TW200306373A - Antimicrobial polyeter-containing articles and process for their preparation - Google Patents

Abstract

This invention relates to antimicrobial polyester-containing articles and methodology for the preparation of antimicrobial polyester-containing articles utilizing chitosan and chitosan-metal complexes as the antimicrobial agent.

Description

200306373 玖 玖, description of the invention (the description of the invention shall state: the technical field to which the invention belongs, prior art, content, embodiments, and a brief description of the drawings) TECHNICAL FIELD This case is the US application SN 10 filed on May 10, 2002 / 143,380 (incorporated in its entirety as part of it), claims priority to US Provisional Application Serial No. 60 / 290,297 filed on May 11, 2001. The present invention relates to antimicrobial-containing polyester articles and methods for preparing antimicrobial-containing polyester articles, which use deacetylated chitin and deacetylated chitin-metal complex as antimicrobial agents. Prior Art The present invention relates to the use of chitosan and chitosan-metal complexes to produce polyester-containing articles having antimicrobial properties. PCT application WO 00/49219 discloses the preparation of substrates having biocidal properties. Among other materials, especially the dissolved chitosan was deposited on polyester, followed by treatment with silver salts, the reduction of the silver salt and the cross-linking of the chitosan were reported to produce durable biocidal properties object. The application also discloses that the chitosan chitosan is crosslinked after application, before or after the silver salt treatment. JP Kokai H9-291478 discloses a method for applying a chitosan derivative to a polyester fabric, which comprises treating the polyester fabric with ultraviolet light, and then applying a quaternary ammonium base derived from chitosan. The ultraviolet light irradiation is used to generate free radicals on the surface of the polyester fabric, and the free radicals are subsequently connected to the chitosan. H. Shin et al., Sen-I Gakkaishi, 54 (8), 400-406 (1998) disclose similar UV fabric treatments and low-temperature air plasma treatments before chitosan treatment. JP Kokai H8-22772 discloses a method for manufacturing antibacterial acrylic yarn, 200306373 Description of the invention continued page

It involves immersing the wet spinning yarn obtained from a polymer solution mainly composed of acrylonitrile in an acidic chitosan aqueous solution, neutralizing it with a test solution, drying and pressing. The method is performed batchwise or continuously. The chitosan is adsorbed on the surface of the yarn, and is deposited in micropores in the yarn before drying. S. Matsukawa et al., Sen-I Gakkaishi, 51 (1), 51-56 (1995) disclose modification of polyester fabrics with chitosan. This polyester was neutralized with caustic soda hydrolyzation 'with a 1% acetic acid solution, treated with a chitosan solution, and optionally treated with a crosslinking agent. SUMMARY OF THE INVENTION The present invention provides an antimicrobial polyester-containing article having chitosan grafted on the article and optionally containing one or more metal salts, one or more carboxyl-containing polymers, or a combination thereof . In addition, a method for preparing an antimicrobial-containing polyester article is disclosed, including the following continuous steps: (a) providing a polyvinegar-containing article; (b) bringing the polyester-containing article into contact with an alkaline solution; (c) a washing step as appropriate ( 1}) the article produced; (d) contact the article produced in step (b) or step (c) with a strong inorganic acid solution; (e) the article washing step (the article produced in the sentence) ; (F) removing the article prepared in step (d) or step (e) from a substance selected from the group consisting of chitosan, chitosan salt, chitosan salt and chitosan derivative Contact with the solution of acetamidine chitin reagent; (g) heating the object prepared in step as appropriate; 200306373 (3) description of the invention continued (h) single step 骡 (f) or step g (g) And (1) optionally heating the object detached in step (h) at a temperature higher than step (g). In addition, a continuous method for manufacturing antimicrobial polyester-containing objects is disclosed, including the following continuous steps骡: (a) Provide a feeding table equipped with a polyester object and a take-up station that can receive the polyester object (b) pulling the object from the child feeding station through the first processing station, wherein the object is exposed to an alkaline solution; the object treated in step (b), the object treated in step (b) or step (c) Organic acid solution; the object treated in step (d), which (c) is pulled through the second processing table as appropriate, where the object is exposed to water; (d) the warp step is pulled through the third processing table, where The object is exposed to the absence of (e) through the fourth treatment stage as appropriate? In the case of the object is exposed to deionized 7 right U) or the solution of step (e) deacetylated chitin reagent (f) The chanting piece is pulled through the fifth processing table, where the object is exposed to the liquid; (g) the object that has been treated with multiple steps (f) after it leaves the deacetylation shell; and The condition heating is received by the step piece and accumulated at the take-up (h) (step (f) or stepwise)! Of # on the stage. The hair

The invention includes antimicrobial containing grafted deacetylated husks and polysaccharides containing polysaccharides. 200306373 Description of the invention continued (4) Preparation of pieces. Chitosan is commonly used under the name poly-Π4] -β-D-glucosamine. Chitosan is chemically derived from chitin, which is poly- [1-4] -β-N-acetylglucosamine, and chitin is derived from the cell walls of fungi, insects, and (especially) crustaceans Derivatives of classes. The term "graft" used in the present invention means that the chitosan is bonded to the polyester substrate by ionic (electrostatic) or covalent bonding. The grafting of the chitosan to the polyester article can be confirmed by electronic spectrum (ESCA) of chemical analysis [see, for example, Xin Qu, Anders Wirsen, Bjorn Orlander, Anne-Christine Albertsson, Polymer Bulletin, (2001), vol. 46 ”pp.223-229 and Huh, M.W ·, Kang, I ·, Lee, D · H ·, Kim, W. S ·, Lee, D. H ·, Park, L. S ·, Mln. K. E., and Seo, K. H., J. Appl. Polym. Sci. (2001), vol. 81, p. 2769]. Grafting was also performed at Ga-er Yu, Frederick G. Morin, Geffory A.R. Nobes, and Robert H. Marchessault, recognized in the literature records of Macromolecules (1999), vol. 32, ρρ 518-520). ESCA data proves that the polyester-containing article of the present invention has been deacetylated. The composition of the chitin-modified surface is similar to the starting material of deacetylated chitin. ESCA data also show that these surfaces have important concentrations of nitrogen incorporated in the form of salts, providing the chitosan with each other via ionicity Evidence of physical binding to the surface. Polymeric esters include polymers made from glycols and dibasic acids. They can be used to prepare polymers Ester dicarboxylic acids include-but are not limited to-unsubstituted and substituted aromatic, aliphatic, unsaturated, and cycloaliphatic dicarboxylic acids, and low fever with dicarboxylic acids ranging from 2 to 36 carbons S. Specific examples of the required diacid component include terephthalic acid, dimethyl terephthalate, isophthalic acid, dimethyl isophthalate, 2,6-¾: dicarboxylic acid, Methyl 2,6-fluorenedicarboxylic acid, 2,7-fluorenedicarboxylic acid '2,7- 200306373 (5) Description of the invention continued page

Dimethyl dicarboxylate, 3,4, diphenyl ether dicarboxylic acid, 3,4, diphenyl ether dicarboxylic acid dimethyl, 4,4'-diphenyl ether dicarboxylic acid, 4, 4, diphenyl Dimethyl ether dicarboxylate, 3,4'-diphenyl sulfide dicarboxylic acid, 3,4, dimethyl diphenyl sulfide dicarboxylic acid '4,4'-diphenyl sulfide dicarboxylic acid, 4 , 4'-Diphenylsulfide dicarboxylic acid dimethyl ester, 3,4, diphenylarsine dicarboxylic acid, 3,4'-diphenylarsine dicarboxylic acid dimethyl, 4,4 'diphenylarsine dicarboxylic acid Acid, dimethyl 4,4'-diphenylhydrazone dicarboxylic acid, 3,4, benzophenone dicarboxylic acid, dimethyl 3,4'-benzophenone dicarboxylic acid, 4,4'- Benzophenone dicarboxylic acid, 4,4, dimethyl benzophenone dicarboxylic acid, 1,4-fluorenedicarboxylic acid, dimethyl 1,4-fluorenedicarboxylic acid, 4,4'-methylene Bis (gallic acid), 4,4'-methylenebis (gallic acid) dimethyl, oxalic acid, dimethyl oxalate, malonic acid, dimethyl malonate, succinic acid, dimethyl succinate, Methyl succinic acid, glutaric acid, dimethyl glutarate, 2-methylglutaric acid, 3-methylglutaric acid, adipic acid, dimethyl adipate, 3-methyladipate , 2,2,5,5-tetramethyladipate, pimelic acid, suberic acid, azelaic acid, Dimethyl azelaate, sebacic acid, 1,11-undecanedicarboxylic acid, 1,10-decanedicarboxylic acid, undecanedicarboxylic acid, 1,12-dodecanedicarboxylic acid, hexane Diacid, behenic acid, behenic acid, dimer acid, 1,4-cyclohexanedicarboxylic acid, dimethyl 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexane Alkanedicarboxylic acid, dimethyl 1,3-cyclohexanedicarboxylic acid, 1,1-cyclohexanediacetic acid, metal salt of 5-sulfo-dimethylisophthalic acid, fumaric acid , Maleic anhydride, maleic acid, hexahydrophthalic acid, phthalic acid, and the like and their derived mixtures. Diols that can be used in the preparation of polyesters include, but are not limited to, unsubstituted, substituted, linear, branched, cyclic aliphatic, aliphatic-aromatic, having from 2 to 36 carbon atoms Or aromatic diols. Specific examples of required diol components include ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,2-, 1,3-, and 1,4-butane-ίο-200306373 说明 Description of the invention continued Page alcohol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,19 · dodecanediol, 1,14-ten Tetradecanediol, ι, ι6-hexadecanediol, dimer diol, isosorbide, 4,8-bis (hydroxymethyl) -tricyclo [5 ^ .0 / 2.6] decane, 丨, 2_, 1,3- and ι, 4-cyclohexyl dimethanol, and long-chain diols and polyols prepared by the reaction products of diols or polyhydric alcohols and oxidative associations, including di (ethylene glycol ), Tris (ethylene glycol), poly (ether ether) glycol, poly (butylene ether) glycol, and the like and their derived mixtures. Preferred polyesters that can be used in the present invention are poly (ethylene terephthalate) ("2GT"), poly (trimethylene terephthalate) ("3GT"), and blends thereof and Copolymer. The term "item containing polyester" used in the present invention means an article having a surface composition of at least 10% polyester by area. In clothing applications, polyester-containing clothes often include other ingredients such as propionate, wool, silk, cotton, linen, flax, hemp, lynx, cellulose, wood pulp, cellulose Acetate or triacetate, Nylon 6 or Nylon 66, Poly (m-xylylene meta-phenylenediamine) (ς ΜΙΑ ', EI I. du Pont de Nemours and Company, Wilmington, DE, USA Sold under the trademark Nomex®), poly (terephthalamide-p-phenylenediamine) (4PPTA ', sold by E. I. du Pont de Nemours and Company, trademark Kevlar®), polyfluorenes such as polypropylene and polyethylene Women's, fiberglass' Lycra® spandex (sold by EI du Pont de Nemours and Company), and elastomers. It may contain polyester other than poly (ethylene terephthalate), for example, a copolymer having a low melting temperature as a binder fiber in a fiber filler. The composition of the aforementioned fibers can be used in the present invention to obtain other advantages 200306373 (7) Continued description of the invention. The fiber composition can be prepared by any means known to those skilled in the art. During the spinning process, two polymers can be formed side by side or arranged into a "bicomponent" filament in a sheath-core configuration. 2GT / 3GT bicomponent fibers such as those disclosed in U.S. Patent No. 3,671,379-incorporated herein by reference-are examples which can be used in the present invention.

Another way to prepare a fiber composition is to fully blend short fibers; that is, when spinning a short yarn, different fibers can be combined during carding or drawing. The fiber composition can also be prepared by weaving or weaving yarns, staple fibers or filaments having different compositions into the same fabric. In the case of Lycra® Spandex (E. I. de Nemours and Company, Wilmington, DE), the Spandex is added to the staple fiber yarn during the spinning step or during fabric manufacturing, such as when adding yarn during weaving.

The first step of the method of the present invention is to pre-treat objects containing polyester. The pretreatment involves hydrolyzing the surface of the polyester-containing article to allow subsequent attachment of the chitosan groups. This pretreatment is achieved by hydrolytic cleavage of part of the ester bonds in the polyester-containing article to generate carboxylate.

The hydrolysis treatment includes exposing a polyester-containing article to an alkaline aqueous solution. All soluble Group I, II and III hydroxides, ammonium hydroxides and hydroxides of alkyl-substituted ammonium can be used for hydrolysis. The base is soluble in water or a mixture of water and one or more water-soluble organic solvents. Examples of suitable water-soluble organic solvents include methanol, ethanol, propanol, ethylene glycol, propylene glycol, acetonitrile, dimethylformamide, and dimethylacetamide. The base which can be used in the present invention is generally an alkali metal hydroxide, and sodium hydroxide is most preferred. The concentration of alkali in this aqueous solution is not important, it depends on the alkali used -12- 200306373 (8) I Invention description continued page and processing temperature. In the case of sodium hydroxide, the concentration may be from 1-4% by weight. The processing temperature is not important and room temperature is preferred. A temperature ranging from 10 to 9 ° C can be used. A lower temperature is better than 4 for a higher concentration of alkali. The object is exposed to the alkali 'under the solution of Shengluo' until its weight decreases from 1 to 30%, so that 1 to 10 percent is better. The processing time depends on the concentration and temperature of the alkaline solution; the higher the concentration of the alkaline solution, the higher the temperature used, the shorter the processing time. It can be successfully used as short as 2 Time to 30 seconds. The object is then washed with water as necessary to remove most of the alkaline solution. After the hydrolysis treatment, the object is acidified by a strong inorganic acid treatment until the pH is lower than or equal to that by the hydrolysis treatment. The pKa of the resulting carboxylate. The object can be directly acidified with an aqueous solution of an inorganic or organic acid without involving water washing. However, water washing helps to minimize the amount of acid used. The term "strong, inorganic acid" used in the present invention Means acids whose pH is lower than pH 2. The inorganic acids used in the present invention include, for example, hydrochloric acid, sulfuric acid, and phosphoric acid. The most preferred is hydrochloric acid. The time and temperature of the acidification step are not important; they can be successfully used at room temperature. 2 seconds to 30 minutes. The object is washed again with water, as appropriate, to remove most of the inorganic acid. The object is then used directly in subsequent steps, or may be dried as appropriate. Without wishing to be bound by any particular theory, it is believed to be below carboxylic acid. Acidification at the pKa of the acid radicals results in the formation of free carboxylates, increasing the rate and efficiency of the reaction between the compounded substance and chitosan in subsequent steps. After the acidification step, the object uses chitosan Treatment. This treatment involves impregnating or wetting the object with a solution containing a chitosan reagent. The "chitosan reagent" used in the present invention, in the meaning of 200306373 (9) Description of the invention continued on All parts that are mainly made of chitosan, including chitosan, chitosan salt, and chitosan derivatives. Solutions containing chitosan reagents can be aqueous. However, Since chitosan itself is insoluble in water, the chitosan can be solubilized in a solution. The solubility is obtained by adding the chitosan to mono-, di- and polycarboxylates. It is obtained in a dilute solution of a water-soluble organic acid. This allows the chitosan to react with an acid to form a water-soluble salt, referred to herein as a "chitosan salt." "Chitin derivatives" includes N- and 0-carboxyalkyl chitosan which can be used directly in water instead of chitosan salt. Chitosan can also be used in lithium chloride or N- Methyl-morpholine-N-oxide is dissolved in a specific solvent such as dimethylacetamide. In the present invention, the solubilized chitosan solution can be used instead of containing chitosan An aqueous solution of salt or chitosan derivative. The chitosan solution is generally an acetic acid aqueous solution, for example, containing 2% chitosan and 0.75% acetic acid or 2% chitosan and 1.5% acetic acid. Aqueous solution. The treatment time is generally 5 to 30 minutes. The processing temperature is not important, but room temperature is preferred. After treatment with the chitosan solution, the excess solution can be removed by dripping, or it can be removed by rolling or spinning. The treated object is then dried by drying or a combination of ambient air drying and drying, as appropriate. The articles prepared by the aforementioned method have antimicrobial properties. The term "antimicrobial" as used in the present invention means both bactericidal and fungicidal. In addition, the treated fibers and yarns have good physical properties such as toughness, elongation and feel. The antimicrobial properties may be determined by soluble metal salts such as soluble 200306373 _ (10) Description of the invention continued page

The silver salt, the soluble copper salt, and the soluble zinc salt are further improved by treatment. The preferred metal salt of the present invention is an aqueous solution of zinc sulfate, copper sulfate or silver nitrate. The metal salt is generally applied by dipping or padding a dilute (0.1 to 5%) solution of the salt in water. The degree of improvement depends on the specific metal salt used, its concentration, exposure time and temperature, and the particular chitosan treatment-the type of chitosan reagent, its concentration, temperature, and exposure time. Examples 3, 4, 5, 6 and 7; Figures 7, 8, 9, 10 and 11; and Table 1 illustrate the effect of metal salts in the method of the present invention. Articles prepared by the aforementioned method of the present invention also have improved antistatic properties. Antistatic properties mean the ability of a fabric to dissipate static charges and prevent the buildup of static electricity. (Dictionary of Fiber & Textile Technology, Hoechst Celanese Corp., Charlotte, NC (1990), p. 8) o

Another optional post-treatment involves applying a polymer containing a carboxyl group to a deacetylated chitin-treated object, or a metal salt-treated deacetylated polysaccharide-treated object. The "carboxyl-containing polymer" used in the present invention means a polymer containing a carboxylic acid group in a side chain connected to the main chain of the polymer. The carboxyl-containing polymer, preferably polyacrylic acid, is generally applied from a dilute aqueous solution by impregnation or padding. Any of the aforementioned chitosan-treated articles, metal salt-treated articles, or carboxyl-containing polymer-treated articles can benefit from further deacetylated chitin solution treatment. The objects included in the scope of the present invention which are subjected to the first treatment with chitosan by the method of the present invention are further performed one or more times with any metal salt, carboxyl group-containing polymer and / or additional chitosan in any order The prerequisite for the treatment is that the surface of the final object is treated with -15-200306373 _ (11) Description of the Invention Continued metal salt or chitosan solution. In a preferred embodiment, the method of the present invention further comprises heating the polyester-containing object grafted with chitosan under nitrogen or an ambient atmosphere to a temperature from 35 ° c to 190 ° C for 30 seconds to 20 hours, The object was washed with deionized water and dried at a temperature of 35 ° C to 19 ° C for 30 seconds to 20 hours. The object of the present invention can also be prepared by a continuous method. This method is illustrated by Figure 20 of the accompanying drawings of the present invention . Now referring to FIG. 20, the figure shows the following invention

Device for continuous steps: (a) Set the feeding table (2), with the polyester-containing object (1) above it. The feed table generally comprises one or more feed rollers (10). (b) The object is pulled out from the feeding station and passed through the first processing station (4), in which the object is exposed to an alkaline solution. The processing station here is generally an immersion bath or tank.

(c) The object is pulled out from the first processing station via the second processing station (5), and the object treated in step (b)-is exposed to water in this station. Optionally, one or any number of pull rollers (11) are used to help guide the object between the processing stations. A draw roller, such as a draw roller (11), can be placed at any step in a continuous process, as is well known in the art. (d) The object from the second processing station is drawn through the second processing station (6), where the object treated in step (c)-is exposed to a strong inorganic acid solution. (e) The objects from the third processing station are drawn through the fourth processing station (7) as appropriate, in which the objects treated by step (d)-are exposed to water. (f) The object is then pulled through the fifth processing station (8), in which the object treated in step (d)-or step (e)-is exposed to a solution containing chitosan-16 -200306373 (12) Description of the invention Continuing solution of reagents. As discussed earlier, the chitosan reagent is selected from chitosan, chitosan salt, and chitosan derivatives. The processing station is generally an immersion bath tray or tank.

(g) The step (f) -treated object is heated by a heater such as a heater roller assembly (9) after leaving the chitosan processing station as appropriate.

(h) The processed object (f > or step (g)-) is then received and accumulated on the take-up table (3). The processed object is usually wound around the coil by a lateral guide (12) On the take-up table (3), this table is generally one or more rigid paper or resin bobbins to form a spinning shuttle.

The feed table, processing table, heater, and take-up assembly can be any convenient mechanism known in the art to continuously process fibers and yarns (see, for example, Ullmann's Encyclopedia of Industrial Chemistry, Fifth Edition, Wolfgang Gerhartz, Executive Editor, Volume A10, VCH Verlagsgesellschaftg, Weinheim, Federal Republic of Germany (1987), "Fibers, 3. General Production Technology," H. Lucker, W. Kagi, U. Kemp, and W. Stibal Pp. 51 1-566). The continuous method is particularly suitable for processing polyester-containing fibers or yarns on an industrial scale. The method and articles of the present invention do not use a cross-linking agent, making this method an existing method that requires the use of a cross-linking agent. More effective and more economical. The term "crosslinking agent" encompasses bi- or tri-functional cross-linking agents commonly used in the technical field. The carboxyl-containing polymer such as polyacrylic acid cannot be interpreted as a cross-linking agent in the present invention. The articles of the present invention are preferably fibers; fabrics such as woven and non-woven fabrics; fibers, films, and articles and structures made therefrom. Biological objects shall be applicable to applications such as clothing, including sports-17-200306373 (13) I Description of the invention Continuing clothing, active clothing, lingerie, swimwear and medical outerwear; health care, including medical fabrics, antimicrobial wipes, surfaces ( Counters, floors, walls), personal hygiene products and medical packaging; household items, including stuffing, beds, window treatments and surfaces; and food handling / appliances, including absorbents for packaging, meat packaging, antimicrobial pads, antimicrobials Wipes and surfaces Example materials and methods:

The following examples use the following fiber-based materials. Woven and woven fabrics were also tested as described in the examples. 1. Poly (ethylene terephthalate) ("2GT") fibers, woven fabrics and microfiber woven fabrics, available from EI du Pont de Nemours and Company (Wilmington, DE) o 2. Sorona® Poly (trimethylene terephthalate) ("3GT") yarn, 70 denier, 34 filaments, circular cross-section, manufactured by EI du Pont de Nemours and Company (Wilmington, DE).

The chitosan material used in this study was purchased from Primex Ingredients ASA, Norway under the trademark Chitoclear® chitosan and was used in the form of purchase. All examples demonstrate the use of chitosan, that is, chitosan dissolved in acetic acid, as the chitosan reagent of the present invention. Treated items are tested for antimicrobial properties by the Shake Flask Test for Antimicrobial Testing of Materials: 1. A single isolated colony from a bacterial or yeast agar dish culture is inoculated in a sterile flask from 15 to 25 ml of pancreas digested soy flour broth (TBS). At 25 -18- 200306373 (14) I Description of Invention Continued to 37 ° C (using the highest growth temperature for specific microorganisms) Incubate 16 to 24 with or without shaking (select appropriate aeration conditions for specific strains) hour. For filamentous fungi, spore-forming culture lines were prepared on agar culture1. 2. The overnight yeast culture was diluted in a sterile phosphate buffer pH 6.0 to 7.0 (see below) to obtain about 105 colony forming units (cfu / ml) per milliliter. The total volume of phosphate buffer required is 50 ml X number of test flasks f (including control group). For filamentous fungi, prepare a spore / ml spore suspension. Spore suspensions are prepared by gently resuspending spores from agar culture m-which have been filled with sterile saline or phosphate buffer-. To obtain the original inoculation count, inoculate pancreatic digested soybean agar (TSA) culture dishes in duplicate at 10-4 and 10.3 final dilutions (prepared in phosphate buffer). Petri dishes were incubated overnight at 25 to 37 ° C. 3.50 ml of inoculated phosphate buffer is transferred into each sterility test flask containing 0.5 g of the material to be tested. Control flasks inoculated with phosphate buffer and without phosphate buffer were also prepared without test materials. 4. All flasks were placed on a pendulum shaker and incubated at room temperature under vigorous shaking. All flasks were sampled regularly, and appropriate dilution plates were inoculated on Ding SA petri dishes. The TSA petri dishes were incubated at 25 to 37 ° C for 16 to 48 hours, and colonies were counted. 5. Colony count is recorded as the number of colony forming units per milliliter (cfu / ml). 6. The value of the activity constant Δί is calculated as follows: Δΐ = (> B, where At is the activity constant of contact time t, and C is the average ogiQ density of the microorganisms in the untreated control material flask after being cultivated for X hours, and β system is the average density of 10 giG of microorganisms after being treated for X hours in the He Ke flask after treatment 200306373 (15) Description of the invention. M_ is generally calculated at 4, 6 or 24 hours, and can be expressed as Δ, Masterbatch salt transfer buffer: 22.4 grams of monopotassium phosphate, 26.0 grams of dipotassium phosphate, 56.0 grams of deionized water. The pH of the phospholipid buffer was increased to pH 6.0 with NaOH or HC1. 0. This parental tellurate buffer is filtered, sterilized, and stored at 4 C before use. The osmate buffer is prepared by diluting 1 ml of the masterbatch phosphate buffer with 800 ml of sterile deionized water. Example 1 Weaving 2GT and 3GT woven fabrics into the g fabric (8 inches x 9 inches; 3GT fabric weighs 21.8 grams, 2GT fabric weighs 19 5 grams) sighed to 10% hydrogen In the sodium oxide aqueous solution, shake gently for 90 minutes. Each time is k; first; After 30 minutes in an aqueous solution of hydrochloric acid, deionized water was used; first it was stripped and dried in 2 hours for 1 hour. Then each was immersed in an aqueous solution containing 1.5% acetic acid < After 30 minutes, I only know that the chitosan used in Example 1 is a food-grade Chitoclear® enzyme pr (mex Ingredients aSA, Norway). The degree of N-deacetylation of this sample is More than 90%, this can be confirmed by proton and carbon 13 NMR spectra ^ ^ The molecular weight of this sample is estimated using the standard relative viscosity measurement described in the literature. The excess of chitosan was dropped, air-dried for one hour, and then 8) Dry under nitrogen at 16 ° C. The weight of the woven group grafted with chitosan was 3GT, 24.06 g; 2GT, 21.32 g. The fabric was then washed with water-20- 200306373 (16) Description of the invention, continued washing at 80 ° C for 16 hours, resulting in a 3GT sample weighing 23.3 grams and a 2GT sample weighing 20.6 grams (individual 6.8 and 5.6% Acetyl chitin incorporation). The antimicrobial effect of these fabrics was measured as previously described. Figure 1 shows the anti-biological effect of chitosan grafted on 3GT woven fabrics on Listeria monocytogenes ATCC 153 13. Fig. 2 shows the antimicrobial effect of deacetylated polysaccharide grafted on 2GT woven fabrics on Klebsiella pneumoniae ATCC 4352. Fig. 3 shows the antimicrobial effect of acetochelan polysaccharide grafted on 2GT woven fabric on Candida albicans ATCC 10231. Fig. 4 shows the anti-biological effect of chitosan grafted on 3GT woven fabric on Staphylococcus aureus ATCC 6538. Chitosan grafted on 2GT and 3GT polyester fabrics demonstrated at least 3-log reduction in the following microorganisms in 4 to 6 hours: E. coli ATCC 25922 E. coli ATCC 49106 (enteric toxicity / enteric hemorrhagic) Large intestine Bacillus 〇 157: H7 (enteric toxicity / enterohemorrhagic) Salmonella cholerae ATCC 9239 Staphylococcus aureus ATCC 6538 Bacillus subtilis ATCC 6633 Enterococcus faecalis ATCC 29212 Klebsiella pneumoniae ATCC 4352 Listeria monocytogenes ATCC 15313 Listeria welshimeri ATCC 35897 200306373 (17) Description of the invention Continued Pseudomonas aeruginosa ATCC 27853 Candida albicans ATCC 10231 Acinetobacter albicans Acinetobacter sp. ATCC 14291 Micrococcus iuteus ATCC 4698 Staphylococcus cohnii ATCC 49330 Human Staphylococcus hominus ATCC 27844 Example 2 Chitosan with different molecular structures Evaluation of grafting and formation of test specimens on 2GT fabrics Over 80% and molecular weight between 950,000 (Pfansteihl, USA), 630,000 (Sigma Chemical Company, USA), 290,000 (Kitomer, Canada), 104,000 (Chitoclear®, industrial grade, Primex Ingredients ASA, Norway), 83,000 (Chitoclear® , Industrial grade, Primex Ingredients ASA, Norway), 74,00 (Chitoclear®, food grade, Primex Ingredients ASA, Norway), 39,000 (chitoclear®, food grade, Primex Ingredients ASA, Norway) and 33 〇〇〇 (chitoclear®, food grade, Primex Ingredients ASA,

Samples of chitosan in the range of Norway were grafted on polyester fabrics to evaluate the effect of molecular weight of chitosan on antimicrobial activity. A 1% solution of each commercially available chitosan in a 0.75% aqueous acetic acid solution was used in the grafting method as described in Example 1. As shown in Fig. 5 (2GT; E. coli ATCC 25922) and Fig. 6 (2GT; Staphylococcus aureus ATCC 29213), the method of the present invention can be performed using chitosan having a molecular weight in a wide range. Example 3 -22- (18) (18) 200306373 Description of the Invention Continued page B-chitosan grafted weaving example method 3GT woven fabric (22.8g) grafted with deacetylated chitosan was immersed in 2 After 30 minutes in a% silver nitrate aqueous solution, it was thoroughly washed with water and dried at 37 c for 16 hours. The weight of the resulting fabric was 230 grams. Similarly, the 3GT woven fabric (23.1 g) grafted with deacetylated chitin prepared by the method of male example 丨 was treated with a 2% sulfuric acid steel solution as described above, so as to reduce to 4 copper-containing fabrics. (23.7 g). As shown in the results obtained, the metal # 4 of the chitosan-grafted polyester can be used to increase antimicrobial activity β silver nitrate (Figure 7), copper sulphate (Figure 8) or-by the same method -Zinc sulfate is successfully used as a metal dopant. Figure 7 illustrates the results of 3GT fabrics grafted with chitosan with or without silver nitrate dopant against Salmonella cholerasuis ATCC 9239. Fig. 8 shows the results of 3GT fabrics prepared using grafted deacetylated chitosan with and without copper sulfate treatment against E. coli 0 157: H7. Chitosan, which has been grafted on 2GT and 3GT polyesters and has been doped with metal, has been shown to make at least 3-10 g of the following antimicrobial agents more resistant to antimicrobial agents within 4 to 6 hours. Reduced: E. coli ATCC 49106 (enteric toxicity / enterohemorrhagic) E. coli 〇 157: H7 (enteric toxicity / enterohemorrhagic) Salmonella choleraesuis ATCC 9239 will use Example 4 Chitosan-grafted fabrics are in use _ different concentrations of silver nitrate Manufacture after solution treatment ^ -23-200306373 (19) Description of the invention Continuation sheet The (5) 2GT knitted fabric in the form of socks is immersed in water to remove excess water, and then treated with 40% sodium hydroxide aqueous solution for 2 minutes. These ceremonies were thoroughly washed with water, immersed in a 1 M aqueous hydrochloric acid solution for 2 minutes, and then washed with water. The socks were then immersed in a 1% aqueous solution of chitoclear (Chitoclear®, food grade, molecular weight 74,000, Primex Ingredients ASA, Norway) containing 0.75% acetic acid. After 2 minutes, the excess solution was eliminated, and the temperature was at 85 ° C. The socks were dried under nitrogen for 16 hours. These dried samples were washed with water and dried again. Four samples were individually treated with 0.5%, 0.25%, 0.125% and 0.0625% silver nitrate aqueous solutions for 2 minutes, washed with water, and dried at 45 ° C for 16 hours. Evaluate the antimicrobial activity of these 4 samples and "control group containing only chitosan," Figure 9 shows the antimicrobial effect of these 5 samples on S. aureus ATCC 6538. Even the lowest concentration of silver nitrate (0.0625% ), Can still be very effective against Staphylococcus aureus ATCC 6538, as shown in Figure 10, and 0.001 ° /. Silver nitrate doping agent can just fight microorganisms that can only be killed with chitosan-silver , Such as E. coli 0157: Η7. It is inferred that a low concentration of silver is used in conjunction with deacetylated husks and multi-bran to achieve this effect. Cream Example 5 Zhengyi uses various deacetylated bismuth for 4 hours to use And without using ^^ 丄 〇 / 〇 筮 nitrate_: after treatment, preparation of deacetylated chitosan grafted 2GT fabric samples was hydrolyzed and treated with 2% deacetylated chitin using the method of Example 4 In different places, the chitosan treatment time is individually 0.5, 1 or 2 minutes. Each part of the three samples is treated with a 0.1% silver nitrate solution, as shown in Example 4. Figure 10 shows the connection Chitosan branched on 2GT fabrics was used after these different hydrolysis times. And -24- (20) 200306373 without the use of 0.1% silver nitrate post-treatment Description of the invention Continuing the antimicrobial effect on the large intestine face 157 ... Washing test (with and without _ 1 acid silver post-treatment) 3GT fabric samples grafted with sugar in the deacetylation department-with and without silver nitrate treatment (individual Yushen # 7 ^ in actual case 3) And the 3GT sample prepared in Example 1) was subjected to an AATCC RA 88 "C" washing cycle. The following table shows the results of these shake flask samples of E. coli ATCC 25922 washed with 3GT fabrics. At is the log reduction between the inoculation pair and 4 samples. As shown in Table 1, all deacetylated polysaccharides and deacetylated chitin + silver-treated fabrics were exposed to 4 hours after exposure to reduce the live population of large intestinal club face ATCC 25922 by at least 3 logarithms. Table shows the use of 3GT woven fabrics prepared with grafted chitosan with and without silver nitrate post-treatment against E.coli ATCC 25922. At 3 l of fabric at 4 h of At 3 GT control group without washing. 0.000 0.000 3GT control group, after washing 0.267 0.160 3GT + chitosan, without washing 4.869 5.415 3 GT + chitosan, after washing 2.315 3.813 3GT + chitosan + Ag, without washing 5.568 5.415 3GT + Acetyl chitosan + Ag, washed 5.568 5.415 Example 7 Free deacetylated chitosan, 2GT grafted with deacetylated polysaccharide, and silver nitrate post-treatment treated with deacetylated chitin-grafted 2GT Antimicrobial activity test Two pieces of 2GT polyS fabric were subjected to a standard machine (individually 5.56 and 5.9 grams) as described in Example 1 by grafting with 2% deacetylated chitin solution to produce deacetylated brew Chitosan-grafted fabrics (the individual weights after grafting are 6.2 grams and 6.6 grams) ° Houyi-25-200306373 Description of the invention Continuation sheet Wash with water at 37 ° C

Ethyl chitosan powder was tested in the shake flask as it is. Figure 11 shows the free deacetylated chitin, which was dipped in 0.5% silver nitrate solution on a grafted fabric sheet (6.6 grams) and dried and grafted. Antimicrobial activity of polysaccharides and chitosan grafted with silver nitrate on Staphylococcus aureus ATCC 6538. Free chitosan showed lower antimicrobial activity, and compared with chitosan grafted on polyester with or without silver nitrate post-treatment, it had more bacteriostatic characteristics. For the 2GT fabric, four 2GT fabrics (sample AD, individually 19.5, 18.8, 19.5, 19.7 g) were used as the multilayer rolls of chitosan and polyenoic acid. Graft as described in Example 1. To chitosan. The weights of the products A-D were individually 21.3, 20.4, 21.2 and 21.1 grams. Fabric samples A and B were immersed in a 2% polyacrylic acid solution for 30 minutes, air-dried and washed with water, and then dried at 80 ° C to produce a fabric coated with chitosan polyacrylic acid Y (21.5 G) and B, (20.6 g). A part of fabric A (10.3 g) was treated with a 2% chitosan solution, dried at 85 ° C for 16 hours, and then washed with water and dried to produce A " (10.5 g). A. Another part (11.2 g) was immersed in a 2% silver nitrate solution for 30 minutes, washed with water and dried at 37 ° C for 16 hours to produce A '". The weight of A ... is 11.02 grams. Figure 12 shows 2GT + chitosan (A); 2GT + chitosan deca-acrylic acid (Af '); 2G1 > chitosan + polypropionic acid + chitosan (A "); and 2GT + chitosan + polyacrylic acid + silver nitrate (A ...) and three kinds- 26- 200306373 ^ 22) Description of the invention Continuing the antimicrobial activity of different control groups against E. coli 25922. Example 9 Chitosan-grafted fibers prepared in commercially available prototype equipment The chitosan chemistry described in the previous examples can also be applied to fibers as standard using standard fiber processing equipment. Explained by the alkaline hydrolysis, acidification, and deacetylation chitosan grafting steps in a roll dyeing machine, and by the alkaline hydrolysis and acidification in a roll dyeing machine, and deacetylation chitin in a single end sizing machine Method for preparing antimicrobial fibers by grafting. Fig. 13 shows the antimicrobial performance of 2GT fibers grafted with chitosan as a result of treatment in a roll stainer against E. coli ATCC 25922. Fig. 14 shows the antimicrobial performance of 2GT fibers applied with grafted chitosan due to treatment in a roll dyeing machine and a single-end sizing machine relative to E. coli ATCC 25922. Example 10 Bicomponent fiber treated with chitosan: 2GT / Lycra (R) blend

Lycra® Spandex / 2GT Blend (containing 10% 10 Daniel Lycra® and 90% 150 Daniel Dacron® Lycra® Spandex / 2GT Blended Fiber, EI du Pont de Nemours and Company, (Wilmington, DE) (Production) As in Example 1, an alkali treatment was used. The treated fibers were passed through a chitosan solution in a single-end sizing machine as in Example 9. Figure 15 shows the antimicrobial effect of the chitosan-treated fiber relative to E. coli ATCC 25922. Example Π Deacetylated chitosan treatment of polyester yarns usually combined with fabrics-27- 200306373 Description of the invention continued (23) Cotton yarn (yarn count 30 / lcc, Parkdale Mills, Inc. (Gastonia, NC )), Soft White® 24 acrylic acid yarn (1/24 worsted yarn count, 1 1/2 " warp length, 100% free-end spinning, with top, Amital Spinning Corporation (New Bern, (Manufactured by NC), and Tactei® 6 ° (30 denier dressing (E. du Pont de Nemours and Company, Wilmington, DE)) were treated with alkali as in Example 1. The treated fiber was passed through the chitosan solution as in Example 9. Figure 6 shows the antimicrobial effect of the chitosan-treated yarn relative to E. coli ATCC 25922.

Example 12 Chitosan-treated polyester / polyester non-woven cloth sold by Sontara © wipes (E. I. du Pont de Nemours and Company (Wilmington, DE)) ) Was treated as in Example 1, one of the samples was treated using only the alkali treatment described therein, and one was treated with a fully deacetylated chitin graft treatment. The antimicrobial effect of the chitosan grafting treatment on E. coli ATCC 25922 is shown in Fig. 17.

Example 13 Chitosan-treated polyester / cellulose nonwoven cloth sold by Sontara® rag (E · I · du Pont de Nemours and Company (Wilmington, DE)) ) Was treated as in Example 1, one of the samples was treated using only the alkali treatment described therein, and one was treated with a fully deacetylated chitin graft treatment. The antimicrobial effect of the chitosan grafting treatment on E. coli ATCC 25922 is shown in FIG. 18. -28- 200306373 Description of Invention Continued (24) Examples 14 to 18 (a) Preparation of 2GT fiber with undercoat on the surface 2GT fiber (150-200 g, 229 g) was passed at a rate of about 8 m / min A series of solution plates containing a 10% aqueous solution of hydroxide bromide '1.0 M aqueous hydrochloric acid' and water sequentially. Excess solution was removed from the fibers using sponge. The fiber was then wound on a drum heated to about 130 ° C for drying. The fiber was then wound using a tension final yarn machine, and then the fiber was heat-set at 160 ° C by winding a heated drum at that temperature and winding at a speed of 60 m / min. The yield of the fiber was 218.7 grams, with a loss of 4.5 weight percent. This method proves that the hydrolysis treatment results in fiber weight loss. This method results in the formation of carboxyl groups on the surface of the fiber, as evidenced by the dyeing of the fiber with a blue dye for acidic groups. (b) Preparation of 2GT fibers and fabrics treated with chitosan. 2GT fibers (150-200 g) were passed through a series of 10% aqueous steel hydroxide solution, 1.0 M at a rate of about 8 m / min. A solution tray of a solution of hydrochloric acid in water, water, and chitoclear® (Primex Ingredient, Norway) in a 1% aqueous solution of acetic acid. The concentration of chitosan is from 0.25 to 2 weight percent, as shown in Table 1. Use sponge to remove excess solution from the fiber. The fiber was dried by winding it on a drum heated to about 130 ° C. The fiber was then wound using a tension winder, and then the fiber was heat-set at 160t by winding a heating roller at that temperature and winding at a speed of 60 m / min. In this case, the fiber treated with chitosan was dried using Orange II, and the orange color showed that the chitosan was located on the surface of the fiber. The fiber has been treated with 2% chitosan solution to make fabric. -29- 200306373 (25), description of the continuation sheet, and drying and dyeing using lamp color II. This strong orange color shows that chitosan is present on the surface of the fabric. Table 2 Examples of original weight (g) Final weight (g) Weight change (%) Chitosan concentration (% by weight) Surface surface coating only 229 218.7 -4.5 0 -4.5 14 207 231 11.6 2 15 141 154 9.2 1.5 16 165 174 5.5 1 17 119 133 11.8 0.5 18 216 237 9.7 0.25 Example 20 Preparation of antimicrobial chitosan-2GT / 3GT fiber was borrowed from E. du Pont de Nemours and Company (Wilmington , DE) 2GT / 3GT bicomponent fibers pass through a series of 歹 at a rate of about 8 meters / minute, j sequentially contains 10 ° /. Solution dish of a solution of sodium hydroxide aqueous solution, 1.0 M hydrochloric acid aqueous solution, water, and 0.25% chitoclear (Chitoclear®, Primex Ingredient ASA, Norway) in a 1% acetic acid aqueous solution. Use sponge to remove excess solution from the fiber. The fibers were dried by winding on a drum heated to about not. The fiber was then wound using a tension winder, and then the fiber was heat-set at 160t by being heated at a temperature of a heating drum at this temperature and being wound at a speed of 60 m / min. Two samples were taken from different parts of the fiber and subjected to antimicrobial evaluation. The antimicrobial effect of the chitosan grafting treatment on E. coli ATCC 25922 is shown in FIG. 19. :; -30- 200306373 (26) Description of the Invention Continued Brief Description of Drawings The drawing has 20 of the following drawings:

FIG. 1 is a graph showing the antimicrobial effect of chitosan grafted on a 3GT woven fabric on Listeria monocytogenes ATCC 153 13.

Figure 2 is a graph showing the antimicrobial effect of chitosan grafted on 2GT woven fabrics on Klebsiella pneumoniae ATCC 4352. Fig. 3 is a graph showing the antimicrobial effect of chitosan grafted on 2GT woven fabric on Candida albicans ATCC 10231. Figure 4 is a graph showing the antimicrobial effect of chitosan grafted on 3GT woven fabrics on Staphylococcus aureus ATCC 6538. Figure 5 is a graph showing the antimicrobial effect of chitosan of various molecular weights grafted on 2GT woven fabrics against E. coli ATCC 25922.

Figure 6 is a graph showing the antimicrobial effect of chitosan of various molecular weights grafted on 2GT woven fabrics against Staphylococcus aureus ATCC 29213.

Fig. 7 is a graph showing the antimicrobial effect of chitosan grafted on 3GT fabric on Salmonella cholerasuis ATCC 9239 with and without silver nitrate treatment. Figure 8 shows the deacetylacetin grafted on 3GT fabric to E. coli 0157: H7-31-200306373 with and without copper sulfate treatment. Description of the invention continued page (27 ) Diagram of antimicrobial effect. Figure 9 is a graph showing the antimicrobial effect of chitosan grafted on 2GT fabric on Staphylococcus aureus ATCC 6538 when treated with various concentrations of silver nitrate solution after treatment. Figure 10 shows the antimicrobial activity of Escherichia coli (E. coli) 〇157: H7 grafted on 2GT fabric after various hydrolysis times with and without the use of 0.1% silver nitrate post-treatment. Effect illustration. Figure 11 is a graph showing the antimicrobial activity of free chitosan relative to chitosan grafted on 2GT fabrics against S. aureus ATCC 6538. Figure 12 shows the antimicrobial activity of Escherichia coli 25922 grafted on 2GT woven fabrics with various polyacrylic acid post-treatments, additional chitosan and / or silver nitrate treatment. Fig. 13 is a graph showing the antimicrobial effect of diacetylacetin grafted on 2GT fibers by treatment in a packaging dryer relative to E. coli ATCC 25922. Fig. 14 is a graph showing the antimicrobial effect of chitosan grafted on 2GT fibers by treatment in a package dryer and a single-end sizing machine relative to E. coli 922. FIG. 15 is a graph showing the effect of chitosan-treated polyester and Lycra® blended fibers on the microorganisms of E. coli ΔΓΓΓ P ^ " Aid 2d922. The figure shows the antimicrobial effect of a small amount of chitosan used in polyester blends on E. coli ATCC 25922. Figure 〃 is a polyester / polyester non-woven cloth that has not been treated with chitosan-32- Description of the Invention Continued 200306373 (28) Antimicrobial effect on E. coli ATCC 25922. Figure 18 shows Antimicrobial effect of chitosan-treated polyester / water slurry nonwoven on E. coli ATCC 25922. Figure 19 shows the two-component (2GT / 3GT) polyester fiber pair treated with chitosan. The antimicrobial effect of E. coli ATCC 25922. Fig. 20 is a flow chart of a continuous method for manufacturing antimicrobial-containing polyester articles according to the present invention. Symbol representations of the drawings 1 Polyester-containing articles 2 Feeding table 3 Winding table 4 A processing table 5 a second processing table 6 a third processing table 7 a fourth processing table 8 a fifth processing table 9 a heater roller assembly 10 a feeding roller 11 a drawing roller 12 a lateral guide Λ ^ -JJ-

Claims (1)

200306373 Patent application scope 1. A method for preparing antimicrobial polyester-containing articles, comprising the following successive steps: (j) providing polyester-containing articles; (k) contacting the polyi-containing article with a test solution; (l) Wash the articles prepared in step (b) as appropriate; (m) Contact the articles prepared in step (b) or step (c) with a strong inorganic acid solution; (η) Wash the steps (d) as appropriate ); (0) contacting the article prepared in step (d) or step (e) with a solution containing a chitosan reagent, the reagent is selected from the group consisting of chitosan, Contact of the solution of the group consisting of the chitosan salt and the chitosan derivative; (P) heating the article prepared in step (f) as appropriate; (q) step (f) or step of separation (G) the article produced; and (r) optionally the article heated in step (h) at a temperature higher than that of step (g). 2. —A method for manufacturing antimicrobial-containing polyester articles, including the following successive steps: (a) providing a feeding table equipped with articles containing polyg, and a take-up table capable of receiving the polyester articles; ( b) pulling the object from the feeding table through the first processing station, where the object is exposed to the test solution; (c) drawing the step (b) -processed object to pass The second processing station, where the object is exposed to water; 200306373 Patent Application Continued (d) Pulling the objects treated by step (b)-or step (c)-to pass through the third processing station, the The object is here exposed to an inorganic acid solution; (e) if necessary, the object treated in step (d)-is drawn to pass through the fourth processing station, where the object is exposed to deionized water; ( f) pulling the object treated in step (d)-or step (e)-to pass through the fifth processing station, where the object is exposed to a solution containing a chitosan reagent; (g) in its After leaving the chitosan processing station, the objects treated in step (f)-are heated as appropriate; and (h) after step (f) -or Step (g)-The processed items are received by the take-up station and accumulated there. 3. The method of claim 2 in which the steps of (b) and (c) are performed together for a time sufficient to reduce the weight of the item by 1 to 30 percent. 4. The method according to item 2 of the patent application, wherein steps (b) and (c) are performed together for a time sufficient to reduce the weight of the object by 1 to 10 percent. 5. The method of claim 1 or claim 2, wherein the alkaline solution comprises a solution selected from the group consisting of soluble Group I hydroxides, soluble Group II hydroxides, soluble Group III hydroxides, and ammonium hydroxide And a base composed of an alkyl-substituted ammonium hydroxide; and the base is dissolved in water or a mixture of water and one or more water-soluble organic solvents, the organic solvent is selected from the group consisting of methanol, ethanol, and propanol , Ethylene glycol, propylene glycol, acetonitrile, dimethylformamide, and dimethylacetamide. 6. The method of claim 1 or 2, wherein step (b) is performed at a temperature of 10 ° C to 90 ° C. 200306373 Scope of Patent Application Continued 7. The method according to item 1 or 2 of the scope of patent application, wherein the strong inorganic acid solution comprises a strong inorganic acid with a pKa of less than 2. 8. The method of claim 1 or 2, wherein the solution comprising the chitosan reagent is a solution of chitosan in a water-soluble dilute organic acid, and the organic acid is selected from the mono- , Di- and polycarboxylic acids. 9. The method according to item 1 or 2 of the scope of patent application, wherein the solution comprising the deacetylated polysaccharide reagent is deacetylated polysaccharide in a dilute aqueous acetic acid solution. 10. The method according to item 9 of the patent application range, wherein the solution comprises a dilute aqueous acetic acid solution in an amount of 0.25% to 5.0% by volume and chitosan in an amount of 0.25% to 8.0% by weight of the solution. 11. The method according to item 1 of the patent application range, wherein the washing in step (c) and step (e) is performed using deionized water. 12. The method of claim 1 or 2, wherein the heating in step (g) is performed at a temperature of 35 ° C to 190 ° C. 13. The method of claim 1 or 2, wherein the heating in step (g) is performed for 30 seconds to 20 hours. 14. The method according to item 3 of the patent application, wherein the time sufficient to reduce the weight of the object is 2 seconds to 30 seconds. 15. The method of claim 1, further comprising combining the article prepared in step (f), (g), (h) or (i) with a solution including a metal salt, including a polymer having a carboxyl group Contact with the solution, the additional solution including the chitosan reagent, or the composition thereof, wherein the surface of the manufactured article comprises chitosan, metal salt, or a combination thereof, which is the scope of the patent application for deacetylation 200306373. 16. If the method of claim 2 is applied, it further includes pulling the object treated by step (f)-, step (g)-or step (h)-to pass through the subsequent stage, and this stage is installed Contact with a solution containing a metal salt, a solution including a polymer with an end group, an additional solution including a chitosan reagent, or a combination thereof, in which the surface of the produced object contains chitosan, a metal salt , Or a combination thereof. 17. The method of claim 15 or 16, wherein the metal salt is selected from the group consisting of a soluble silver salt, a soluble copper salt, and a soluble zinc salt. 18. The method of claim 15 or 16, wherein the metal salt is selected from the group consisting of silver nitrate, copper sulfate, and zinc sulfate. 19. The method of claim 15 or 16, wherein the carboxyl group-containing polymer is polyacrylic acid or sodium carboxymethyl cellulose. 20. The method of claim 1 or 2, wherein the polyester-containing article is in the form of a filament, fiber, yarn, fabric or film. 21. The method of claim 1 or 2, wherein the polyester is selected from the group consisting of polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, And its copolymers and blends. 22. The method of claim 1 or 2, wherein the polyester-containing article is in the form of a two-component fiber, which is basically made of polyethylene terephthalate and polytrimethylene terephthalate. composition. 23. —An antimicrobial and polyester-containing article, which is produced by the method described in item 1 of the scope of patent application. 200306373 Scope of Patent Application Continued Page 24 · —An antimicrobial and polyester-containing article, which is made by the method in the second scope of patent application. 25. —An antimicrobial and polyester-containing article 'having an upper layer grafted with acetopolysaccharide. 26. If the antimicrobial and polyester-containing article of the scope of application for the patent No. 23, 24 or 25 further comprises one or more groups selected from the group consisting of metal salts, polymers containing several groups, and combinations thereof compound of. 27. If the antimicrobial and polyester-containing article of item 26 of the patent application scope, wherein the surface of the article includes chitosan, metal salt or its group of characters Item 25 containing polyester, wherein the polyester is polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, or a copolymer or blend thereof Compound y 29. As for the articles containing polyester in item 23 of the scope of patent application, the 1 tang jia articles are in the form of two-component fiber, which is basically made of polyparaben-Tian #, Purpose and composition of polytrimethylene terephthalate. 30. If the scope of the patent application is No. 23, 24 or 25, this article is used to esterify the k 1 3, wherein the article is a filament, fiber, yarn, fabric or fabric. 31. If the scope of the patent application is No. 26, Contains polyester sclerophylla spp., &Gt;, Aibai '', in which the metal salt is grouped. And soluble zinc salt group 32. If the scope of the patent application is No. 26, the content of the polyester is 仵, wherein the metal salt is selected from the group consisting of silver nitrate, copper sulfate, and zinc sulfate. Item containing polyester ^ See, take-in pieces, where the containing residue <complex is polyacrylic acid or carboxymethyl cellulose sodium