TW200918703A - Lyocell fibers with antimicrobial activity - Google Patents

Abstract

Meltblown lyocell fibers are disclosed which show a high degree of antimicrobial activity against E. coli and C. albicans. The fibers are prepared by adding inorganic and organic compounds to the NMNO dope prior to spinning. The additives are uniformly distributed throughout the fiber cross section and longitudinal sections show relatively smooth or grainy, rough surfaces depending on the additive used.

Description

200918703 IX. DESCRIPTION OF THE INVENTION: TECHNICAL FIELD OF THE INVENTION The present invention relates to ly〇ceii fibers having antimicrobial activity. [Prior Art] There is a need for a low-cost disposable product such as a rag and a towel that can be used in a specific end-use application. The anti-microbial activity of the slewing sleek fiber is particularly suitable for non-woven fabrics. Application because of its special features soft hand, water absorption, micron diameter size, biodegradability and the ability of these fibers to combine during spinning to form self-adhesive or spunlace mesh. 2. Pulp with high hemicellulose content The fibers produced by the phase are particularly suitable for this application because hemicellulose increases the interfiber bonding. Eight: The base fiber is self-processed to remove the non-cellulose group 疋 hemicellulose from high quality wood. These highly processed pulps are called dissolved grades or sorghum, and are identified as -,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, Therefore, '焉(^浆面合右古1-8 ratio of cellulose and (4) a low percentage of other components, especially the semi-fibrous females, significantly increased the demand for Leo Saiwei only "South alpha pulp" Plus as... fiber and made from it The cost of the product.- The cellulose coniferous wood used for such alpha pulps usually has a longer fiber than the broad apple # and conifer wood; and j wood. Because of the customary kraft paper oven _, the non-remaining hemicellulose is prevented from getting into the acceptable quality and dissolved: the relative carbonyl content of the subsequent substances of the kraft pulp - phase:: (4) pulp. The steel value reflecting the low fiber count The requirement for the manufacture of Leo Sai 132564.doc 200918703 Weizhi Paibai, Tian Fan # & before, dissolved because it is generally believed to dissolve and degrade in the amine oxide solvent. Today, high copper value leads to cellulose and Solvent solution ° Hai degradation solvent can be used to save the sheep set + $ 丄 often do not expect to abandon the solvent. 胄 or regeneration 'however because of its cost = metal content system - used to make Leo Sai fiber The desired properties are due to undesired degradation of, for example, transition metal gallium, methyl repair oxides in the Leoise process. In order to manufacture the industrial grade of dissolved grade cypress, it is preferable to use the sorghum dissolved grade slurry (4) as a raw material for Leoise. Low CX (e.g., high yield) pulp can be used to make Leosite fibers. Preferably, the desired low CX pulp will have a low copper value, a low lignin content, and a desirable low transition metal content but a broad molecular weight distribution. Polyamides that meet these requirements are manufactured by the assignee of the present application and are described in US 6,797 '113, US 6,686, 〇93AUS I. Although high purity pulp is also suitable for use in the present invention, it is suitable for low cost systems such as Bu-8, Grand Prairie Softwood and c_Pine (both can be deduced from 1). These polybenzins have low cost and good benefits for non-woven textile applications & good bonding due to their high hemicellulose content. The selected cypress properties are not shown in Table 1. Table 1: Zhongbai nature pulp Rio Rl8% polyxylose · -__ % nectar aggregate · α-cellulose 86 Peach 85 88 7.05 6.10 Grand Prairie Softwood 19* 7.59 6.2 5.86 C-Pine 87.4 88.0 7.50 132564.doc 200918703 *18% Solubility Measured according to TAPPI T235 [Summary of the Invention] The present invention relates to a Leosite fiber having antimicrobial activity. More particularly, it relates to a Leosite fiber comprising an antimicrobial agent, wherein the fiber is extruded by a meltblowing process. The lower molecular weight component degraded in the pulp used in the present invention is measured by the R" and R1〇 content as described in TAPPI 235. &◦ represents the remaining amount of undissolved material left after extracting the pulp with 1% by weight of caustic, and Ru represents the remaining amount of undissolved material left after extracting the pulp with an 18% caustic solution. Typically, hemicellulose and chemically degraded short chain cellulose are dissolved and removed in solution in a 10% caustic solution. Conversely, only hemicellulose is dissolved and removed in an 18% caustic solution. Thus, the difference between the value and the value of R18, 'represents the amount of chemically degraded short-chain cellulose present in the sample of the cypress, U Example +, which has a ΔΙΙ of about 2 to a force of 10. In another embodiment, this is from about 4 to about 6. The term hemicellulose represents a heterogeneous group of low molecular weight carbohydrate sigma species associated with cellulose in wood. Hemicellulose-based amorphous, branched polymers, and, in contrast, cellulose-based polymers. The main monosaccharide-forming D-glucose, D-xylose, d-mannose, arabinose, d-galactose, D-glucuronic acid and D-galacturonic acid are combined to form hemicellulose. Hemicellulose in leech and fiber is used for sugar analysis as follows: Method 仃 and represents the sum of the xylan and mannan content of the pulp or fiber. The prepared Leosite fibers can be spun from cellulose in 132564.doc 200918703 NMMO by various methods. In one embodiment, the fibers are spun by meltblowing. When the term meltblowing is used, it is understood to mean a process similar to that used to make thermoplastic fibers, although the cellulose is in solution and the spinning temperature is only moderately elevated. In another embodiment the fibers are spun by a centrifugal spinning process, and in another embodiment the fibers are spun by dry spray spinning, and in yet another embodiment the fibers are. Spinning by spinning. The fibers formed by the meltblowing process may be continuous or discontinuous, depending on the air f, the velocity of the process gas, the temperature of the air, the viscosity of the solution, the degree of polymerization of the cellulose 1 and combinations thereof; in a continuous process, The fiber is wound from a roll, and it is stretched. In an embodiment for making a nonwoven web, the fibers are contacted by a spray with a non-solvent such as water, then wound onto a moving carrier, the fibers are washed and dried. The fibers formed by this method can be a -bonded nonwoven web' depending on the degree of agglomeration or:. Spunlaces include shots with a spout. - A slightly similar method =, square sticking method in which the fiber is extruded into a tube and elongated with a G = air flow through the tube. Generally, the ratio of spunbond fibers is: ",": the length of the spray fibers is usually discrete and short. Another, called, 'the difference in the holes on the side walls of the centrifuge is the difference between the polymer and the polymer from a fast rotating cylinder. Lengthening. Iron and two of these fibers are rotated by the air resistance with the air resistance, and the flow is slightly dry, /, M soil, r flow. Another technique, in a y method, the filaments ejected from the orifice are in Immersed in a liquid bath and condensed before it is used to make a nonwoven fabric. _° All four methods can be used in the embodiment, the fiber consists of a 3 weight I% semi-fiber 132564.doc 200918703 Made in 粕. In another example, the fiber is made from a pulp with more than 8 weights of hemicellulose - with a richness of more than 12% by weight: another implementation In the example, the cellulose-rich pulp is made. In one embodiment, the cage MA丄,·, '隹έ has about 4 to 18% by weight of the semi-fibers. The fibers contain from 7 to 14% by weight of the hemicelluloses. In yet another embodiment, the fibers comprise from 9% to 12% by weight of hemicellulose. In only a few examples, the degree of polymerization of the fibers is from about 200 to about. In another embodiment, the degree of polymerization is from about 35 Å to about 9 (9), and in yet another embodiment the degree of polymerization is from about 400 to about _. The degree of polymerization (abbreviation D.P.) as defined herein refers to the number of dehydrated D-glucose units in the cellulose chain. The degree of polymerization is determined according to ASTM test 1795-86. Antimicrobial fibers can be found in a variety of fibrous products, including fabrics and garments (including sportswear, incontinence pants, and medical apparel), air filters and water filters, wound and burn care dressings, medical rags, and medical robes. , shoe components and household and household furniture fabrics including bed sheets, pillow towels, mattresses, blanket towels, curtains, bedspreads, pillow cases, carpets, floor mats, napkins, linen, wall coverings, cloth furniture, linings, linings Bed mattress fillings - pillow fillings, carpet mats, upholstery fabrics and the like. The antimicrobial agent can be an inorganic or organic compound. The inorganic compound includes, but is, a compound having tin, copper, silver, and zinc, and may be in the form of an oxide or carried in a compound such as squaric acid, zeolite or the like. Other inorganic compounds such as potassium, magnesium and calcium can also be used as antimicrobial agents. Inorganic antimicrobial agents include silver zeolite complexes, which are produced by (6) ^ 132564.doc 200918703

Chemical is sold by ALPHASAN and sold by Agion Technologies as AGION. In the present application, a zeolite of the formula Ag84Na2(AlO2)86(SiO2) 106xH2〇 was obtained as a particulate silver ion exchanged zeolite from Aldrich and milled to pass through a mesh of less than 20 microns. AZO 66 USP grade zinc oxide was obtained from US Zinc; more than 99.9% of the particles passed through a M5 mesh screen. Calcium carbonate was obtained from Aldrich (CAS 471-34-1) with a particle size of less than 10 micrometers.

In one embodiment, the inorganic antimicrobial agent is added at a level of from about 5% by weight relative to the pulp to about 40% by weight relative to the cellulose. In another embodiment, the additive is added at a level of from 1% by weight relative to the cellulose to about 25% by weight relative to the cellulose. In yet another embodiment, the additive is added at a level of from about 15% by weight relative to the pulp to about 2% by weight relative to the cellulose. In one embodiment, the inorganic antimicrobial agent is present in the fiber in an amount from about 1% by weight to (4% by weight). In another embodiment, the additive is present in the fiber in an amount from 1 Gg to about 25% by weight. In another embodiment, the amount in the fibers is from about 15% by weight to about 2% by weight. Organic compounds that can be used as antimicrobial agents include, but are not limited to, triclosan, tetraammonium compounds, diammonium cyclic compounds, M. L ^ T salt, N-haloamine oxime and gas. The organic compound depends on the antimicrobial agent that needs to be leached or migrated from the inside of the fiber to the surface. The treatment of the fibers containing the antimicrobial agent and the fiber properties are as shown in Tables 2 and 4, and Table 3 and Table 5 show the meltblowns. Antimicrobial test knot for sprayed fibers 132564.doc •10- 200918703

In this case, the Seiko 8 and 2 series manufactured by Ink Corporation of Korea were used as an organic silver complex compound having a water concentration of 5%. The anti-microbial agent is equally effective and can be used to significantly reduce colony forming units using very low levels. In one embodiment, the additive is added in an amount of from about 5% to about 5% by weight of the organic silver complex compound solution (relative to cellulose). In another embodiment, the additive is added in an amount of from about 0.5 to about 3% by weight of the organic silver complex compound solution (relative to cellulose). In the examples, the fibers have about 5 to ppm silver. The lightness of the Leosite fiber containing the silver compound is lower than that of the control sample, but the silver-based antimicrobial agent is mixed with zinc oxide or carbonic acid to increase the fiber brightness (sample U, Table 4, sample 10, Table 2' and sample n, respectively). For the sample, Table 4). At the same time, compared with the control group, the solvent-soluble leostat fiber containing the inorganic zinc compound reduced the Escherichia coli (IV) forming unit by at least 98% in 24 hours. At the same time, compared with the control group, the number of Candida albicans decreased by at least 95% at 4 hours and 24 hours, and the inorganic additive calcium carbonate and the organic additive SILVI containing organic = complex compound were in 4 In the small day, (4), the colony forming units of Coriolis enteric acid were all reduced by more than 95%. At the same time, compared with the control group, zinc oxide reduced the colony forming unit of Candida albicans by at least 95% at 4 hours, and reduced the colony forming unit of Escherichia coli and Candida albicans by at least 95% at 24 hours. The melt-blown Leosite fibers containing various antimicrobial agents are shown in Figures 2 to 6 ^ Figure 1 is a scanning electron micrograph (SEM) of a control sample showing a longitudinal cross-section and cross-section of a 4-fold fiber that is magnified 1 time. section. The fibers are relatively smooth ellipsoid to circular cross sections. Figure 2 is a SEM image of a 2000-fold magnification of the cross-section of Sample 6, 132564.doc 200918703 Uniformly distributed zinc oxide particles and a granular surface. Figure 3: Amplification of the cross-section of the two fibers _ times the backscattered electron microscopy π-plate (BSE) ′ shows the uniform distribution of zinc in these Λ t ^ θ. Fig. 4 is a 1000-fold magnification of a longitudinal section of a melt-blown fiber sheet containing a SILVIO of about 1.1% by weight. S fibers with this additive have a relatively smooth surface. Fig. 5 is a SEM at 1000 times magnification of the meltblown Leosite fiber containing 22.39% by weight of carbonic acid in the fiber and about 15 minutes of the melt port of the mouth of the mouth. The fiber has a rough and granular shape: the surface. Figure 6 shows the weight of the buckle in the fiber. /. The cross section of the sample 13 of the kiln and the distribution of zinc in the fiber and the surface of the fiber are doubled. Depending on a number of factors such as air velocity, air pressure, air temperature, solution viscosity, degree of cellulose polymerization, and combinations thereof, multi-fiber properties can be obtained by dazzle spraying. In an embodiment, the fibers have a fiber diameter of from about 10 μ to about 3 μμ, and in yet another embodiment, the fibers have about 15 to 20 μ fiber diameter. Fiber diameter measurements represent (10) randomly selected fibers and averaged by optical microscopy. The birefringence of the antimicrobial fibers indicates a high molecular orientation of the cellulose fibers that are visually indistinguishable from the control. The control values are in the range of (4) to 〇_〇34, and the sample containing the oxidized word is unchanged as ο·. %. This description is not adversely affected by the molecular orientation despite the zinc oxide additive. In an embodiment, the birefringence is at least 〇·〇2. In another embodiment, the birefringence is at least 0.025. The birefringence was measured by the method described below. The typical birefringence value of Leoise is 0.045, and the slime staple fiber is two, 132564.doc -12· 200918703

Modal is 0,038, cotton rabbit. "/, ^ is decorated as 0.047, Ning Ma is 0.074, and NB416 (purchased from

Weyerhaeuser's commercially available commercial pulp) is 〇 〇 26. The fiber availability was measured according to TAPH T4 5 2 . [Examples] In the example, in the case of I1, Peeah8 (a bleached kraft paper Southern Pine Polycymine available from Weyerhaeuser Co., Federal Way, Washington) was acidified and treated with sodium hydride. The amount of hemicellulose content (10) in the average degree of polymerization was about 420 and the amount of hemicellulose (6.5% and 5.5% by weight of xylan and mannan, respectively) was about 77 and 87, respectively. This pulp was dissolved in νμ_ν·decylmorpholinium-oxide in the following manner. In a 25 Α bucket = wool liter two-necked flask, for example, 66 · 4 g 97% ΝΜΜΟ, 24 7 吉 s 〇 0 / " νην / ην / ΐΆ " no 50 /. ]^/1]^〇, 1〇 4g pulp, 〇 克 食 酸 酸 酸 酸 酸 酸 酸 酸 酸 酸 酸 酸 酸 酸 酸 酸 酸 酸 酸Limb # & Zinc Zinc immersed the flask in a 120. (In the oil bath, 'insert a granter and give up the wall.'] 丨n main. Now, it is only about 1 hour. It produces a liquid that is easy to flow and is suitable for spinning. The cellulose concentration is about 12% by weight. The desert liquid is extruded at a rate of U g/hole/min from a melt blow mold having three nozzles having a pore size of A" micron. 5. Keep the nozzle at a temperature of 95 ° C. Poor, *, squeeze the / Chen liquid into a 30 cm long air gap = after the condensation in the water, and in a continuous or discontinuous The filaments are collected on a mesh screen, which depends on the rheology and material conditions of the dope. The air is connected to the head with a temperature of 95 C and a waste force of about 。. The air friction to 3 psi is the same as the different fiber diameters shown in Table 2 and Table 4. 132564.doc •13- 200918703 铋趄费缒^sf^w 螓妒绂sf#荽 Cup ♦ Sample No. 〇66.4 24.7 o | 10.4 1 cs o 10.25 ZnO Τ~Η 14.4 9-57 11.21 20.00 15.2 t 80300 1- 1 i 4.81 4.07 55.7 〇66.4 24.7 o 10.4 10.25 ZnO Ό ΓΟ 34.6 25.71 13.3 2 | 30.00 I 〇〇od 72.4 0.026 | 00 66.4 1 24.7 o 10.4 | 10.25 I ZnO Ό rn 1 34.6 25.71 13.32 20.00 15.6 188000 3.95 3.47 0.026 卜 66.4 L24.Z o Li〇-4 10.25 ZnO inch (Ν 23.1 18.75 112.32 30.00 10.8 146000 3.84 3.48 ,51.2 0.026 丨66.4 24-1 ! o |j〇.4 J 1 10.25 1 ZnO inch <Ν 18.75 12.32 1 20.00 inch JA10QQ 4.34 3.77 0.026 | 66.4 | L^z_1 o 110.4 | 10.25 | ZnO <Ν 11.54 1 10.34 11.30 |Mixed | V) Inch* rn Inch·inch | 66.4 | "24.7 TM o ί 10.4 10.25 [ZnO | (Ν 1—^ 11.54 [10.34 [11.30 | [35.00 Os (N — 5 | 0.026 | | 66.4 | 124,7ί o \ΛΜi | 10.25 | 1 ZnO | fN 11.54 | 10.34 | | 11.30 | | 20.00 | m | 0.026 | (N 66.4 | 24.7 o 10.4 | 10.25 | ZnO CN I 11.54 10.34 ; | 11.30 10.00 32.3 77000 0.026 | 66.4 ^24.7 o 110.4 ΓΪ0-25 Π ZnO (Ν ! 11.54 1 10.34 | ΓΪ1.30 | 5.00 | 1 44.5 j 4.45 4.26 Control group Q i 66.4 25.4 o 10.4 | 10.18 | Ο Ο 0.00 10.18 20.00 oo 1 4.76 4.59 0.034 U | 66.4 1 25.4 o 110.4 1 | 10.18 1 Ο ο 0.00 10.18 10.00 1 19.9 | Inch to 5.02 4.72 | 0.026 1 ffi 66.4 I 1 25.4... o 丨10.4 | 10.18 | ο ο 0.00 | 10.18 [lo.oo | 17.5—” 1 4.82 4.61 610.026 < | 66.4 | |2^4_ o Li〇^_ | 10.18 1 ο ο | 0.00 | 10.18 1 8-30 1 00 — 卜o Ϊ Os Ci〇〇1 propyl gallate g slurry粕g 3 § C/3 Cellulose % Additive Additive gf ί Μ. Check i ♦1 Additive weight % of fiber in fiber (solid weight %): air pressure (psi) diameter (micron) zinc ppm silver, ppm > N 漤Μ 漤Μ s s? Good _1 Mannan, weight % in fiber Brightness ISO | Birefringence 132564.doc • 14· 200918703 132564.doc Sample number 〇17500 <100 <100 2000 <100 I <100 Os 00 17500 10150 <100 2000 <100 <100 卜17500 5550 <100 2000 <100 <100 Ό 17500 8400 <!〇〇I 2000 |<ιοο 1 <100 < n inch m (N — | against QU CQ < 17500 4150 8800 2000 2350 3500 sgs? B * Μ 4 hours, 24 hours and 0 hours of Candida albicans (CFU / ml) Heng inch 24 hours 钽蜱 钽蜱 * -15- 200918703 / 3⁄43⁄4 铋趄 fee 缱 ^ SE^W 资缒运蘅荽^^杯^1< Sample No. 66.2 24.5 s 420 10.4 CS ο 10.29 CaC03 • ο :9.77 11.17 14.6 33300 4.83 4.01 48.1 Ό 66.2 24.5 Ξ 420 10.4 10.29 CaC03 m 28.9 22.39 12.87 10.3 1 | 83300 79.3 66.2 24.5 5 420 10.4 10.29 CaC〇3 28.9 22.39 12.87 20.00 14.5 80600 4.19 3.59 inch 66.2 24.5 a 420 10.4 10.29 <N Ο σν 1.89 10.46 30.00 12.2 ΓΛ 66.2 ! 24.5 S 420 1 10.4 <Ν Ο 10.29 Zeolite CM Ο 00 10.46 30.00 15.7 730 940 4.44 1 3.92 Ν 66.2 24.5 420 10.4 (Ν Ο 10.29 SILVIO (Ν Ξ Ξ 0.095 10.46 30.00 CS ii 66.2 24.5 Ξ 420 10.4 CS ο 10.29 SILVO fN Ο _ 0.095 10.46 20.00 15.5 216 5.19 — :37.89 Control Q 66.4 25.4 S 420 10.4 10.18 Ο 0.00 | 10.18 20.00 m 00 4.76 4.59 0.034 U 66.4 25.4 - 420 10.4 10. 18 Ο 0.00 10.18 10.00 19.9 5.02 4.72 ;0.026 CQ 66.4 25.4 - 420 j 10.4 1 10.18 ο 0.00 10.18 10.00 17.5 4.82 4.61 〇:0.026 < 66.4 25.4 5 420 ! 10.4 10.18 ο 0.00 10.18 8-30 〇〇 — 4.74 DO 〇 2 50%NMMOg & 0 Warm pulp 粕 Polymerization pulp 3 g 3 Ο 1 woven vitamin % Additive additive g Additive weight % (relative to pulp) Additive weight % in fiber Solid (total weight %) Air pressure ( Psi) Diameter, (micron) Silver, ppm Calcium, ppm Polyxylose, Weight Mannan in Fiber, Weight % in Fiber Brightness, ISO Birefringence 132564.doc -16- 200918703 132564.doc Sample Number Bu 17500 &lt 100 <100 17500 <100 | <100 I inch CO 2000 ! <100 | <100 CN 2000 <100 <100 1 - 1 17500 <100 <100 2000 <100 <100 Control QU CQ < 17500 1 4150 1 1 8800 | 2000 2350 3500 Zero time E. coli (CFU/ml)* 4 hours 24 hours zero time white Cocci (CFU/ml) 4 hours 钽衅 钽衅 钽衅 * • 17- 200918703 Determination of birefringence of fibers by polarized light microscopy Theoretically, fibers are characterized by a parallel (axial) to the fiber axis The refractive index and the refractive index birefringence perpendicular to the fiber axis are the difference between the two refractive indices. The convention is from the vertical axis R.L (refractive index). The axial direction R·1. is usually represented by the Greek letter ω, and the vertical R_I· is represented by the letter ε. The birefringence is generally expressed as Δ = (ω_ε) β refractive index oil, and an oil having a known refractive index also at a specific excitation light wavelength and a specific temperature. These fibers are compared to Cargile refractive index oils. Polarization Using the transmitted light in an optical microscope, the refractive index is measured using a depolarizing mirror. The excitation light is polarized in a direction parallel to the fiber axis, and the amount of axial refractive index can be measured. The polarizing filter can then be rotated 9 G degrees and the refractive index perpendicular to the s-fiber axis is measured. When the refractive index of the field fiber is matched with the index of the oil to which it is placed, the image of the fiber disappears. Conversely, when the fiber is placed in an oil having a large refractive index difference, the fiber image is observed with high contrast. When the refractive index of the fiber is close to the refractive index of the oil, a technique is used to determine whether the refractive index of the fiber is higher or lower than the oil. The slides are first used to control the fibers that are illuminated with properly positioned polarizing filters into the sharp focus of the microscope. H The slide is slightly (four). If the slide is raised with it. The image of the Λ fiber, 隹 〉 appears brighter, and the fiber has a higher refractive index than the oil. Conversely, if the fiber appears darker as the stage is raised, the fiber fold 132564.doc 200918703 is less than the oil. The fibers were placed in the refractive index oil and examined until a satisfactory refractive index match was obtained. The axial and vertical components are measured and the birefringence is calculated. Sugar Analysis This method is suitable for the preparation and analysis of (4) and wood samples. The sample is used to determine the amount of the following pulp sugars using "energy anion exchange chromatography and m-current current detector (HPAEC/PAD): trehalose, arab bran,

Galactose, rhamnose, glucose, xylose and mannose. Method Overview By hydrolysis with sulfuric acid, the polymer of 粕 sugar is converted into monomer. The sample is ground, weighed, hydrolyzed and diluted to a final volume of 2 GG ml, filtered, and diluted again (1. 〇 ml + 8 〇 ml H2 〇 Prepare for MHpAEc/pAD analysis Sampling, sample handling and storage Dry samples are dried or dried at 25 ± 5 ° C. Equipment required for high pressure steel ' Market Forge, model STM_E, serial number c_18 〇 8. 〇χ ίο ml vial , diaphragm, cap, Di〇nex serial number. Rotary water bath shaker, model G76 or some equivalent. Month t* is enough to scale to ± 〇.01 mg of balance, such as Mettier hl52 analytical balance.

Tho_-Wiley laboratory intermediate grinder, 4 mesh screen. NAC 15 06 vacuum drying oven or equivalent. 〇.45-μ GHP filter ' Gelman A/E type, (4 7 (10) glass fiber 132564.doc -19· 200918703 piece, without organic binder) Thick-walled test tube with pouring spout, 2.5 X 20 cm

Comply SteriGage Pressure Steam Sterilization Kit Chemical Indicator GP 5〇Dionex Non-Metal Gradient Delivery Pump with Four Solvent Inlets The Di〇nex ed 40 pulsating current detector with gold working electrode and solid reference electrode has a column , the ED 40 element and the insulated chamber of the syringe ring

Dionex autosampler as 50. Dionex PC 10 pneumatic solvent addition unit with 1 liter plastic bottle 3 2 liter Dionex polyethylene solvent bottles with solvent outlet and helium inlet cap 〇玨1^〇?3〇?81(〇丨〇1^\ ?/;^ 03 5391) Ion exchange column, 4 mm X 250 mm

CarboPac PAl (Dionex P/N 043096) protection column, 4 mm χ 50 mm microporous solvent filtration unit with ΗΑ-45 μ filter or equivalent reagents All Η20 system Millipore Η20 72% sulfuric acid solution (1^8〇4)_ Move ι 83 ml of water to a 2 liter Erlenmeyer flask. The flask was placed in ice in a Rubbermaid bucket in a hood and the flask was allowed to cool. 470 ml of 96.6% h2S04 was slowly and carefully injected into the flask while stirring. Allow the solution to cool. Carefully move to the bottle containing the 5 ml dispenser. Set the dispenser to 1 ml. JT Baker 5 0% sodium hydroxide solution, batch number Baker 3 727-01, [πιο- I32564.doc 20· 200918703 73-2].

Dionex sodium acetate, anhydrous (82.0 ± 0.5 g / 1 liter H20), lot 59326, [127-09-3]. Standards Internal standards Trehalose is used in kraft paper and dissolving pulp samples. 2-Deoxy-D-glucose was used for wood pulp samples. Trehalose, internal standard, 12.00 ± 0.005 g of trehalose, Sigma batch F 2252, [2438-80-4] was dissolved in 200.0 ml of water to give a concentration of 60.00 ± 0.005 mg/ml. This standard is stored in the refrigerator. 2-deoxy-D-glucose, internal standard, 12.00±0·005 g 2-deoxy-D-glucose, Fluka batch 32948 g [101-77-9] dissolved in 200.0 ml water to produce 60.00±0.005 mg/ml concentration. This standard is stored in the refrigerator. Kraft pulp stock solution Standard solution Kraft pulp sugar Standard concentration Sugar Manufacturer purity g/200 mL Arabinose Sigma 99% 0.070 Galactose Sigma 99% 0.060 Glucose Sigma 99% 4.800 Xylose Sigma 99% 0.640 Mannose Sigma 99% 0.560 Kraft Pulp Operating Solution - Weigh each sugar to 4 significant digits and transfer to the same 200 ml volumetric flask. Dissolve the sugar in a small amount of water. Make up to volume with water, mix well and transfer contents 132564.doc -21 - 200918703 to two clean 4 plates brown bottles. Label and store in the refrigerator. Make the working standards for the following table. Kraft pulp pulp standard concentration

mL/200 mL/200 mL mL/200 mL mL/200 mL mL/200 mL Trehalose mLO.70 1.40_2Λ0_180_3.50

Sugar mg/mL ug/mL ug/mL ug/mL ug/mL ug/mL trehalose 60.00 300.00 300.00 300.00 300.00 300.00 arabinose 0.36 1.2 2.5 3.8 5.00 6.508 galactose 0.30 1.1 2.2 3.30 4.40 5.555 glucose 24.0 84 168.0 252.0 336.0 420.7 Xylose 3.20 11 22.0 33.80 45.00 56.05 Mannose 2.80 9.80 19.0 29.0 39.0 49.07 Dissolved grade pulp stock solution standard solution dissolving pulp sugar standard concentration sugar manufacturer purity g/100 mL glucose Sigma 99% 6.40 xylose Sigma 99% 0.120 nectar Sugar Sigma 99% 0.080 Dissolving Pulp Operating Solution Weigh each sugar to 4 significant digits and transfer to the same 200 ml volumetric flask. Dissolve the sugar in a small amount of water. Dilute with water, mix well and transfer the contents into two clean 4 oz brown bottles. Label and store in an ice bin. Make the working standards for the following table. Standard concentration of pulp and syrup in dissolving pulp

mL/200 mL/200 mL mL/200 mL mL/200 mL mL/200 mL Trehalose mL 0.70 1.40 2.10 2.80 3.50 Sugar mg/mL ug/mL ug/mL ug/mL ug/mL ug/mL Trehalose 60.00 300.00 300.00 300.00 300.00 300.00 Glucose 64.64 226.24 452.48 678.72 904.96 1131.20 Xylose 1.266 4.43 8.86 13.29 17.72 22.16 Mannose 0.8070 2.82 5.65 8.47 11.30 14.12 -22- 132564.doc 200918703 Wood pulp stock standard solution wood pulp sugar standard concentration sugar manufacturer purity g /200 mL Glucose Sigma 99% 12.00 Rhamnose Sigma 99% 0.0701 A 1 ml trehalose solution was dispensed into a 200 ml flask and made up to the final volume. The final concentration will be 0.3 mg/ml. Wood pulp working solution The kraft pulp stock solution and the trehalose and rhamnose stock solution are used. Make the working standards for the following table. Kraft pulp pulp standard concentration 2-deoxy-D-glucose mg/mL mL/200 mL 0.70 ug/mL mL/200 mL 1.40 mL/200 mL 2.10 mL/200 mL 2.80 mL/200 mL 3.50 ug/ mL ug/mL ug/mL ug/mL 2-DG 60.00 300.00 300.00 300.00 300.00 300.00 Trehalose 0.300 1.05 2.10 3.15 4.20 6.50 Arabinose 0.36 1.2 2.5 3.8 5.00 6.508 Galactose 0.30 1.1 2.2 3.30 4.40 5.555 Rhamnose 0.3500 1.225 2.450 3.675 4.900 6.125 Glucose 24.00 84 168.0 252.0 336.0 420.7 Xylose 3.20 11 22.0 33.80 45.00 56.05 Mannose 2.80 9.80 19:0 29.0 39.0 49.07 Procedure Sample Preparation A 0.2 ± 05 gram sample was ground to a 40 mesh screen size using a Wiley mill. Approximately 200 mg of the sample was transferred to a 40 ml Teflon container and capped. It was dried overnight in a vacuum drying oven at 50 °C. 1.0 ml of 72% H2S〇4 was added to the test tube -23 - 132564.doc 200918703 using a Brinkman dispenser. Stir and crush for one minute with a round head of a broken or Teflon stir bar to turn on the heating of the rotary water bath shaker. The settings are as follows: Heating: High Control thermostat: 7. 〇 Safety thermostat: 25. (: Speed · 'Close the shaker: Close the test tube holder into the rotary water bath shaker. Mix each sample 3 times, the first - 20-40 minutes #, the second time. 6 minutes, the third minute. Remove the sample after 9 minutes. Dispense the internal standard (trehalose) into the kraft paper sample. Cover the sample and the standard flask with U tightly to ensure that (4) does not fall off in the pressure cooker. The chemical indicator in the compact steriGageM steam sterilization kit is placed in the high-pressure steel and heated with high-pressure steel for 6 () minutes at a temperature of 14.16 psi (95_1G5 kpa) and greater than 260T (127 °C:). The sample is removed from the pressure cooker. The sample is cooled. The sample is transferred to a milliliter bottle + force u into 2_deoxy_D_glucose into the wood sample. The flask is filled with water to the final capacity. For kraft paper and dissolved Paddle sample: An aliquot of the GHP 45·45 μ 过 琴 / 恩 恩 恩 置 置 置 置 置 置 置 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于 对于Try not to interfere with the granules 132564.doc -24· 200918703 and pass GHP 0.45丨』,·者3? 'Wind. _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ An aliquot of 1 〇〇 ml of the filtered sample was added to 8.0 ml of water. The sample into the Dionex vial was tested in the Dionex AS/100 system. See the following chromatographic procedure. 0 Chromatography Procedure Solvent Preparation Solvent A Distilled and deionized water (18 million ohms), while being immersed in a crucible, was stirred with a crucible for at least 2 minutes while maintaining the crucible coating regardless of whether the system was opened or closed. B system 400 mM NaOH.Inject solvent B into the bottle to make up to volume with water and stir it for 20 minutes. Add appropriate amount of 5% NaOH (50.0 g NaOH/100 g solution)* (1 m〇i NaOH/40.0 g NaOH) * (1_53 g solution / 1 mL solution) * (looo mL solution / 1 l solution) = 19.1 M NaOH in a 50/50 w/w NaOH container.

〇·400 M NaOH* (1000 mL water/19.1 M NaOH)=20.8 mL NaOH To facilitate the removal of 20.8 ml or less:

19.1 M* (20.0 ml x mL) = 0.400 M NaOH x niL = 956 mL Solvent D is 200 mM sodium acetate. Approximately 45 0 mL of deionized water was added to the Dionex acetate nanocontainer using 18 million ohms of water. Replace the tip and shake until the contents are completely dissolved. The sodium acetate solution was transferred to a 1 liter vial. The 500 ml sodium acetate container was washed with 100 ml of water, and the cleaning 132564.doc -25-200918703 was transferred into the measuring flask. Repeat the cleaning twice. After washing, the contents of the measuring flask were made up to 1 liter with water. The solution solution was thoroughly mixed. Measure 3 60 ± 10 ml into a 2 liter graduated cylinder. Make up to 10 ml of 1800 soil. It was filtered into a 2000 ml branched tube flask using a microfiltration device having a 0.45 pm HA type film. This was added to a solvent D bottle and bubbled with helium while stirring for 20 minutes.

The solvent was added to the column followed by 300 mM NaOH. It was added after the column to detect a sugar as an anion at pH > 12 '3. Transfer 15 ± 5 ml of 5 〇 0 / 〇 NaOH to a graduated cylinder and make up to 96 〇 ± 1 () ml with water. (50.0 g NaOH/100 g solution)* um〇1 Na〇H/4〇〇g Na〇H) * (1.53 g solution / 1 mL solution) (1 mL solution / 丨L solution) = 5 〇/5〇w/w NaOH container is m μ NaOH.

0.300 M NaOH * (looo ml h2〇 /19j μ Na〇H)=15 7 mL

NaOH will discard 1 5.7 mL or less:

19.1M*(15.〇mL/x mL) = 〇.3〇〇M NaOH x mL = 956 mL (round 956 red to 960. Because the pH value in the 0.300 M Na0H region is stable, it does not need to be exactly 956 mL of water) Set the AS 5 0 process. For all samples injected into the helmet is 5 UL, the injection type is "complete", the intercept volume is 10 uL, the injection read sore is 1 #, the speed is 3, and all samples and standards have sample type ''samples''. The weight and &# _ 夂 internal standard values are set to 1. These five standards were tested at the beginning of the test in the following order: 132564.doc -26 - 200918703 Standard A1 STAN ( (STANDARD A1 DATE) Standard B 1 Date (STANDARD B 1 DATE) Standard Cl DATE (STANDARD Cl DATE) Standard D1 Date (STANDARD D1 DATE) Standard El Date (STANDARD El DATE) After the final sample has been tested, the intermediate standard is again tested as a continuous calibration confirmation. .

Control samples were tested at the sample points between the initial and final standard tests. Test sample. Calculate the weight percentage of pulp sugar to calculate the normalized sugar area = (sugar area) * (pg / mL trehalose) (trehalose) IS corrected amount of sugar (pg / mL = ((normalized sugar area) - (cut Distance))(¥ί)

% by weight of monomer sugar = IS - amount of modified sugar (pg/mL) * sample weight. (mg) Example of arabinose: % by weight of monomer sugar = Arabic _@ *20 = 0.043% 70.71 mg arabinose polymer % by weight = (% by weight of sample sugar) * (〇·88) Example of arabinose: % by weight of polymer sugar = (〇.〇43% by weight) *(0.88) = 0.038 by weight Note: Xylose and arabinose The amount was corrected by 88%, trehalose, galacto 132564.doc -27- 200918703 Sugar, rhamnose, glucose and mannose were corrected by 9〇%. Results reported as percentage of dried sugar Growth medium study procedure 1 · Phosphate buffer solution a. Stock solution PBS (1 liter):

Na2HP04 12.36 g NaH2P04 1.8 〇 g NaCl 85.00 g H2 〇 1.0 liter (preparation solution for 6 samples) b. 9:1 diluted PBS working solution. (Move it into a separate screw cap flask and sterilize it). Four samples require 72 liters of operating solution; one sample requires 9 liters of sample. C. Adjust the pH to 7. 〇 _ 7.2 using a tamper probe immersed in the working solution; titrate with dilute hydrochloric acid (1 or 2 N). 2. Add to the minimum growth medium (MGM) in PBS: a. Prepare 100 ml of 1% and 10% peptone, and sterilize in an autoclave. b. Make 100 ml of 1% (Nh4) 2S〇4 solution and sterilize by filtration. C_ Obtain BME vitamin “10〇X from sigma B-6891. d. Make 1 ml of inorganic salt medium (MSM) for sterilization 1. MgS04 5.0 g 2. ZnS04 0·01 g 3 · FeS04 0_05 g 4 · MnS04 0·01 g 132564.doc -28 - 200918703 5. Concentrated hydrochloric acid 1.5 ml 6. H20 100 ml 3. Cultured microorganism preparation: Staphylococcus aureus: Culti-Loop was prepared in 1.0 ml of sterile TSB for 10 minutes. ATCC 0538 To the TSA bevel and grow for 24 hours at 35 ° C. E. coli: Culti-Loop was prepared in 1 〇 ml sterile TSB for 10 minutes. ATCC 8739 was streaked to the TSA bevel and grown at 35 ° C for 24 hours. S. cerevisiae: Preparation Culti-Loop was prepared in 1. ml of sterile dilute pBS. ATCC 10231 was dissolved for 1 min. Draw to SDA and grow for 24 hours at 35 < 3 (: 4) Other medium: SDA: 400 ML, sand-type glucose 瑷月: Prepare the bevel and burn. 〇TSA: UOO ml egg (four) Soy agar: Prepare the bevel and flask. 5. Dilute the culture: a. Prepare 9.0 ml of diluted PBSf. Remove from the slope ( Washing each of the cultured microorganisms and adding them to the PBS tube. To match the .5 solution (in the editor) ° it is the stock solution culture solution (Golden "Rustococcus, Candida albicans" 囷Θ b. For Staphylococcus aureus solid Candida albicans, stock culture The dilution of the solution and the dilute solution of the hair 7 至 I I32564.doc -29· 200918703 MGM. (about 103 final flora) c. For Candida albicans, add 1 liter of stock solution to 1.0 l MMG. (About 103 final flora) 6. Special MGM solution for each microorganism: a. Staphylococcus aureus: 94.4 ml stock solution pBS + 849 6 ml deionized water 'pH adjustment and sterilization. (or 994 ml Pre-diluted just solution () 2 (+2) 2 (9) 〇 ml is for X.

Additive: 1.0 ml MSM 50 ml ΒΜΕ vitamin. 5 ml of 1% protein gland. 1. 〇 pen liter diluted bacterial culture (prefabricated) b. E. coli · · 94_9 ml stock solution PBS + 854 1 ml deionized water ' adjust pH and sterilize. (or 9493⁄4 liters of pre-dilution ρΒ§ stock solution) β (2χ+2)2〇〇=2(10)〇 ML is 4 for X.

Additive: 1.0 ml MSM 5 〇 ml BME vitamins. 1. 〇ml diluted bacterial culture (prefabricated) 1 Candida albicans: 92.9 ml of stock solution 1^8 + 836.1 ml of deionized water was adjusted to pH and sterilized. (or 929 ml pre-diluted PBS stock solution). (2X+2) 200 = 2000 ml for X is 4.

Additive: 1.0 ml MSM 132564.doc -30- 200918703 50 ml BME vitamins. 20 ml of 10% peptone. 10 ml 10% (NH4)2SO4 1.0 house liter of undiluted bacterial culture (prefabricated) 7. Tested product a. Prepare enough sterile 250 plastic bottles to treat each microbial plus positive control and negative control for 2 replicates. (45 flasks are required to test 6 products) b. Label all plastic bottles containing microorganisms (Staphylococcus aureus, Escherichia coli, Candida albicans), plus serial number (Wq, W-2._. W-45). c. Add 2.0 grams of each product to be tested to each plastic bottle (or add to the aseptic blender if the sample is not soft), then add 2 ml of inoculated MGM. Inoculate, while shaking at 3rc (wire in the milk box - attached to the shaker water bath - plus one or two plastic boxes) for 4 and 24 hours. Repeat the test. Samples were taken for microwaves at zero time (blank and first Weyerhaeuser samples), 4 hours and 24 hours. d· Repeat item 3 above for each microorganism and each product. e· for each microbial test two mgm containing 2 ml of inoculation

The view of the Weyerhaeuser sample. It is a blank group. f. For each microbial type, test the positive control group instead of the sample (see below). 8 ·Cultivation and counting a• After preparing all the bottles, each “blank, control and product bottle micro-132564.doc •31 · 200918703 The object is applied to the TSB or SDA' depending on the microorganism. Zero time. b All cultures and product inoculated flasks were incubated at 37 C for 4 hours and 24 hours. Use a milk cart attached to a shaker; in an indoor incubator adjusted to 37 ° C. c. And after 24 hours' aliquots were removed from all burnt and flattened (for, no product) control groups for CFU present. Use TSA: For S. aureus and E. coli (4 hours for culture plates at 3rc) use SDA. For Candida albicans (at 20 (5 days of culture plate) d. : Prepared for experimentation There are 4 microbial dilutions of ι〇3 to ι〇 on the product plate and blank group; the positive control will be higher. 9. Positive control: Prepared for each microorganism - flask with about _ml modified mgm solution (total of three) The flask was incubated for 4 and 24 hours at 37t.

J a• Staphylococcus aureus: 100 ml TSB 0.1 ml MSM 5_0 ml BME vitamin 〇·5 ml 1% peptone

0.1 ml diluted Staphylococcus bacterial culture b. E. coli: 100 ml TSB

〇 _ 1 ml MSM 5.0 ml BME vitamins. 0.1 ml diluted E. coli bacterial culture 132564.doc -32- 200918703

c• Candida albicans: loo ml TSB

O.l ml MSM 5·〇ml BME vitamins. 2.0 ml 10% protein practice 1.0 ml (nh4) 2so4 〇·1 house liter undiluted Candida albicans bacterial culture d. Inoculate golden yellow (four) cocci and large intestine rod with 1 ml of liquid storage formula 1/ 1 00 dilution. The σ nutrient solution e. inoculated with Candida albicans + with 01 ml of stock culture control group. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a scanning electron microscope magnified 1000 times magnification of a longitudinal section of a control sample A. Fig. 2 is a scanning electron micrograph at 2000 magnification of a cross section of sample 6. Figure 3 is a backscattered electron micrograph of a cross-section of sample 7 magnified 2000 times. Figure 4 is a scanning electron of a longitudinal section of sample 11 magnified 1 times. Figure 5 is a 1000-fold magnification of the longitudinal section of sample 15. Scanning electron microscopy photomicrograph Photograph 6 Series sample 13 cross-section magnified 1000 times backscattered electron microscopy 132564.doc -33·

Claims (1)

200918703 X. Patent application scope: Sprayed lesoteric fiber, which comprises at least one antimicrobial agent, the agent is hooked across the entire section of the fiber, and the fibers include 4 to 18% by weight of hemicellulose, And the ISO brightness is at least 3 5 ° 2. The fiber according to item 1, wherein the above antimicrobial agent is an inorganic compound. 3. The fiber according to claim 2, wherein the antimicrobial agent is selected from the group consisting of a compound containing one or more of copper, silver, potassium, magnesium, calcium, or a combination thereof. 4', wherein the fiber of claim 3, wherein the antimicrobial agent comprises a compound. 5. The fiber of claim 3, wherein the antimicrobial agent is a compound containing silver. The fiber of member 3, wherein the antimicrobial agent contains about a compound. . 7. The fiber of claim 1, wherein the antimicrobial agent is an organic compound. 〇 8. The fiber of claim 7, wherein the antimicrobial agent is an organic compound containing silver, such as the fiber of the item 8 wherein the fiber contains from about 5 to about 1000 grams of silver. 132564.doc 1 〇. The fibers of claim 2, wherein the fibers comprise from about 0.1 to about 4 weight percent of an antimicrobial agent. 200918703 11 • An antimicrobial agent as claimed in item 1. Wherein the fibers comprise from about 10 to about 25% by weight of the antimicrobial agent of the fibers of claim. 13. Fibre shot as requested. Wherein the fibers comprise from about 5 to about 2% by weight, wherein the fibers such as §Hai have a double fold of at least 〇2 14. 14. If the request is 1515, the diameter of the request is from about 2 to about 50 microns. . 16. The claimed item wherein the fiber diameter is from about 5 to about 35 microns. Meter. The fiber of the fiber wherein the fiber diameter is from about 10 to about 20 microliters. 7. The fiber of claim 1 is reduced by 18%. The fiber of the fiber of claim 1 is reduced, wherein at least 95% of the fiber is relative to a control group. Colonies formed a single fiber at position 0 in 24 hours, wherein at least 950/〇 of Candida albicans colony forming units were present at 24 hours relative to a control group. 132564.doc 200918703 VII. Designated representative map: (1) The representative representative of the case is: (2). (2) A brief description of the symbol of the representative figure: (No description of the symbol of the component) 8. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: (none) 132564.doc -4-