contains 0.01 ~ 10wt% of nano silver and the added quantity of nano silver is to be 10-l,000ppra of total polypropylene resin of polypropylene span bond non-woven fabric or polypropylene span bond, Melt blown span bond, multilayer non-woven fabric, polypropylene chip have 20 ~ 80g/10min Melt Flow Rate(MFR) as a main raw material through the melt, mix, homogenize on the extruder, melt spinning through the spinneret, formed filament after cooling, drawing, formed web on the porous conveyer belt, move to the calendar for heating bond process and then they have stability of formation.

<63> According to the above-mentioned Patent No.10-643515, silica of below lOnm is combined to silver of l-3nm level; however, there is no description on the detail method of it. Though we assume this is the case silica is used as inclusion body as usual, the silica particles do not require the inclusion body except a special case. The abovementioned technology may reach the result of decreasing the increased energy with increased surface of nano particles because the surface area is decreased if silver particles of the pure metal are contained in the inside of silica, inclusion body.

<64> The way to combine silver and silica without using silica as inclusion body becomes the decisive factor of cut in spinning process regardless of it is used as binder to be coupled.

<65> And, crushing the inorganic silica with physical method, it can be just lOnm level under the current technology level due to the manufacturing technology of related crusher, tolerance in process and related materials.

<66> Accordingly, the technical explanation is different from the one that uses silver of l-3nm to non-woven fabrics directly as described because it must be considered that the nano particle size exceeds 50nra if the size of combined silica with silver is 50nm even though the silver size is l-3nm.

<67> And, if the patent describes that they use silver Ion instead of silver metal, it is common to use silica or zeolite as inclusion body for the stability, which is different from the nano technological materials and the silica must be foreign materials to polypropylene as it is used together with silica for stability even though it uses silver metal. Accordingly, if we compare it to the case of mixing nano silver particles into thermostatic plastic resin, the productivity (increase of pressure in the cylinder, wear out of screws and nozzles) and reliability (tensile strength, shrinking rate, stain ability and etc.) may not be enough.

<68> And, the above-mentioned Korean patent No.10-643515 describes the manufacturing method of non-woven fabrics with nano silver particles by mixing to polypropylene materials only.

<69> It does not describe on the manufacturing method of non-woven fabrics that use Viscose Rayon and polyester or others as raw materials for the fabrics. [Disclosure] [Technical Problem!

<70> This invention has been made considering the past technology and its first objective is to provide a manufacture method of antimicrobial and anti- fungus wet tissues by mixing non-woven fabrics of less contamination level or cotton fabrics or papers into antimicrobial water which contain nano particles of either one of platinum, gold, silver, germanium, selenium and zinc or more than 2 of selected metals.

<7i> The second objective of this invention is to provide a manufacture method of antimicrobial and anti-fungus wet tissues with non-woven fabrics which already have antimicrobial and anti-fungus functions by adding nano particles of either one of platinum, gold, silver, germanium, selenium, zinc, copper and tungsten or more than 2 of selected metals, and, mix this fabrics material into distilled water of purified water so that the wet issue can have optimistic level of antimicrobial and anti-fungus function.

<72> The third objective of this invention is to provide a manufacture method of antimicrobial and anti-fungus wet tissue by mixing nano particles of one or one metals of gold, platinum, silver, germanium, selenium, zinc, copper and tungsten into fabric materials such as viscose rayon, polyester, polyethylene, polypropylene, cotton and pulp to have those fabrics itself antimicrobial and anti-fungus function, and mix this treated fabrics into antimicrobial and anti-fungus water prepared by mixing one or one metal particles of gold, platinum, silver, germanium, selenium and zinc so that both of fabrics and water have antimicrobial and anti-fungus functions. [Technical Solution]

<73> According to this invention, to achieve above objectives, the 1st objective provides the manufacture method of antimicrobial and anti-fungus wet tissue with selected non-woven fabrics of blended one or one materials of viscose rayon, polyester, polyethylene, and polypropylene or cotton or pulp by mixing into antimicrobial water which contains nano metal particles of one or more than one of platinum, gold, silver, germanium, selenium and zinc.

<74> According to the second objective of this invention, the manufacture method of antimicrobial and anti-fungus wet tissue comprises a step of forming the antimicrobial and anti-fungus fabrics by mixing one or more that one metal nano particles of platinum, gold, silver, germanium, selenium, zinc, copper and tungsten into blended fabrics of one or more than one out of viscose rayon, polyester, polyethylene, polypropylene, cotton and pulp, and a step of fabricating antimicrobial and anti-fungus tissue by dipping the antimicrobial and anti-fungus fabrics into distilled water or purified water.

<75> According to the thidd objective of this Patent, it provides the manufacturing method of antimicrobial and anti-fungus wet tissue with selected antimicrobial and anti-fungus fabrics which is formed with one or more than one nano metal particles out of gold, platinum, germanium, selenium, zinc, copper and tungsten and antimicrobial water which contains one of more than one of metal particles out of gold, platinum, germanium, selenium, zinc, copper and tungsten.

<76> According to this patent, in the above-mentioned viscose rayon manufacturing process as fabric materials, one or more than one nano metal particles out of germanium, selenium, zinc, copper and tungsten are added before spinning of rayon yarn, and process with master batch chips or compounding chips produced by mixing one or more than one nano metal particles out of above mentioned gold, platinum, silver, germanium, selenium, zinc, copper and tungsten with thermostatic plastic resin into above mentioned polyester, polyethylene and polypropylene.

<77> And then, spin the master batch chip treated materials after mixing 3- 10% ratio into its raw materials or spin 100% of treated compounding chips.

<78> Above cotton is dipped into above mentioned nano metal contained liquid or mixed spin with the nano metal particles.

<79> And the nano metal particles is mixed into water for dispersion process of pulp materials, or mix above nano metal particles into adhesive agent which is used in the process of pulp to have certain thickness and form, or it is mixed with the method of spraying above nano metal particles after the pulp is formed as fabrics. [Advantageous Effects]

<80> As described in above, According to the manufacturing method of antimicrobial and anti-fungus tissue based on this invention, the fist example can provide enough antimicrobial and anti-fungus efficiency without color changes for long time as it is manufactured hygienical Iy with antimicrobial and anti-fungus water and one or more than one of nano metal particles of gold, platinum, silver, germanium, selenium and zinc into non- woven fabrics or cotton fabrics or pulp which are relatively less contaminated.

<8i> In case of the second example, as there are still possibility for the non-woven fabrics to be contaminated and infected during the manufacturing process, transportation and warehousing, and the non-woven fabrics can be the place where the organic materials contained in the wet tissue can be the feeds to bacteria and fungus to live, the increase of bacteria and fungus from wet tissues can be inhibited for long period by dipping antimicrobial and anti-fungus non-woven fabrics into distilled water or purified water after providing antimicrobial and anti-fungus function to raw fabrics of textile materials by mixing one or more than one of nano metal particles out of gold, platinum, silver, germanium, selenium and zinc. <82> And according to the third example, as the antimicrobial and anti- fungus function is achieved by dipping antimicrobial and anti-fungus textile fabrics of viscose rayon, polyester, polyethylene, polypropylene and cotton which was mixed and formed the web with one or more than one of nano metal particles out of gold, platinum, silver, germanium, selenium, zinc, copper and tungsten into antimicrobial and anti-fungus water which one or more than one of nano metal particles out of gold, platinum, silver, germanium, selenium and zinc, the propagation of microbes which cause the contamination are inhibited from the manufacturing process of non-woven fabrics as textile fabrics, and it is also possible to inhibit the increase of bacteria and fungus even though there are organic materials from the materials contained in wet tissues.

<83> Therefore, it is possible to manufacture multi-function wet tissue that both of customers and manufacturers want regardless of additive raw materials as it protects even the functional additives of skin-beauty and moisturizer functions from being the feeds to bacteria and fungus.

<84> As the antimicrobial and anti-fungus function is added to both of raw fabrics and manufacturing water for tissue in the third example, it is possible to manufacture cheaper but high stability wet tissues by reducing 30-50% in concentration level of nano metal particles comparing to apply it to one of method of either raw fabrics or manufacturing water for tissue even though individual concentration level is different.

<85> Accordingly, this invention considers contamination level of the fabrics (non-woven fabric), hygienic level of its manufacturing process and the contents of the organic additives which are being used to manufacture wet tissues. It is possible to use nano metal particles to either non-woven fabrics or manufacturing water for wet tissue to manufacture wet tissues under this invention. Or, it is possible to use the nano metal particles to each of these one materials (fabrics and water) separately.

<86> And it is possible to control different mixing ratio and quantity of nano metal particles for wet tissue per its fabric materials and water for tissue as shown in the above-mentioned examples 1,2 and 3. <87> As the wet tissues manufactured with this invention does not use chemical preservatives which can give irritation to skin, it can provide of less irritation to skin of human-being as well as it minimizes the skin irritation and provides safety wet tissues as the chemical preservatives are not used even when many other additives of moisturizer and natural organic materials are added to manufacture multi function wet tissues.

[Description of Drawings] <88> Figure 1 is a TEM(Transmission Electron Microscope) picture of Platinum

Nano metal particles applied to manufacturing antimicrobial and anti-fungus wet tissue according to this invention. <89> Figure 2 is a TEM picture of Gold nano metal particle applied to this invention. <90> Figure 3 is a TEM picture and its distribution chart of Silver nano metal particle applied to this invention. <9i> Figure 4 is a TEM picture of Copper nano metal particle applied to this invention. <92> Figure 5 is a TEM picture of Zinc nano metal particle applied to this invention. <93> Figure 6 is a TEM picture of Germanium and Selenium nano particles applied to this invention. <94> Figure 7 is a TEM picture of Selenium nano particle applied to this invention. <95> Figure 8 is a TEM picture of Gold Tungsten(Wolfram) metal particle applied to this invention. <96> Figure 9 is a SEM(Scanning Electron Microscope) picture of Germanium and Selenium nano particles that shows the mixtures with Viscose Rayon as non-woven fabrics materials to manufacture wet tissues under this invention. <97> Figure 10 is a SEM picture of silver as nano metal particles of mixed spin yarn with polypropylene under this invention. <98> Figure 11 is a SEM picture of silver as nano metal particles of mixed spin yarn with polyester under this invention.

<99> Figure 12 is a SEM picture of Silver nano metal particles added to Viscose Rayon yarn. [Best Mode]

<ioo> Now, preferred embodiments of this invention will be described in detail with reference to the accompanying drawings(that is, pictures).

<ioi> At first, according to the first embodiment of this invention, it applies to tissue manufacturing water of antimicrobial and anti-fungus function in tissue fabric with nano metal particles to guarantee antimicrobial and anti-fungus effects without chemical preservatives or antimicrobial and anti-fungus materials to manufacture wet tissues with raw tissue fabrics which have certain measurement, tensile strength and flexibility.

<iO2> Hopefully, the Tissue Fabrics applied to the first embodiment of this invention does not limit to only non-woven fabrics of less contamination possibility of bacteria infection caused by external or internal reasons during its manufacturing process, distribution and warehousing but includes also cotton fabrics and pulps.

<1O3> According to the first embodiment of this invention, the nano metal particles mixed to tissue manufacturing water to have antimicrobial and anti- fungus functions include one or more than one of selected mixtures out of platinum, gold, silver, germanium, selenium and zinc.

<iO4> Referring to Figure 1, the nano metal particles applied to this invention to provide antimicrobial and anti-fungus functions, the Platinum (Pt: refer to TEM picture of Figure 1) has the function of antimicrobial and deodorizer and recognized widely as functional catalyst. In this invention, particle size of l-50nm with final concentration level of 0.00001- 0.0005wt%(0.1-5ppm) of the weight to tissue manufacturing water is used.

<i05> The Gold (refer to TEM picture of Figure 2) out of the above-mentioned nano metal particles have not only antimicrobial function but also inhibitive action against aggregation of nano particles by direct contact, coupling and aggregation. In this invention, particle size of l-30nm with final concentration level of 0.00001-0.001 wt%(0.1-10ppm) is used.

<iO6> And, the Silver (refer to Figure 3, TEM picture and distribution chart) as nano metal particles applied in this invention provides antimicrobial and anti-fungus function and particle size of l-20nm with final concentration of 0.0001-0.002wt% (l-20ppm) to weight of tissue water.

<iO7> According to this invention, as the nano silver particles may cause color contamination if it reacts to ultra violet light, or it can be aggregated or precipitated if it reacts to remaining sulfides which is used in the manufacturing process of viscose rayon yarn, it is recommended to minimize to use 0.00001-0.002wt%(0.1-20ppm).

<i08> As the Zinc (refer to Figure 5, TEM picture) out of nano metal particles applied to this invention shows antimicrobial effect at 30ppm and anti-fungus effect with above 300ppm, this invention is using the zinc of 1- 5nm particle size with final concentration of 0.003-0.03wt%(30-300ppm) to tissue manufacturing water.

<iO9> The Germanium (organic germanium: refer to TEM picture of Figure 6) as nano metal particles were proved through experiment that it has functions of inhibiting increase of spore of mushrooms and fungi.

<πo> According to this invention, germanium of l-50nm particle size with final concentration of 0.0001=0.01wt%(1-lOOppm) to weight of tissue manufacturing water is used.

<iπ> The Selenium (refer to TEM picture of Figure 7) as nano metal particles applied to this invention has been proved through experiments that it shows antimicrobial effect against spore of fungus bacteria with below 50ppm.

<ii2> According to this invention, selenium of l-50nm particle size with final concentration of 0.0001-0.01wt%(l-100ρρm) to the weight of tissue manufacturing water is used.

<ii3> [Table 1] <114>

<115>

Referring to the table 1, the hydrogen peroxide (H₂O₂) (Z) is mixed of into tissue manufacturing water which one or more than one of nano metal particles out of platinum, gold, silver, germanium, selenium and zinc is mixed. Hopefully, mix the hydrogen peroxide to be its concentration 10-450ppm (0.001-0.045%).

<116> It is to minimize the color change problem, by having the oxygen (O₂) of hydrogen peroxide (H₂O₂) react, in tissue fabrics caused by aggregation or reaction of nano particles in the tissue manufacturing water.

<117> The total concentration of the nano metal particles of the above- mentioned platinum, gold, silver, germanium, selenium and zinc does not exceed 0.01wt% (lOOppm) of tissue manufacturing water for wet tissue when more than one of those are mixed into tissue manufacturing water. This is because it can provide enough antimicrobial and anti-fungus effects with maximum concentration of 0.01wt% (lOOppm) even though more than one of the above-mentioned nano metal particles are mixed with mixing rate of any combination.

<118> Among the above-mentioned nano metal particles mixed into tissue manufacturing water applied to the example 1, the nano platinum particles include chemical compound of platinum, the material obtained from the basic raw materials; [Ammonium hexachloroplatinum(IV); (NEt)₂[PtCIe] , Diamine

Dinitritoplatinum( II ) !Pt(NO₂MNHa)₂, Hexachloroplatinum(IV)acid hydrate !H₂(PtCl₆) ^• 6H₂O, Hexahydoxoplatinum(IV)acid;H₂Pt(0H₆)_I Platinum acetylacetonate;Pt(C5H7O₂)₂₎ Platinum chloride;PtCl, PtCl₂, PtCl₄, Platinum iodide;PtI₂, Platinum oxide;PtO, PtO₂, Pt₂O₃, Platinum sulfide;PtS₂] by dissociation and reduction of ion to extract metal platinum from the selected materials and platinum nano particles formed by crushing the platinum into small pieces with physical impact.

<H9> The nano particles of platinum extracted from above-mentioned chemical compound of platinum include the one obtained by dissociation and reduction of ion to extract metal platinum with surfactant as liquid, the one gained through the stabilization with one out of silica, zeolite and phosphoric zirconium as a carrier after extracting metal platinum by dissociation and reduction of ion from chemical compound contained platinum and the one gained through gamma ray after melting the chemical compound of platinum with high molecule stabilizer into water or non-water solvent and purge nitrogen after irradiating gamma ray.

<i20> Above nano particles of gold include chemical compound of gold; [Gold sulfide ; AU2S, Gold hydroxide i AuOH, Au(0H)3, Gold iodide ,' AuI, Gold oxide

; Au2θ,Au₂θ3, Gold oxide hydrate ; AU2O3 ^• xH₂0, Gold chloride ; AuCl, AuCl₃, Gold chloride trihydrate ; HAuCl₄ ^• 3H₂O] gained through dissociation of selected materials from raw materials with pure water, ethanol and Isopropyl alcohol and reduction of ion to extract gold metal, and gold particles formed after crushing into small pieces with physical impact.

<i2i> Above gold nano particles from chemical compound of gold include the one manufactured with gold extracted by dissociation and reduction of ion from chemical compound contains gold with water as surfactant, the one gained through the stabilization with one out of silica, zeolite and phosphoric zirconium as a carrier after extracting metal platinum by dissociation and reduction of ion from chemical compound contained gold and the one gained through gamma ray after melting the chemical compound of gold with high molecule stabilizer into water or non-water solvent and purge nitrogen.

<i22> Above silver nano particles include the one manufactured with the selected materials from basic raw materials of the metal salt and its chemical compound [Silver nitrate ;AgN03, Silver chloride ; AgCl, Silver chlorate ; AgClOa, AgClO₄), Silver sulfate ; Ag₂SO₄, Silver sulfite ; Ag₂SOs, Silver sulfide ; Ag₂S, Silver acetate ; CH₃COOAg, Silver selenide ; Ag₂Se,

Silver citrate hydra ;Ag02CCH2C(0H)(C02Ag)CH2C02AgxH2], the one crushed silver particles in small pieces by physical method and the one manufactured by electrical explosion.

<i23> Above Silver nano particles include the one manufactured with silver extracted by dissociation and reduction of ion from chemical compound contains gold with water as surfactant, the one gained through the stabilization with silica, zeolite and phosphoric zirconium as a carrier after extracting metal silver by dissociation and reduction of ion from metal salt and chemical compound contained silver, and the one gained through gamma ray after melting metal salt and chemical compound with high molecule stabilizer into water or non-water solvent and purge nitrogen.

<i24> The silver nano particles of the above-mentioned chemical compound of silver manufactured with nitrogen silver (AgNO₃) are the colloidal silver particles which Nitrogen (NO₃) radicals, counter ion against silver ion generated during the production of silver particles, are eliminated by passing through ion exchange resin or vacuum distillation method.

<125> Above zinc nano particles include the one manufactured by dissociation of selected material from the basic raw materials of chemical compound of [Zinc acetate ; (CH₃CO₂^Zn, Zinc acetate dihydrate ; Zn(CH₃COO)₂ ^• 2H₂O, Zinc acrylate ; (H2C=CHC0₂)2Zn, zinc chloride ; ZnCl₂, Zinc iodide ; ZnI₂, Zinc phthalocyanine ; C₃₂HIeNgZn, Zinc selenide ; ZnSe, zinc sulfate ; ZnSO₄, Zinc sulfide ; ZnS, Zinc 29/Sl/Hetrabenzol [b,g,l,q] porphyrin ; C₃6H₂0N4Zn] and reduction of ion to extract metal zinc, and the one manufactured by electrical explosion.

<i26> Above zinc nano particles include the one manufactured with zinc extracted by dissociation and reduction of ion from chemical compound contains zinc with water as surfactant, the one gained through the stabilization with one of silica, zeolite and phosphoric zirconium as a carrier after extracting metal zinc by dissociation and reduction of ion from chemical compound contained zinc, and the one gained through gamma ray after melting chemical compound with high molecule stabilizer into water or non^¬ aqueous catalyst and purge nitrogen.

<127> Above germanium nano particles include the one gained by extracting germanium metal by dissociation and reduction of ion from the selected materials from basic raw materials [Germanium chloride; GeCU, Germanium chloride dioxane complex; C₄H₈CbGe(^, Germanium fluoride GeF₄, Germanium iodide; Gel2, GeI₄, Germanium isopropoxide; Ge(0CH(CH₃)₂)3, Germanium methoxide; Ge(OCHs)₄, Germanium nitride; GesN₄, Germanium oxide; Geθ2, Germanium selenide; GeSe, GeSβ2, Germanium sulfide; GeS, the one of organic germanium compound.

<128> [Table 2] <129> (Unit : ppm)

<130> Division (DViscose ©Poly(S)Po Iy- ©Po Iv^¬ ©Cotton ©Pulp <132> -ravon ester ethvlene or opv lene

Pt 0. 5~30 0. 5~30 0 5~30 0 5~30 0 5~30

Au 0. 5~50 0. 5^~50 0 5^~50 0 5~50 0 5~50

Ae 5^' ^"200 5^" ^"200 5 ^~200 5 ~100 5 ~100 je l^~300 1^" ^"300 1^" ^"300 1 ^~300 1 ~300 1 ~300

Se l~100 V ^"100 1^" ^"100 1 ~100 1 ~100 1 ~100

Zn 30 ~ 1.000 30 ~ 1.000 30 ~ 1.000 30 ~ 1.000 30 ~ 500 30 ~ 500

Cu 10 ~ 200 10 ~200 10 ~200 10 ^~200

10-300 10 -300 10 -300 10- -300

According to the table 2, the nano metal particle size mixed to provide antimicrobial and anti-fungus functions under the second embodiment of this invention is l-50nm of platinum(refer to TEM picture of Figure 1) and the final concentration is 0.00005~0.003wt%(0.5~30ppm) to the weight of wet tissue fabrics(non-woven fabric).

<134> The nano metal particle size of the above-mentioned gold (refer to the TEM picture of Figure 2) is l-30nm and the final concentration is 0.00005~0.005wt%(0.5~50ppm to the weight of wet tissue fabrics(non-woven fabrics).

<i35> And, the size of nano metal particles of silver (refer to TEM picture of Figure 3) is l-20nm and the final concentration is 0.0005-0.02wt%(5~ 200ppm) to the weight of wet tissue fabrics(non-woven fabrics).

<i36> The size of nano metal particles of the above-mentioned copper (refer to TEM picture of Figure 4) is l-50nm and the final concentration is 0.001~0.02wt%(10~200ppm) to the weight of tissue fabrics(non-woven fabrics).

<i37> The size of nano metal particles of the above-mentioned zinc (refer to the TEM picture of Figure 5) is l-50nm and the final concentration is 0.003-0. lwt%(30 ~ l,000ppm) to the weight of tissue fabrics(non-woven fabrics).

<i38> The size of nano metal particles of the above-mentioned germanium (Organic germanium, refer to the TEM picture of Figure 6) is l-50nm and the final concentration is 0.0001~0.03wt%(l~300ppm) to the weight of tissue fabrics(non-woven fabrics).

<i39> The size of nano metal particles of the above-mentioned selenium (refer to the TEM picture of Figure 7) is l-50nm and the final concentration is 0.0001-0.01wt%(l~ lOOppm) to the weight of tissue fabrics(non-woven fabrics).

<i40> The size of nano metal particles of the above-mentioned tungsten(W; wolframXrefer to the TEM picture of Figure 8) is l-50nm and the final concentration is 0.001~0.03wt%(10~300ppm) to the weight of tissue fabrics(non-woven fabrics).

<i4i> According to the second embodiment, it is possible to use non-woven fabrics of nano metal particles mixed to any fabric materials of non-woven fabrics of φviscose rayon ©polyester ©polyethylene ©polypropylene (B cotton ©pulp, or mixed yarn with proper mixing ratio of each non-woven fabrics materials contained nano metal particles selectively.

<i42> However, considering the possibility of aggregation caused by reaction of nano metal particles of sulfide which is a raw materials used in the manufacturing process, platinum, gold and silver from above listed nano metal particles are not used for viscose rayon. <i43> And, considering the possibility of separation of nano metal particles from pulp and cotton materials as mixing status is not strong enough than the polymerization of nano particles and high molecule polymer in pulp and cotton, the particles of copper and tungsten are not used, which may give irritation to the skin relatively. And use reduced quantity of silver of 0.0005-0.01wt%(5~100ppm) and zinc of 0.003~0.05wt%(30~500ppm) respectively to the weight of tissue fabrics.

<i44> On the other hand, to make the nano metal particles of the above- mentioned metals to be mixed as shown in the table 2, the mixing method of one or more than one of selected nano metal particles from the above- mentioned platinum, gold, silver, germanium, selenium, zinc, copper and tungsten into the manufacturing process of ©polyester (3)Polyethylene(PE), @ polypropylene(PP) out of φviscose rayon ©Polyester ©polyethylene(PE, © polypropylene(PP) ©Cotton ©pulp is applied.

<145> According to this invention, viscose rayon is produced by adding one or more than one of selected nano metal particles from the above-mentioned germanium, selenium, zinc and copper to the side feeding process of extruder of materials just before spin the fabric materials prepared.

<i46> In other words, Viscose is manufactured by mixing and melting the cellulose compound [(CδH9θ4-OCS2Na)n] with carbon disulfide (CS2) after producing alkali-cellulose [(C₆H₉O₄-ONa)n] through dipping, pressing and pulverizing process after mixing sodium hydroxide (NaOH) into pulp. It is manufactured by spinning the selected one or more than one of the above- mentioned nano metal particles mixed in the side feeding process.

<!4?> According to this innovation, in case of not using carbon disulfide (CS₂) or using the nano metal particles produced with increase quantity of stabilizers or additives to minimize the reaction against sulfide in the manufacturing process of viscose, it is suggested to manufacture antimicrobial and anti-fungus rayon fabrics by mixing nano metal particles in the process of producing viscose as it increases the dispersibility of final rayon fabrics [(C₆HiOO₅)Ii].

<148> And according to this invention, in case of <© Cotton, the method of spin mixed with nano metal particles or the method of dipping cotton materials into the liquid contained nano particles in the manufacturing process of non-woven fabric or yarn.

<i49> For ©Pulp, the method of mixing above mentioned nano metal particles selectively into manufacturing water which is used for dispersing process of pulp materials in the pulp manufacturing process, mixing the above-mentioned nano metal particles to the adhesive agents mixed into manufacturing process of pulp to have the pulp certain thickness and shape and mixing the above selected nano metal particles by spraying nano particles after pulp is formed as raw fabrics.

<i50> And according to this invention, ©Polyester(PET), ©polyethylene(PE), (Dpolypropylene(PP), as authorized to this applicant suggested by Korean Patent No. 10-0599532 for each resin materials to be mixed with high concentration nano metal particles, master-batch chips or compounding chips are produced by mixing the selected nano metal particles of platinum, gold, silver and etc. with certain ration into thermostatic plastic resin which is raw materials for plastic products.

<i5i> Afterwards, the antimicrobial and anti-fungus yarns are produced by mixing the treat master-batch or compounding chips (3-10% of master-batch chips and 100% of compounding chips) to the raw materials and spin.

<i52> In above process, the materials of antimicrobial and anti-fungus (D viscose rayon, <2)polyester(PET), ©polyethylene(PE), (Dpolypropylene(PP), (E) cotton and ©pulp which nano metal particles are treated to selectively is used independently or as mixtures of more than one of it. And those are a lied to manufacture textile fabrics (specially non-woven fabrics) that require antimicrobial and anti-fungus functions including wet tissues as an examp1e.

<i53> And the total concentration of the nano metal particles used for final raw fabrics of wet tissues is limited not to exceed 0.1w't%(l,000ppm to the weight of wet tissue when the nano metal particles of platinum, gold, silver, germanium, selenium, zinc, copper and tungsten independently or mixture of more than one are mixed into above textile materials of φviscose rayon, φ polyester, (B)polyethylene(PE), polypropylene(PP), ©cotton and ©pulp, and the wet tissues manufactured with the textile materials independently or mixtures of more than one of each raw fabric.

<i54> This is because that the antimicrobial and anti-fungus functions become effective within the limit of 0.1wt%(l,000ppm) to the weight of non-woven fabric as the final concentration to be used even though the mixing rate is fixed with any combination when more than one nano particles are mixed.

<i55> According to the second embodiment of this invention, it is possible to manufacture antimicrobial and anti-fungus wet tissue with general tissue manufacturing water (distilled or purified water) by mixing selected one or more than one of nano metal particles of gold, platinum, silver, germanium, selenium, zinc and tungsten into textile materials to have antimicrobial and anti-fungus functions to manufacture non-woven fabrics.

<i56> Figure 10 is a SEM picture of the fiber of mixed spin of silver as nano metal particles together with polypropylene, Figure 11 is a SEM picture of the fiber of mixed spin of silver as nano metal particles together with polyester and Figure 12 is a SEM picture of the fiber of mixed spin of silver as nano metal particles together with viscose rayon based on this invention.

<157> Followings are the explanation on the manufacturing method of antimicrobial and anti-fungus wet tissues with the 3rd example of this invention.

<i58> The first embodiment is the manufacturing method of antimicrobial and anti-fungus wet tissue by dipping the non-woven fabric into tissue manufacturing water that contain nano metal particles assuming the non-woven fabric as raw textile fabric which is treated well to have antimicrobial, anti-fungus and antipollution functions.

<i59> The second example is the manufacturing method of antimicrobial and anti-fungus wet tissue is by mixing nano metal particles of antimicrobial and anti-fungus functions into non-woven fabrics as raw fabrics, and then dipping the non-woven fabrics into general tissue manufacturing water such as distilled or purified water.

<i60> Under the third embodiment of this invention, the antimicrobial and anti-fungus wet tissue is manufactured by having the nano metal particles contained into both of fabrics and tissue manufacturing water to gain better antimicrobial and anti-fungus function economically compared to the method of mixing the nano metal particles into one of non-woven fabrics or tissue manufacturing water to gain antimicrobial and anti-fungus functions as explained in the first and second embodiments.

<i6i> Again, according to the third embodiment of this invention, the first antimicrobial and anti-fungus functions are gained by mixing the nano metal particles of antimicrobial and anti-fungus to fabrics for wet tissue, and the secondary antimicrobial and anti-fungus functions are gained by having the tissue manufacturing water of antimicrobial and anti-fungus non-woven fabrics contain nano metal particles of antimicrobial and anti-fungus functions.

<i62> With the above-mentioned first and second embodiments, the enough concentration needs to be considered to manufacture wet tissues of enough antimicrobial and anti-fungus function, however, with this third embodiment, the overall concentration of 30-50% of nano metal particles which are used for tissue manufacturing water or tissue fabrics of the first and second embodiments as the nano metal particles are mixed into both of tissue fabrics and tissue manufacturing water.

<i63> According to the third embodiment of this invention, the nano metal particles to mix to non-woven fabrics as raw fabric materials and tissue manufacturing water are selected one or mixtures of one from gold, platinum, silver, germanium, selenium, zinc, copper and tungsten.

<i64> As to the above-mentioned textile fabrics, as explained in the second embodiment, the nano metal particles of one or mixture of more than one from the above-mentioned gold, platinum, silver, germanium, selenium, zinc, copper and tungsten are mixed into raw fabrics of viscose rayon, polyester, polyethylene, polypropylene and cotton.

<165> According to the third embodiment of this invention, ∑s to the non- woven fabrics to manufacture wet tissue, as the type and its ratio are decided per the mixing ration of fabrics of viscose rayon, polyester, polyethylene, polypropylene and cotton, the mixing rate of Ihe nano metal particles can be lower than the second embodiment consideri ig that it is dipped into tissue manufacturing water which already have antimicrobial and anti-fungus function.

<166> The table 3 in the below shows the mixing ratio of ihe nano metal particles mixed into above-mentioned fabrics considering the fact that the non-woven fabrics are mixed into antimicrobial and anti- fungus fabric materials contained nano metal particles.

<167> [Table 3] <168> (Unit : ppm)

<169> Division φViscose ©Poly^¬ ©Poly^¬ (DPoIy- ©Cotton ©Pulp

<171B> -ravon ester ethylene proϋvlene

Pt 0.5~10 0.5~10 0 5~10 0 5~10 0.5 ~ 10

Au 0.5~10 0.5~10 0 5~10 0 5~10 0.5 ~ 10

Ag 5~100 5~100 5 ~100 5 ~20 5~,!0

Ge 1~ 50 l~50 l~50 1 ~50 1 ~50 1~ i0

Se 1~ 50 l~50 l~50 1 ~50 1 ~50 1~ SO

Zn 30 ~300 30 ~ 300 30 ~ 300 30 ^~300 3⁽ )~200 30 ^" 200

Cu 10 ~100 10 ~ 100 10 ~ 100 10 ^~100

V 10 ~100 10 ~ 100 10 ~ 100 10 ^~100

The size of nano particles of platinum (refer to Figure 1) in the second embodiment of this invention to provide antimicrobial ; nd anti-fungus functions to tissue fabric is l-50nm and its final concentration is 0.00005-0.00lwt%(0.5 ~ lOppm) to the weight of fabrics.

<173> The nano particle size of the above-mentioned gold (refer to TEM of Figure 2) is l-30nm and its final concentration is 0.00005 -0.001wt%(0.5 ~ lOppm) to the weight of fabrics.

<174> The nano particle size of the above-mentioned silver (refer to TEM of Figure 3) is l-20nm and its final concentration is 0.0005-0.0 Lwt%(5~ lOOppm) to the weight of fabrics. <i75> The nano particle size of the above-mentioned copper (refer to TEM of Figure 4) is l-50nm and its final concentration is 0.001-0.01wt%(10 ^~ lOOppm) to the weight of fabrics.

<i76> The nano particle size of the above-mentioned zinc (refer to TEM of Figure 5) is l-50nm and its final concentration is 0.003~0.03wt%(30~300ppm) to the weight of fabrics.

<177> The nano particle size of the above-mentioned organic germanium (refer to TEM of Figure 6) is l-50nm and its final concentration is 0.0001~0.005wt%(l~50ppm) to the weight of fabrics.

<i78> The nano particle size of the above-mentioned selenium (refer to TEM of Figure 7) is l-50nm and its final concentration is 0.0001-0.005wt%(l~ 50ppm) to the weight of fabrics.

<i79> The nano particle size of the above-mentioned tungsten (refer to TEM of Figure 8) is l-50nm and its final concentration is 0.001~0.01wt%(10~ lOOppm) to the weight of fabrics.

<18O> According to the third embodiment, same or similar to the second embodiment, each fiber material of non-woven fabrics of ©viscose rayon, φ polyester, ©polyethylene, ©polypropylene, ©cotton and ©pulp that are mixed with selected nano metal particles per the ratio of the table 3, or form of compound fiber of non-woven fabric material that contained selected nano metal particles are possible to use to manufacture non-woven fabrics.

<i8i> In the third embodiment, considering the possibility of aggregation by reaction of sulfide which is the material to manufacture viscose rayon, the nano metal particles of platinum, gold and silver are not used.

<i82> And, considering the possibility of separation of nano metal particles from pulp and cotton materials as mixing status is not strong enough than the polymerization of nano particles and high molecule polymer in pulp and cotton, the particles of copper and tungsten are not used, which may give irritation to the skin relatively.

<i83> And, considering the high possibility of color change by reaction to adhesive agents of pulp, the silver particles of 0.0005-0.002wt% (5~20ppm) concentration to the weight of fabrics are used considering the fact of using antimicrobial tissue water together.

<i84> To make the above-mentioned nano metal particles mix as shown in the table 3, the mixing method of selected one or mixture of more than one from the above-mentioned gold, platinum, silver, germanium, selenium, zinc, copper and tungsten into the manufacturing process if the above-mentioned materials of φ viscose rayon, ©polyester, ©polyethylene, ©polypropylene, ©cotton and ©pulp is used.

<185> As explained in the second embodiment, viscose rayon is manufactured by adding one or more than one of nano metal particles of the above-mentioned germanium, selenium, zinc and copper to its fabric materials before spin in the adding process of raw materials to extruder.

<i86> According to this invention, in the case of that do not use the Carbon Di Sulfide(CS₂) or use the nano metal particles produced by increased quantity of stabilizer or additives to minimize the reaction against sulfide in the manufacturing process of viscose, it is suggested that the nano metal particles are mixed in the forming step of viscose, because it increases the dispersibility of nano particles of the final rayon fiber [(C6Hi_OO₅)n] .

<i87> According to the third embodiment for ©Cotton, in the manufacturing process of non-woven fabrics or spin yarn out of cotton, it is applied that the method of dipping the cotton materials into nano particles contained water or the method of spinning with mixed nano particles.

<i88> For ©Pulp, selectively mixing method of the above-mentioned nano metal particles into manufacturing water which is used for dispersion of pulp material in the pulp manufacturing process, or mixing method of the above- mentioned nano metal particles into adhesive agents which are mixed into the manufacturing process of pulp to certain thickness and shapes, or the method of having the selected nano metal particles into the pulp by spraying the nano particles after it is formed as shape of fabrics are applied.

<189> And for the above-mentioned ©polyester, ©polyethylene, © polypropylene, as suggested in the afore-mentioned Korean Patent No.10- 0599532, after producing master batch chips or compounding chips by mixing selected nano metal particles from platinum, gold and silver with certain ratio into thermostatic plastic resins, the antimicrobial and anti-fungus yarns is manufactured by mix and spin the master batch chips with ratio of 3- 10wt% to the weight of total amount resins or spin 100% of the compounding chips.

<i90> The antimicrobial and anti-fungus materials of ©viscose rayon, φ polyester, ©polyethylene, ©polypropylene, © Cotton and ©Pulp through treatment of nano metal particles selectively are used independently or as combined. For example, it can be used to manufacture fabrics for antimicrobial and anti-fungus products specially non-woven fabrics including wet t issues.

<i9i> And, the final concentration of nano metal particles of the fabric materials which use each of the above-mentioned nano metal particles of platinum, gold, silver, germanium, selenium, zinc, copper and tungsten mixed into one or mixtures of more than one fabric materials of above φviscose rayon, (2)polyester(PET), ©polyethylene (PE), ©polypropylene(PP), © Cotton and © Pulp, and the final fabric of wet tissues produced with one or mixtures of more than one of the fabric materials shall not exceed 0.03wt% (300ppm) to the weight of fabrics.

<192> This is because of that it is possible to have enough antimicrobial and anti-fungus function of final wet tissues as the antimicrobial and anti- fungus tissue manufacturing water is able to have the secondary functions in addition to preliminary antimicrobial and anti-fungus functions within the limited concentration of nano metal particles of 0.03wt%(300ppm) to the non- woven fabrics finally used even though the mixing ratio of any combination of more than one nano metal particles is decided.

<i93> In the tissue manufacturing water to achieve antimicrobial and anti- fungus functions as shown in the table 3 of the third embodiment of this invention, platinum, gold, silver, zinc, germanium and selenium is mixed independently or more than one of those selected material with the ratio shown in table 4. As for the tissue manufacturing water of this third embodiment, relatively lower mixing ratio is applied than above 1st example considering that it is used as mixtures with antimicrobial an anti-fungus fabrics.

<194> [Table 4] <195>

<196>

According to the table 4, the size of nano platinum particles mixed into the above-mentioned tissue manufacturing water to have additional antimicrobial and anti-fungus to antimicrobial and anti-fungus tissue fabrics shown in the table 3 is l-50nm and the final concentration is 0.00001~0.0003wt%(0.1~3ppm) to the weight of tissue manufacturing water.

<197> The size of nano gold particles mixed into the tissue manufacturing water is l-30nm and its final concentration is 0.00001~0.0005wt%(0.1~ 5ppm) to the weight of tissue manufacturing water.

<198> The size of nano silver particles mixed into the tissue manufacturing water is l-20nm and its final concentration is 0.00001~0.0001wt%(0.1~ lOppm) to the weight of tissue manufacturing water.

<199> The size of nano zinc particles mixed into the tissue manufacturing water is l-50nm and its final concentration is 0.0001—0.005wt%(l~50ppm) to the weight of tissue manufacturing water.

<200> The size of nano germanium particles mixed into the tissue manufacturing water is l-50nm and its final concentration is 0.0001~0.005wt%(l~50ppm) to the weight of tissue manufacturing water.

<201> The size of nano selenium particles mixed into the tissue manufacturing water is l-50nm and its final concentration is 0.0001~0.005wt%(l~50ppm) to the weight of tissue manufacturing water.

<202> And the final concentration of the nano metal particles which make more than one nano metal particles of each of the above-mentioned platinum, gold, silver, germanium, selenium and zinc dip into the tissue manufacturing water of the third embodiment 3 which already have bit of antimicrobial and anti- fungus functions shall not exceed 0.005wt%(50ppm) to the weight of tissue manufacturing water .

<203> This is because of that it is possible to have enough antimicrobial and anti-fungus function of final wet tissues as the nano metal particles mixed in the non-woven fabrics get additional antimicrobial and anti-fungus effects to the antimicrobial and anti-fungus effect from the antimicrobial and anti- fungus tissue manufacturing water is able to have the secondary functions in addition to preliminary antimicrobial and anti-fungus functions within the limited concentration of nano metal particles of 0.005wt%(50ppm) to the non- woven fabrics finally used even though the mixing ratio of any combination of more than one nano metal particles is decided.

<204> This is because of that enough antimicrobial and anti-fungus function can be obtained in the final wet tissue as the nano metal particles contained in non-woven fabrics provide additional antimicrobial and anti-fungus effects in addition to the effects from the final concentration of 0.005wt%(50ppm) to the weight of tissue manufacturing water even though the mixing rate of any combination of the mixture of more than one of above nano metal particles is decided.

<205> The same manufacturing method as explained in the first and second embodiments to select and use nano metal particles from the raw materials of platinum, gold, silver, germanium, selenium, zinc, copper and tungsten for non-woven fabrics and its manufacturing water of the third embodiment to manufacture each nano particles, additives such as reduction materials and stabilizers and the manufacturing method to the specifications of each nano metal particles are equally applied.

<206> (How to execute this invention)

<207> The following is the representative case of execution of the manufacturing method of wet tissue with antimicrobial and anti-fungus fabrics under this invention. <208> (Case of execute) <209> At first, do mix and spin germanium, selenium, zinc and copper respectively to viscose rayon with concentrations of 0.001wt%(10ppm), 0.0035wt%(35ppm), 0.01wt%(lOOppm) , 0.005wt%(50ppm) .

<210> [Table 5] <211> (Unit : ppm) <212>

And produce master-batch chips by mixing silver, zinc and tungsten into polyester terephthalate (PET) to have the concentration of 0.06wt%(600ppm) , 0.3wt%(3,000ppm), 0.15wt%(l,500ppm) to the weight of fabrics, and spin after mix plastic master-batch chips of 10wt% to the total weight of raw materials of polyester with raw materials of polyester. And make the concentration of nano metal particles of silver 0.006wt%(60ppm), zinc 0.03wt%(300ppm) and tungsten 0.015wt%(150ppm) to the weight of polyester fabrics.

<213> In the next process, manufacture non-woven fabrics for wet tissue with the ration of 70% viscose rayon and 30% polyester. The nano metal particles of silver 0.0018wt%(18ppm), zinc 0.016wt%(160ppm), copper 0.0035wt%(35ppm), germanium 0.0007wt%(7ppm), selenium 0.00105wt%(10.5ppm) and tungsten 0.0045wt%(45ppm) to the weight of fabrics are prepared for the final tissue fabrics of mixtures of 70% viscose rayon and 30% polyester.

<214> And, mix nano particles with the ratio as introduced in table 6 into manufacturing water to produce wet tissue with above non-woven fabrics, and produce wet tissue with non-woven fabrics which contains 3.5 times of tissue manufacturing water to the weight of non-woven fabrics.

<215> [Table 6] <216>

<217>

According to the antimicrobial and anti-fungus test results ofthe wet tissue, the result of the below table 7 was obtained by applying 0.5gr. of bacteria liquid of Aspergillus Niger ATCC 6275 as bacteria samples at 25+TC for 24hours.

<218> [Table 7]

<219> <220>

In the table 7, the reduction rate(%) is from the formula of '[(Ma-Mc) / Mb] x 100' Ma is average numbers of fungus of control sample at the beginning, Mb is average numbers of fungus of control sample after cultivation for 24 hours and Mc is the average numbers of fungus of tested samples after cultivation for 24 hours.

<221> According to the result of antimicrobial test of wet tissue, the result of table 8 was obtained with 5.0gr each of Staphylococcus aurous ATCC 6538 and Klebsiella pneumonia ATCC 4352 as bacteria and Cotton as standard fabric to test antimicrobial level under 'KS K 0693'.

<222> In the table 8, reduction rate of bacteria is obtained with the formula of ' [(Ma-Mc) / Mb] x 100' , Increasing rate(F) is 'Mb/Ma(more than 31.6 times), Ma is numbers of live bacteria (average of 3 bacteria) right after inoculation, Mb is the numbers of live bacteria (average number of 3 bacteria applied) in 18hours after cultivation.

<223> [Table 8] <224> <225>

<226>

As shown in the above-mentioned test result, satisfactory antimicrobial and anti-fungus effect is shown under the situation of ignoring the possibility of non-woven fabric pollution itself by impregnate non-woven fabric with tissue manufacturing water of selected mixed nano metal particles of antimicrobial and anti-fungus function as antimicrobial and anti-fungus fabrics under this invention. [Industrial Applicability]

<227> On the other hand, this invention is not limited to above listed application examples but also possible to change its applications subject to follow its technological basics of this invention.

<228> According to this invention, Even though the second embodiment shows that it is possible to get antimicrobial and anti-fungus function by melt- spinning one or mixture of more than one of nano metal particles (of gold, platinum, silver, germanium, selenium, zinc, copper and tungsten) into fabrics (of viscose rayon, polyester, polyethylene, polypropylene, cotton and pulp) to manufacture antimicrobial and anti-fungus non-woven fabrics, this invention is not limited to only this embodiment. <229> As an another example, it is possible to make the non-woven fabrics have antimicrobial and anti-fungus function by mixing additives such as adhesive agent to one or mixture of nano metal particles (of gold, platinum, silver, germanium, selenium, zinc, copper and tungsten) in the manufacturing process of fabrics (of viscose rayon, polyester, polyethylene, polypropylene, cotton and pulp).

<230> As an example, Chemical-bonding non-woven fabrics made of viscose rayon and polyester or mixture of viscose rayon and polyester can have antimicrobial and anti-fungus function by dipping or spray method with one or mixtures of more than one of above nano metal particles (of gold, platinum, silver, germanium, selenium, zinc, copper and tungsten) mixed with adhesives (water base adhesives, non-water base adhesives, soft type and hard type) used to form the web.

<23i> As an other example, thermal-bonding non-woven fabrics of polypropylene, blended yarn (PET-PE, PP-PE, PET-PP), viscose rayon(hopefully polypropylene or mixture of blended yarn) and polyester can get antimicrobial and anti-fungus function by forming the web through combination of fabric structures by mixing one or mixture of more than of above listed one nano metal particles selected from gold, platinum, silver, germanium, selenium, zinc, copper and tungsten to above fabrics of which fabric materials are attached by heat or melted to the surface.

<232> As another example, span-bond non-woven fabrics can be manufactured to have antimicrobial and anti-fungus function by using polyester, polypropylene or nylon chips and mix one or mixture of more than one of selected nano metal particles from above listed gold, platinum, silver, germanium, selenium, zinc, copper and tungsten in the manufacturing process of melting and spraying, and form the web.

<233> And, air ray non-woven fabrics which are manufactured with compressed air and adhesives to raw materials of fabric can have antimicrobial and anti- fungus function by adding one or mixture of more than one of selected nano metal particles from the above-mentioned gold, platinum, silver, germanium, selenium, zinc, copper and tungsten to above mentioned adhesives.

<234> Spun Lace (Hydro-entanglement) can have antimicrobial and anti-fungus function by adding one or mixture of more than one of selected nano metal particles from the above-mentioned gold, platinum, silver, germanium, selenium, zinc, copper and tungsten to the water to spray to form the web after mixing one or mixture of more than one of viscose rayon, polyester and polypropylene.

<235> And, Melt-blown non-woven fabrics can have antimicrobial and anti- fungus function by mixing one or mixture of more than one of selected nano metal particles from the above-mentioned gold, platinum, silver, germanium, selenium, zinc, copper and tungsten to above melting fabric web in the manufacturing process of homogeneous melting fabric web from spinning synthetic polymer and formed micro fiber by high pressure and hot wind.

Claims

[CLAIMS]

[Claim 1]

<237> A manufacture method of antimicrobial and anti-fungus wet tissue charaterized in that said tissue is wove with one or mixture of more than one of selected tissue fabric from viscose rayon, polyester, polyethylene fiber, polypropylene fiber, cotton and pulp, and by dipping into tissue manufacturing water which contained one or more than one of selected nano metal particles from platinum, gold, silver, germanium, selenium and zinc.

[Claim 2]

<238> The manufacture method according to claim 1, wherein in case of the size of said nano platinum particles, it is l~50nm and final concentration to use is 0.00001~0.0005wt%(0.1~5ppm) to the weight of said tissue manufacturing water, and it includes said nano platinum particles extracted through dissociation of said selected materials and reduction of Ion from platinum compound and platinum oxidize! [Ammonium hexachloroplatinumdV ); (NIU₂[PtCl₆], Diamine Dinitritoplatinum( π); Pt(N0₂)₂(NH3)2,

Hexachloroplatinum(IV) acid hydrate; H₂(PtCIe) ^• 6H₂O, Hexahydoxoplatinum(IV) acid; H₂Pt(OH₆), Platinum acetylacetonate; Pt(C5HτO₂)₂, Platinum chloride; PtCl, PtCl₂, PtCl₄, Platinum iodide; PtI₂, Platinum oxide; PtO, PtO₂, Pt₂O₃, Platinum sulfide; PtS₂], and the one formed with made small platinum particles by the method of physical impact and crush;

<239> in case of the size of said nano gold particles, it is l~30nm and the final concentration to use is 0.00001~0.001wt%(0.1~ lOppm) to the weight of said tissue manufacturing water, and it includes the extracted gold through dissociation of said selected materials with pure water, ethanol and Isopropyl alcohol, and reduction of Ion from gold compound and gold oxidize: [Gold sulfide ; Au₂S, Gold hydroxide ; AuOH, Au(OH)₃, Gold iodide ; AuI, Gold oxide ; Au₂O,Au₂O₃, Gold oxide hydrate ; Au₂O₃-XH₂O, Gold chloride ; AuCl, AuCl₃, Gold chloride trihydrate ; HAuCl₄ ^• 3H₂O] , and the one formed with made small gold particles by the method of physical impact, crush and electrical explosion;

<240> in case of the size of the nano silver particles, it is l~20nm and the final concentration to use is 0.00001~0.002wt%(0.1~20ppm) to the weight of the tissue manufacturing water, and it includes the one manufactured with the selected raw materials of its metal chloride and compound; [Silver nitrate ;AgNO₃, Silver chloride ; AgCl, Silver chlorate ; AgClO₃, AgClO₄), Silver sulfate ; Ag₂SO₄, Silver sulfite ; Ag₂SOs, Silver sulfide ; Ag₂S, Silver acetate ; CH₃COOAg, Silver selenide ; Ag₂Se, Silver citrate hydra !AgO₂CCH₂C(OH)(CO₂Ag)CH₂CO₂AgXH₂], and the one formed with made small silver particles by the method of physical impact, crush and electrical explosion! <24i> in case of the size of the nano zinc particles, it is l~50nm and the final concentration used is 0.003-0.03wt%(30~ 300ppm) to the weight of the tissue manufacturing water, and it includes the extracted zinc through dissociation of the selected materials and reduction of Ion from zinc compound; [Zinc acetate; (CH₃C0₂)₂Zn, Zinc acetate dihydrate; Zn(CH₃COO)₂ ^• 2H₂O,

Zinc acrylate;(H₂C=CHC0₂)₂Zn, Zinc chloride; ZnCl₂, Zinc iodide; ZnI₂, Zinc phthalocyanine; C₃₂H₁₆N₈Zn, Zinc selenide; ZnSe, Zinc sulfate; ZnSO₄, Zinc sulfide; ZnS, Zinc 29//3L^!H;etrabenzol [b,g,l,q] porphyrin; C₃^₂ON₄Zn], and the one formed with made small zinc particles by the method of physical impact, crush and electrical explosion;

<242> in case of the size of the nano germanium particles, it is l~50nm and the final concentration to use is 0.0001~0.01wt%(l ~ lOOppm) to the weight of the wet tissue manufacturing water, and it includes the extracted metal germanium through dissociation of said selected materials and reduction of Ion from germanium compound; [Germanium chloride; GeCl₄, Germanium chloride dioxane complex; C₄HgCl₂GeO₂, Germanium fluoride; GeF₄, Germanium iodide; GeI₂, GeI₄, Germanium isopropoxide; Ge(0CH(CH₃)₂)₃, Germanium methoxide; Ge(0CH₃)₄, Germanium nitride; Ge3N₄, Germanium oxide; Geθ2, Germanium selenide; GeSe, GeSe₂, Germanium sulfide; GeS], and organic compound germanium bis(2- carboxyethyl germanium sesquioxide); 0[Ge(O)CH₂CH₂CO₂H]₂, and the germanium particles crushed through physical impact;

<243> in case of the size of the nano selenium particles, it is 1 ~ 50nm in and the final concentration to use is 0.0001~0.01wt%(l~ lOOppm) to the weight of the tissue manufacturing water, and it includes the extracted metal selenium through dissociation of the selected materials and reduction of Ion from selenium compound; [Selenium oxychloride! SeOCl₂, Selenium sulfide! SeS₂,

Selenium tetrachloride; SeCU, Seleno-L-cystine; C₆Hi₂N₂O₄Se₂, Seleno-L- methionine; CH₃SeCH₂CH₂CH(NH₂)CO₂H, Selenophene; C₄H₄Se, Selenous acid; H₂SeO₃,

Germanium selenide; GeSe, GeSe2], and the one formed with crushed selenium particles by physical impact;

<244> in said tissue manufacturing water mixed with one or more than one of platinum, gold, silver, germanium, selenium and zinc, hydrogen peroxide (H202) of 0.001-0.045wt%(10~450ppm) to the weight of the tissue manufacturing water as final concentration to avoid color changes of fabrics are contained;

<245> said manufacturing method of antimicrobial and anti-fungus wet tissues that contain nano particles which is manufactured with nano particles of platinum, gold, silver, germanium, selenium and zinc made of each materials which is dissociated and resolved from its compound of platinum, gold, silver, germanium, selenium and zinc, and the one obtained by extracting each of platinum, gold, silver, germanium, selenium and zinc which is purged of nitrogen and irradiated with gamma ray after melt into water or non- water(volatile solvent) with high molecule stabilizer,

<246> and said silver nano particles produced from the silver nitrate which is denitrated through an ion exchanger resin or distillation under vacuum and reducing pressure method to remove 'N03-' which is generated in process of silver produce from silver nitrate as a counter ion of Ag+.

[Claim 3]

<247> The manufacture method according to claim 2, wherein the reducing agent which is used in manufacturing process of nano metal particles of gold, platinum, silver, germanium, selenium and zinc include formaldehyde, hydrazine, tocopherol, organic acids! [formic acid, citric acid, acetic acid, maleic acid, organic acid have carbon under 4, methyl ethanolamine HOCH₂CH₂N(CHs)₂] ,

<248> the stability agent of selected one or more than one out of polyethylene, polyacrylonitrile, polymethylmeta-acrylate, polyurethane, polyacrylamide, polyethylene glycol and polyoxyethylene stearate are used in the manufacturing process of said nano metal particles of above gold, platinum, silver, germanium, selenium and zinc,

<249> said manufacture method of antimicrobial and anti-fungus wet tissue with stability agent for silver of selected one or more than one from poly vinyl pyrrol idone-co-acrylic acid, polyoxyethylene stearate, polyvinyl Butyral, polyvinyl alcohol.

[Claim 4]

<250> A manufacture method of antimicrobial and anti-fungus wet tissue charaterized in that ;

<25i> forming antimicrobial and anti-fungus fiber by mixing nano material of selected one or more than one from gold, platinum, silver, germanium, selenium, zinc, copper and tungsten to the fiber material of selected one or more than one from viscose rayon, polyester, polyethylene, polypropylene, cotton and pulp,

<252> and dipping said antimicrobial and anti-fungus fibers into tissue manufacturing water which is purified water or distilled water without preservative.

[Claim 5]

<253> The manufacture method according to claim 4, wherein nano metal particles of selected one or more than one from said germanium, selenium, zinc, copper and tungsten are added and spin in the material adding process before spinning of rayon fiber in the viscose rayon manufacturing process,

<254> in the case of fabric material such as polyester, polyethylene and polypropylene, nano metal particles of selected one or more than one from above platinum, gold, silver, germanium, selenium zinc, copper and tungsten are mixed with thermostatic plastic resin to produce either master-batch chips or compounding chips, and after extruding, mix these made master-batch chips of 3-10wt% to the plastic raw materials with the plastic raw materials or use 100% of above made compounding chips to spin for antimicrobial and antifungal fiber,

<255> in case of cotton, dip the cotton into water which contains nano metal particles of said platinum, gold, silver, zinc, germanium and selenium or spin with these nano metal particles,

<256> in case of pulp, manufacturing method of antimicrobial and anti-fungus wet tissue is that mix selectively said nano metal particles of platinum, gold, silver, zinc, germanium and selenium with processing water which is used in the dispersion process of pulp materials or mix it with adhesive agents which are used in the process of having the pulp in certain thickness and shape or spray the mixture of above nano metal particles of platinum, gold, silver, germanium, selenium and zinc upon the surface of pulp after the pulp gets the shape of fabrics.

[Claim 6]

<257> The manufacture method according to claim 4, wherein said manufacturing method of antimicrobial and anti-fungus wet tissue contain that said fabrics are manufactured with viscose rayon, polyester, polyethylene, polypropylene, cotton and pulp as a fabric material by attach compression, melt and spraying to form the web, and mix nano metal particles of selected one or more than one from said platinum, gold, silver, germanium, selenium, zinc and copper with the adhesive agents for attach, melting fabric materials and spraying water.

[Claim 7]

<258> The manufacture method according to claim 4 or 6, wherein said manufacturing method of antimicrobial and anti-fungus wet tissues is especially as follows;

<259> in case of the size of said nano platinum particles, it is l~50nm and final concentration to use is 0.00005~0.003wt%(0.5~30ppm) to the weight of said tissue manufacturing fabrics, and it includes nano platinum particles extracted through dissociation of the selected materials and reduction of Ion from platinum compound and platinum oxidize; [Ammonium hexachloroplatinumdV ); (NIU)₂[PtCl₆], Diamine Dinitritoplatinum(π); Pt(NO₂MNHs)₂,

Hexachloroplatinum(IV) acid hydrate; H₂(PtCl₆) ^• 6H₂O, Hexahydoxoplatinum(IV) acid; H₂Pt(OH₆), Platinum acetylacetonate; Pt(C5HτO₂)₂, Platinum chloride; PtCl, PtCl₂, PtCl₄, Platinum iodide; PtI₂, Platinum oxide; PtO, PtO₂, Pt₂O₃, Platinum sulfide; PtS₂], and the one formed with made small platinum particles by the method of physical impact and crush;

<260> in case of the size of said nano gold particles, it is l~30nm and the final concentration to use is 0.00005~0.005wt%(0.5~50ppm) to the weight of the tissue manufacturing fabrics, and it includes the extracted gold through dissociation of the selected materials with pure water, ethanol and Isopropyl alcohol, and reduction of Ion from gold compound and gold oxidize: [Gold sulfide ; Au₂S, Gold hydroxide ; AuOH, Au(OH)₃, Gold iodide ; AuI, Gold oxide

; Au₂O,Au₂O₃, Gold oxide hydrate ; Au₂O₃-XH₂O, Gold chloride ; AuCl, AuCl₃, Gold chloride trihydrate ; HAuCU ^• 3H₂O] , and the one formed with made small gold particles by the method of physical impact, crush and electrical explosion;

<26i> in case of the size of said nano silver particles, it is l~20nm and the final concentration to use is 0.0005~0.02wt%(5~200ppm) to the weight of the tissue manufacturing fabrics, and it includes the one manufactured with the selected raw materials of its metal chloride and compound; [Silver nitrate ;AgN0₃, Silver chloride ; AgCl, Silver chlorate ; AgClO₃, AgClO₄), Silver sulfate ; Ag₂SO₄, Silver sulfite ; Ag₂SO₃, Silver sulfide ; Ag₂S, Silver acetate ; CH₃COOAg, Silver selenide ; Ag₂Se, Silver citrate hydra ;Agθ2CCH2C(OH)(CO₂Ag)CH₂CO₂AgXH₂], and the one formed with made small silver particles by the method of physical impact, crush and electrical explosion; <262> in case of the size of said nano zinc particles, it is l~50nm and the final concentration used is 0.003—0. lwt%(30~l,000ppm) to the weight of the tissue manufacturing fabrics, and it includes the extracted zinc through dissociation of the selected materials and reduction of Ion from zinc compound; [Zinc acetate; (Ch^CO^Zn, Zinc acetate dihydrate; Zn(CHsCOO)₂ ^• 2H₂O,

Zinc aery1ate;(H2C=CHC02)2Zn, Zinc chloride; ZnC12, Zinc iodide; ZnI₂, Zinc phthalocyanine; Cs₂Hi₆N₈Zn, Zinc selenide; ZnSe, Zinc sulfate; ZnSO₄, Zinc sulfide; ZnS, Zinc 29Λ81#-tetrabenzol [b,g,l,q] porphyrin; C₃₆H₂ON₄Zn], and the one formed with made small zinc particles by the method of physical impact, crush and electrical explosion;

<263> in case of the size of said nano germanium particles, it is l~50nm and the final concentration to use is 0.0001~0.03wt%(l~300ppm) to the weight of the wet tissue manufacturing fabrics, and it includes the extracted metal germanium through dissociation of the selected materials and reduction of Ion from germanium compound; [Germanium chloride; GeCl₄, Germanium chloride dioxane complex; C₄H₈Cl₂GeO₂, Germanium fluoride; GeF₄, Germanium iodide; GeI₂, GeI4, Germanium isopropoxide; Ge(0CH(CH3)₂)₃, Germanium methoxide; Ge(OCHs)₄, Germanium nitride; Ge₃N₄, Germanium oxide; GeO₂, Germanium selenide; GeSe, GeSe₂, Germanium sulfide; GeS], and organic compound germanium bis(2- carboxyethyl germanium sesquioxide); 0[Ge(O)CH₂CH₂CO₂H]₂, and the germanium particles crushed through physical impact;

<264> in case of the size of said nano selenium particles, it is l~50nm in its particle size and the final concentration to use is 0.0001~0.01wt%(l^~ lOOppm) to the weight of said tissue manufacturing fabrics, and it includes the extracted metal selenium through dissociation of the selected materials and reduction of Ion from selenium compound; [Selenium oxychloridei SeOCl2,

Selenium sulfide; SeS2, Selenium tetrachloride; SeCl₄, Selono-L-cystine; C₆Hi₂N₂O₄Se₂, Seleno-L-methionine; CH₃SeCIkCH₂CH(NH₂)CO₂H, Selenophene; C₄H₄Se, Selenous acid; H₂SeO₃, Germanium selenide; GeSe, GeSe₂], and the one formed with crushed selenium particles by physical impact;

<265> in case of the size of said nano copper particles, it is 1 ~ 50nm and its final concentration to use is 0.001~0.02wt%(10~200ppm) to the weight of the tissue manufacturing fabrics, it includes nano copper particles extracted through dissociation of the selected materials and reduction of Ion from the material group of copper compound(Copper acetate ; CH₃CO₂Cu, coρρer( Il

)acetate; (CH₃C0₂)₂Cu, copper( Il )acetate monohydrate; (CH₃COO)₂Cu ^■ H20, CuBr₂, copper chloride; CuCl, CuCl₂, Copper( Il ) D-gluconate; Ci₂H₂₂CuOi₄, Copper( Il ) phthalocyamine; C₃₂Hi₆CuN₈, Copper( Il ) sulfate; CuSO₄, Copper( Il ) sulfide; Cu₂S, Copper( Il ) selenide; Cu₂Se) and the one formed with made small zinc particles by the method of physical impact, crush and electrical explosion;

<266> in case of the size of said nano tungsten particles, it is l~50nm and its final concentration to use is 0.001-0.03wt%(10 ~300ppm) to the weight of the tissue manufacturing fabrics, it includes nano tungsten particles extracted through dissociation of the selected materials and reduction of Ion from the material group of tungsten compound (Tungsten(IV) carbide; WC, Tungsten(rV) chloride; WCl₄, Tungsten(VI) chloride; WCl₆, Tungsten(VI) dichloride dioxide; WCl₂O₂, Tungsten hexacarbonyl ; W(C0)6, Tungsten(IV) Oxide; W02, Tungsten(VI) Oxide; WO₃, Tungsten(VI) oxychloride; WOCl₄,Tungsten(o) pentacarbonyl-N-pentylison-itri Ie; (C0)₃WCN(CH₂)₄CH₃, Tungsten suicide; WSi₂, Tungsten(IV) sulfide; WS₂) and the one formed with made small tungsten particles by the method of physical impact, crush and electrical explosion;

<267> said manufacturing method of antimicrobial and anti-fungus wet tissues that contain nano particles which is manufactured with nano particles of platinum, gold, silver, germanium, selenium, zinc, copper and tungsten made of each materials which is dissociated and resolved from its compound of platinum, gold, silver, germanium, selenium zinc, copper and tungsten and the one obtained by extracting each of platinum, gold, silver, germanium, selenium zinc, copper and tungsten which is purged of nitrogen and irradiated with gamma ray after melt into water or non-water(volatile solvent) with high molecule stabilizer, and the silver nano particles produced from the silver nitrate which is denitrated through an ion exchanger resin or distillation under vacuum and reducing pressure method to remove 'N03-' which is generated in process of silver produce from silver nitrate as a counter ion of Ag+.

[Claim 8]

<268> The manufacture method according to claim 7, the reducing agent which is used in manufacturing process of nano metal particles of said gold, platinum, silver, germanium, selenium and zinc include formaldehyde, hydrazine, tocopherol, organic acids; [formic acid, citric acid, acetic acid, maleic acid, organic acid have carbon under 4, methyl ethanolamine HOCH₂CH₂N(CHs)₂] ,

<269> the stability agent of selected one or more than one out of polyethylene, polyacrylonitrile, polymethylmeta-acrylate, polyurethane, polyacrylamide, polyethylene glycol and polyoxyethylene stearate are used in the manufacturing process of nano metal particles of above gold, platinum, silver, germanium, selenium and zinc,

<270> said manufacturing method of antimicrobial and anti-fungus wet tissue with stability agent for silver of selected one or more than one from poly vinyl pyrrolidone-co-acrylie acid, polyoxyethylene stearate, polyvinyl Butyral , polyvinyl alcohol.

[Claim 9]

<27i> A manufacture method of antimicrobial and anti-fungus wet tissues to have multiple antimicrobial and anti-fungus functions by both of non-woven fabrics and tissue manufacturing water is that form antimicrobial and anti- fungus non-woven fabrics by mixing and spinning nano material of selected one or more than one from gold, platinum, silver, germanium, selenium, zinc, copper and tungsten to the fiber material of selected one or more than one from viscose rayon, polyester, polyethylene, polypropylene, cotton and pulp, and mixing tissue manufacturing water which contains nano metal particles of selected one or more than one from gold, platinum, silver, germanium, selenium and zinc with above antimicrobial and anti-fungus non-woven fabrics.

[Claim 10]

<272> The manufacture method according to claim 9, wherein said manufacturing method of antimicrobial and anti-fungus wet tissues is especially as follows;

<273> in case of viscose rayon, said nano metal particles of selected one or more than one from germanium, selenium, zinc, copper and tungsten are added in the adding process of raw materials before spinning process of rayon fiber in manufacturing process of viscose rayon as fabric materials, and spin with above selected nano metal particles,

<274> in case of polyester, polyethylene and polypropylene, either mater- batch chip or compounding chip are made by mixing said nano metal particles of selected one or more than one from above gold, platinum, silver, germanium, selenium, zinc, copper and tungsten with thermostatic plastic resin, and the above made master-batch chips are mixed with its plastic raw material with the ratio of 3~10wt% and spin yarn out of mixture of these, and in case of the above compounding chip, spin yarn out of 100wt% of itself,

<275> in case of cotton, it is dipped into the mixture water of said nano metal particles of platinum, gold, silver, zinc, germanium and selenium or spin yarn out of the mixture of cotton and above nano metal particles,

<276> in case of pulp, it is made by mixing said nano metal particles of selected one or more than one from platinum, gold, silver, zinc, germanium and selenium with processing water which is used for dispersion process of pulp materials, and by mix it into adding process of adhesive agent to produce pulp in certain thickness and shape, and by mix the mixture of said nano metal particles into surface of pulp by spray after the pulp is formed as pulp fabric.

[Claim 11]

<277> The manufacture method according to claim 9, wherein said manufacturing method of antimicrobial and anti-fungus wet tissue is especially as follows;

<278> in case of viscose rayon, polyester, polyethylene, polypropylene, cotton and pulp as a fabric material by attach compression, melt and spraying to form the web, and mix nano metal particles of selected one or more than one from said platinum, gold, silver, germanium, selenium, zinc and copper with the adhesive agents for attach, melting fabric materials and spraying water.

[Claim 12]

<279> The manufacture method according to claim 9, wherein among the particles used for above fabric materials and its tissue manufacturing water is especially as follows;

<280> in case of the size of said nano platinum particles, it is l~50nm and the final concentration to use is 0.00005-0.00lwt%(0.5 ~ lOppm) to the weight of the fabric materials, and 0.00001~0.0003wt%(0.1~3ppm) to the weight of the tissue manufacturing water and it includes nano platinum particles extracted through dissociation of the selected materials and reduction of Ion from platinum compound and platinum oxidize; [Ammonium hexachloroplatinum(IV ); (Nm)₂[PtCl₆], Diamine Dinitritoplatinum(π); Pt(N0₂)2(NH₃)2,

Hexachloroplatinum(IV) acid hydrate; H₂(PtCIe) ^• 6H₂O, Hexahydoxoplatinum(lV) acid; H₂Pt(OH₆), Platinum acetylacetonate; Pt(C5HτO₂)₂, Platinum chloride; PtCl, PtCl₂, PtCl₄, Platinum iodide; PtI₂, Platinum oxide; PtO, PtO₂, Pt₂O₃, Platinum sulfide; PtS₂], and the one formed with made small platinum particles by the method of physical impact and crush;

<28i> in case of the size of said nano gold particles, it is l~30nm and the final concentration to use is 0.00005-0.001wt%(0.5 ~ lOppm) to the weight of said fabrics and 0.00001- 0.0005 wt%(0.1^~5ppm) to the weight of the tissue manufacturing water, and it includes the extracted gold through dissociation of the selected materials with pure water, ethanol and Isopropyl alcohol, and reduction of Ion from gold compound and gold oxidize: [Gold sulfide ; AU₂S,

Gold hydroxide ; AuOH, Au(OH)₃, Gold iodide ; AuI, Gold oxide I Au2θ,Au2θ3, Gold oxide hydrate ; Au₂O₃-XH₂O, Gold chloride ; AuCl, AuCl₃, Gold chloride trihydrate ; HAuCU " 3H₂O], and the one formed with made small gold particles by the method of physical impact, crush and electrical explosion;

<282> in case of the size of said nano silver particles, it is l~20nm and the final concentration to use is 0.0005—0.01wt%(5—lOOppm) to the weight of said fabrics and 0.00001~0.0001wt%(0.1-lOppm) to the weight of the tissue manufacturing water, and it includes the one manufactured with the selected raw materials of its metal chloride and compound; [Silver nitrate ;AgN03, Silver chloride ; AgCl, Silver chlorate ; AgClO₃, AgClO₄), Silver sulfate ; Ag₂SO₄, Silver sulfite ; Ag₂SOs, Silver sulfide ; Ag₂S, Silver acetate ; CH₃COOAg, Silver selenide ; Ag₂Se, Silver citrate hydra ;AgO₂CCH₂C(OH)(CO₂Ag)CH₂CO₂AgXH₂], and the one formed with made small silver particles by the method of physical impact, crush and electrical explosion; <283> in case of the size of said nano zinc particles, it is 1 ~ 50nm and the final concentration to use is 0.003~0.03wt%(30~300ppm) to the weight of said fabrics and 0.0001—0.005wt%(l~50ppm) to the weight of said tissue manufacturing water, and it includes the extracted zinc through dissociation of the selected materials and reduction of Ion from zinc compound; [Zinc acetate; (CH₃Cθ2)2Zn, Zinc acetate dihydrate; Zn(CH₃COO)₂ ^• 2H₂O, Zinc acrylate;(H₂C=CHC0₂)₂Zn, Zinc chloride; ZnCl₂, Zinc iodide; ZnI₂, Zinc phthalocyanine; C₃₂Hi6NsZn, Zinc selenide; ZnSe, Zinc sulfate! ZnSO₄, Zinc sulfide; ZnS, Zinc 29/Bl#-tetrabenzol [b,g,l,q] porphyrin; C₃₆H₂ON₄Zn], and the one formed with made small zinc particles by the method of physical impact, crush and electrical explosion;

<284> in case of the size of said nano germanium particles, it is l~50nm and the final concentration to use is 0.0001~0.005wt%(l~50ppm) to the weight of said fabrics and 0.0001-0.005wt%(0.5~30ppm) to the weight of the tissue manufacturing water, and it includes the extracted metal germanium through dissociation of the selected materials and reduction of Ion from germanium compound; [Germanium chloride; GeCU, Germanium chloride dioxane complex;

C₄H₈Cl₂GeO₂, Germanium fluoride; GeF₄, Germanium iodide; Gel2, GeI₄, Germanium isopropoxide; Ge(0CH(CH₃)₂)3, Germanium methoxide; Ge(0CH₃)₄, Germanium nitride; Ge₃N₄, Germanium oxide; GeO₂, Germanium selenide; GeSe, GeSe2,

Germanium sulfide; GeS], and organic compound germanium bis(2-carboxyethyl germanium sesquioxide); 0[Ge(K))CH₂CH₂CO₂H]₂, and the germanium particles crushed through physical impact;

<285> in case of the size of said nano selenium particles, it is l~50nm and the final concentration to use is 0.0001~0.005wt%(l^~50ppm) to the weight of above fabrics and 0.0001—0.005wt%(l—50ppm) to the weight of the tissue manufacturing water, and it includes the extracted metal selenium through dissociation of the selected materials and reduction of Ion from selenium compound; [Selenium oxychloride; SeOCl₂, Selenium sulfide; SeS₂, Selenium tetrachloride; SeCl₄, Seleno-L-cystine! CeHi₂N₂O₄Se₂, Seleno-L-methionine; CHsSeCH₂CH₂CH(NH₂)CO₂H, Selenophene; C₄H₄Se, Selenous acid; H₂SeO₃, Germanium selenide; GeSe, GeSe₂], and the one formed with crushed selenium particles by physical impact;

<286> in case of the size of said nano copper particles, it is l~50nm and the final concentration to use is 0.001~0.01wt%(10^~ lOOppm) to the weight of said fabrics, it includes nano copper particles extracted through dissociation of the selected materials and reduction of Ion from the material group of copper compound(Copper acetate ; CH₃CO₂Cu, copρer( Il )acetate; (CH₃COs)₂Cu, copper( Il )acetate monohydrate; (CH₃COO)₂Cu-H₂O, CuBr₂, copper chloride; CuCl, CuCl₂, Copper( Il ) D-gluconate; C₁₂H₂₂CuOi₄, Copper( Il ) phthalocyamine; C₃₂HIeCuN₈, Copper( Il ) sulfate; CuSO₄, Copper( Il ) sulfide; Cu₂S, Copper( Il ) selenide; Cu₂Se) and the one formed with made small zinc particles by the method of physical impact, crush and electrical explosion;

<287> in case of the size of said nano tungsten particles, it is l~50nm and the final concentration to use is 0.001-0.01wt%(10 ~ lOOppm) to the weight of said fabrics, and it includes nano tungsten particles extracted through dissociation of the selected materials and reduction of Ion from the material group of tungsten compound (Tungsten(IV) carbide; WC, Tungsten(IV) chloride; WC14, Tungsten(VI) chloride; WCl₆, Tungsten(VI) dichloride dioxide; WCl₂O₂,

Tungsten hexacarbonyl ; W(CO)₆, Tungsten(IV) Oxide; WO₂, Tungsten(VI) Oxide; WO₃, Tungsten(VI) oxychloride; WOCl₄,Tungsten(o) pentacarbony1-N-pentyIison- itrile;(C0)₃WCN(CH₂)₄CH₃, Tungsten suicide; WSi₂, Tungsten(IV) sulfide; WS₂) and the one formed with made small tungsten particles by the method of physical impact, crush and electrical explosion;

<288> said manufacturing method of antimicrobial and anti-fungus wet tissues that contain nano particles which is manufactured with nano particles of platinum, gold, silver, germanium, selenium, zinc, copper and tungsten made of each materials which is dissociated and resolved from its compound of platinum, gold, silver, germanium, selenium zinc, copper and tungsten and the one obtained by extracting each of platinum, gold, silver, germanium, selenium zinc, copper and tungsten which is purged of nitrogen and irradiated with gamma ray after melt into water or non-water(volatile solvent) with high molecule stabilizer, and the silver nano particles produced from the silver nitrate which is denitrated through an ion exchanger resin or distillation under vacuum and reducing pressure method to remove 'N03-' which is generated in process of silver produce from silver nitrate as a counter ion of 'Ag+';

<289> said manufacturing method of antimicrobial and anti-fungus wet tissue manufacturing water which contains one or more than one of above nano metal particles (platinum, gold, silver, germanium, selenium and zinc) with hydrogen peroxide (H₂O₂) of 0.001~0.045wtΗl0~450ppm) to the weight of tissue manufacturing water as its final concentration to use for preventing color contamination of above fabrics.

[Claim 13]

<290> The manufacture method according to claim 12, wherein the reducing agent which is used in manufacturing process of nano metal particles of said gold, platinum, silver, germanium, selenium and zinc includes formaldehyde, hydrazine, tocopherol, organic acids! [formic acid, citric acid, acetic acid, maleic acid, organic acid have carbon under 4, methyl ethanolamine HOCH₂CH₂N(CHs)₂] ,

<29i> the stability agent of selected one or more than one out of polyethylene, polyacrylonitrile, polymethylmeta-acrylate, polyurethane, polyacrylamide, polyethylene glycol and polyoxyethylene stearate are used in the manufacturing process of nano metal particles of above gold, platinum, silver, germanium, selenium and zinc,

<292> said manufacturing method of antimicrobial and anti-fungus wet tissue with stability agent for silver of selected one or more than one from poly vinyl pyrrol idone-co-acrylic acid, polyoxyethylene stearate, polyvinyl Butyral , polyvinyl alcohol.