TW434344B - Process for the treatment of textile materials with an antimicrobial agent - Google Patents

Abstract

A process for the incorporation of an antimicrobial agent into a fibre, fabric or piece goods is described comprising treating said material by passing said fibre into an aqueous liquor containing an antimicrobial agent selected from (a) halogeno-o-hydroxydiphenyl compounds; (b) phenol derivatives; (c) benzyl alcohols; (d) chlorohexidine and derivatives thereof; (e) C12-C14 alkylbetaines and C8-C18 fatty acid amidoalkylbetaines; (f) amphoteric surfactants; (g) trihalocarbanilides; (h) quaternary and polyquaternary compounds; and (i) thiazole compounds.

Description

4 34 3 4 4 B7 V. Description of the invention (I)-(read from the back ...; A. *. «· Matters-PI to (small) The present invention relates to the use of antimicrobial agents to treat fabric substances A method comprising an antif [biological agent formulation and a fabric substance treated with the method. There is an increasing demand for fabrics that exhibit antimicrobial properties. Antimicrobial fabrics are known to be completed in the form of surface treated fabrics, For example, US-A-4,408,996. This type of application provides treated fabrics with antimicrobial activity, but the effect is not durable, because the antimicrobial agent is present on the surface of the fabric and will be reduced after washing. In the melt spinning step, the antimicrobial agent is mixed into the fiber melt, preferably in a macromolecular structure. This method enables the antimicrobial agent to be fixed in the fiber and allows it to migrate to the fiber. / Provides a lasting effect on the surface of the fabric, depending on the nature of the polymer used. The effect usually lasts as long as the life cycle of the relevant fabric substance.

Ml '!. Unfortunately, for certain substances, such as polyethylene terephthalate (PET), polybutylene terephthalate, polypropylene, nylon (including nylon-6, nylon- 66), poly (m-phenylene-m-xylylenediamine), poly (p-phenylene-p-phenylenediamine), often involve extremely high temperature (> 280 °) thermal processes in the melt spinning step of the fiber manufacturing method Non-woven materials can also be prepared by this method. Due to the high temperature, it is impossible to incorporate antimicrobial agents, especially organic antimicrobial agents, directly into the molten polymer required by the fiber production method. Because at this temperature Organic antimicrobial agents have been developed. Therefore, a method must be found to 'enable the antimicrobial agents to be incorporated into the macromolecular structure of such fibers' without the need for thermal procedures at extremely high temperatures. Surprisingly, it has been found This purpose can be used to simulate a dyeing party. __4 ^ ________________________________________________________________________ Wood Paper β 屮 ("NS) Λ4 Specification (2l0y Gong) 4 34 34 4 V. The Β7 method is here. @This, this invention is about A method for mixing an antimicrobial agent into fibers and fabrics, comprising treating the substance by pumping the fiber into water containing the antimicrobial agent, and the antimicrobial agent is selected from the group consisting of: Phenyl compounds; (b) phenol derivatives; (c) benzyl alcohol; (d) chlorohexidine and its derivatives; (e) Cn-C14 alkyl betaine and C8-CIS fatty acid amidoalkyl Betaine

I (f) amphoteric surfactants; (g) trihalotriphenylurea; (h) quaternary and polyquaternary compounds; and snoring 4: compounds. Preferably, the antimicrobial agent (a) is a compound selected from the following chemical formula (please read the precautions on the back first and then " ί. 本 Η) ⑴

λ ΐ <: where X is oxygen, sulfur or -CH2-, Y is chloro or bromo, Z is S0H, 1 or [0 2 or οα alkyl r is 0 to 3, 0 is 0 to 3 , Wood paper degree inverse () grid (21〇W7 public power) A7 B7 4 3 4 3 4 4 5. Description of the invention (j ^ P is 0 or 1, m halo 0 or 1, and η is ◦ or 1; And at least one 或 β β of r or 〇 Preferably, in the method of the present invention, the antimicrobial agent (a) of chemical formula (1) is used, wherein X is oxygen, sulfur or -CH2-, and Y is chloro Or bromo, m is 0, η is ◦ or 1, 〇 is 1 or 2, r is 1 or 2, and P is 0. Particularly interesting antimicrobial agents are compounds of the formula:

Where X is -0- or -ch2-; m is 1 to 3: and η is 1 or 2, and the best is the compound of the following formula: )

Wooden paper ruler 4 W 屮 Η κ (C '\ S). (N () x male) A7

4 343 4 4 _____ _B7_ V. Description of the invention) The preferred phenol derivative (b) conforms to the following chemical formula ‘·

OH

R (5) where ratio is hydrogen, hydroxy, alkyl, chloro, nitro, phenyl, or benzyl R2 is hydrogen, hydroxy, CVC6 alkyl, or halogen, R3 is hydrogen, C! -C6 alkyl, hydroxy , Chloro, nitro, or an alkali metal or ammonium salt, R4 is hydrogen or methyl, and

Rs is hydrogen or nitro. These compounds are typically chlorophenols (o-, m-, p-chlorophenol), 2,4-dichlorophenol, p-nitrophenol, picric acid, xylenol, p-chloro-m-xylenol , Methanyl (o-, m-, p-cresol), p-chloro-m-cresol, pyrocatechol, oxocarpine, luteolin, 4-n-hexylresorcinol, pyropyrene Phenol, resorcinol, vanillin, thymol, p-chlorothymol, o-phenylphenol, o-benzylphenol, p-chloro-o-benzylphenol and 4-phenolsulfonic acid. Typical antimicrobial agent (c) conforms to the following chemical formula = where

Ri, R2, R3, I and R5 are each independently related hydrogen or chloro. ___—_________ 7____ Recognition degree of wood and paper; 丨 丨 屮 (('NS) Λ4 叱 格 (] 丨 () 乂 公 筇) I:, * νκη Order ..... II.... Ί-~ 一 {谙 First read the note of 1FJ—item again 垆: +34) 4 34 3 4 4 A7 B7 V. Description of the Invention (" Γ)-Examples of compounds of formula (5) are f-based alcohols, 2,4-, 3,5-, 2,6-dichlorobenzyl and trichlorobenzyl alcohol.

J Antimicrobial agents (d) are chlorohexidine and its salts, such as: 1,1-hexamethylene-bis_ (5- (p-chlorophenyl) -biguanide), and organic and inorganic acids and chloro groups Hexidine derivatives, such as their diacetate, diglucoate or dihydrochloride compounds. The antimicrobial agent is typically OCl8 cocamidopropylbetaine ° Amphoteric surfactants suitable as the antimicrobial agent (f) are C12 alkylaminocarboxylic acids and alkylcarboxylic acids such as alkylaminoethyl Ester or alkylaminopropionate. A typical trihalotriphenylurea suitable for use as an antimicrobial agent (g) is a compound of the formula:

among them

Hal is chloro or bromo, η and m are 1 or 2, and n + m is equal to 3. The quaternary and multiple quaternary compounds that meet the antimicrobial agent (h) have the following chemical formula:

Wood paper 仏 歧 4;! 丨 ((.NS) AWUS (210 郄 247 郄) A7 B7) 5. Description of the invention (where R6: R7, Rs and R9 are unrelated GC 丨 8 alkyl groups, respectively. 8 alkoxy or phenyl-lower alkyl, and Hal is chloro or bromo. Among these salts, compounds of the formula: CH. 3C- (CH such as-CH, where η is from 7 to An integer of 17 is particularly preferred. The compound to be further exemplified is cetyltrimethylethylammonium bromide. Of particular interest as an antimicrobial agent is methylchloroisotahazoline. The antimicrobial agent used in the present invention is zid ^ j cattle or 俥Slightly fall away from water. In this aqueous formulation, they can therefore be applied as aqueous formulations in diluted, soluble, emulsified or dispersed form. 'If the antimicrobial agent is applied in dispersed form, the use of quartz beads and stirring impellers can be convenient They are honed together with a suitable dispersant to a particle size of 1-2 millimeters. Suitable dispersants for use in the antimicrobials of the present invention are:-Acid esters of epoxide adducts or their salts, typically 4 to 40 mol ethylene oxide and 1 mol phenol polymer adduct, or 6 to 3 0 mol ethylene oxide with 1 mol 4-nonylphenol, 1 mol dinonylphenol or preferably from 1 mol to 3 mol unsubstituted or substituted styrene addition to 1 mol (ΪΛ-Please open this and remove this item again ^-: 本 打)

CH

cr ⑼ ii ^ 343 4 4 B; Ί 1., I —------ V. Description of the invention (l) * Esters formed by ortho-acidification polymerization adducts of compounds prepared by otol Or its miners, ί-polystyrene sulfonate,-fatty acid taurine-alkylated diphenyl ether mono- or disulfonate, • polycarboxylate sulfonate, -1 to 60 Mo earrings Polymer adducts of oxyethylene and / or propylene oxide with fatty amines, fatty acids, or fatty alcohols, each polymer adduct contains 8 to 22 carbon atoms in the alkyl chain and 4 to 6 in the alkyl chain Alkyl phenols of 3 carbon atoms, or 3 to 6 carbon alkanols containing 3 to 6 carbon atoms, the polymerization adduct is converted to an acid ester with an organic dicarboxylic acid or an inorganic polyacid, -sulfonic acid Acid lignin, and most preferably-formaldehyde condensates, for example: sulfonic lignin and / or phenol and formaldehyde condensate, formaldehyde and aromatic sulfonic acid condensate, typical of ditolyl sulfonate and toluene Condensates, naphthalenesulfonic acid and / or naphthol · or condensate of naphthylaminesulfonic acid and formaldehyde, phenolsulfonic acid and / or sulfonated dihydroxydibenzene mill and phenol or cresol and formaldehyde and / or Condensates of urea, and condensates of diphenyl ether-disulfonic acid derivatives and formaldehyde. The concentration of the antimicrobial agent in the dispersion is from 0.1% to 30% by weight, preferably 2 to 10% by weight. However, for some low-melting point (i.e., <80 ° C) antimicrobial agents, such a honing process is difficult to put on an industrial scale. Moreover, such procedures significantly increase manufacturing costs. Surprisingly, it has been found that there is no need to carry out the honing process, and ________—____________________ 10_____ (210κ297 public 筇) (please read it first and pay attention to the heng item before π .... / 本 打)-· » You-; 1 A7 4 34 3 4 4 V. Description of the Invention (彳) * (诮 Read the back note first; 6 items before ^-: '本 玎) A method for preparing antimicrobial agents in the form of an aqueous solution, which has proved effective. The antimicrobial agent f is applied in soluble form without the need for a honing process. Suitable solubilizers are anionic, non-ionic or zwitterionic and zwitterionic interfacial active substances. Suitable anionic interfacial active substances are:-sulfates, typically fatty alcohol sulfates, whose alkyl chain contains 8 to 18 carbon atoms, such as sulfated dodecanol;-fatty alcohol ether sulfates, typically 2 to 30 moles Acid esters or salts of the polymerized adduct of ethylene oxide with 1 mole of G-C22 fatty alcohol;-alkali metal, ammonium or amine salts of OCm fatty acids, which are called soaps, typically coconut fatty acids; -Sulfuric acid amine;-Alkylamine sulfate, typically dodecane sulfate monoethanolamine;-Alkylamine sulfate sulfate;-Alkyl sulfate polyaryl ether;-Monoglyceryl sulfate;-Alkanesulfonic acid, alkyl The chain contains 8 to 20 carbon atoms, for example: dodecylsulfonic acid;-alkylamine sulfonate;-alkylaryl sulfonate;-α-olefin sulfonate; '-sulfosuccinic acid derivative , Typical alkyl sulfosuccinates, sulfo-number succinic acid alkyl ethers or alkyl sulfosuccinimide derivatives;-N- [alkylamidoalkyl] amino acids of the following formula: This; (rNS) lattice (2 丨 0X297); ti) Α7 Β7 Γ 434344 V. Description of the invention (1) (1〇) CH3 (CHa) n-CO-N ^ Y, CH-Z-COO'M *

i I χ where X is hydrogen, Ci-C% alkyl or -CCKJM +, Y is nitrogen or C1-C4 radical 'z is-(ch2) —- w, -1 mi is 1 to 5, m is from 6 An integer from 18 to 18, and M is an alkali metal ion or an amine ion; a carboxylic acid alkyl ether and a carboxylic acid alkylaryl ether of the following chemical formula: (10) CH3-XYA, where X is each of the following groups:

Line 'wood paper anti-bin bin out of the flashlight :? (CNS) Λ4 grid (2 丨 0X297 male) 4 34 3 4 4 5. Description of the invention (丨 R is hydrogen or Ci-C% alkyl Y is:-(CHCHO) '1-50 A7 B7 A is: 〇 or:-(CH2) —— COO'M * Η., -P-〇 Μ + 〇ΊνΓ rm is 1 to 6, and M is an alkali metal cation or an amine cation.%, The anionic surfactant used may be further Fatty acid methyl tauride, nodose heteropolysulfate, fatty acid polypeptide condensate, and fatty alcohol phosphate. The alkyl group in these compounds preferably contains 8 to 24 carbon atoms. Anionic surfactants are usually The water-soluble salts such as ammonium or amine salts are obtained. Typical examples of these salts are lithium, sodium, potassium, zinc, triethylamine, ethanolamine, diethanolamine or triethanolamine salts. Sodium or Potassium salt, or ammonium- (NLbRa) salt, in which 1, R2 and R3 are independently unrelated hydrogen, alkyl or G-C4 hydroxyalkyl. 13__ 木 级 延 中 (rNS) 8 4 grids (210X $ 297 4 4 343 4 4 __ V. Description of the invention U 1) (&quot; Notes to read from back to back &quot; · Item 4 10,000) Excellent shade in this novel formulation The surfactant is an alkali metal salt of ethanolamine dodecyl sulfate or fatty alcohol sulfate, preferably sodium dodecyl sulfate, sodium dodecyl ethyl-2 sulfate or sodium cumene sulfonate. Suitable amphoteric ionicity and Amphoteric surfactants are Qin Yifeng Epimedic Acid, Alkyl Amphoteric Carboxylic Acid, Alkyl Amphoteric Carboxylic Acid (e.g. Dodecanal Amphoglycine), and N-Alkyl-β-Aminopropionate or N -Alkyl-β-imino dipropionate. Non-ionic surfactant is a typical derivative of propylene oxide / ethylene oxide adduct, fatty alcohol hydroxyethyl, with a molecular weight of 1000 to 150 ⑼. Base brewing (1-50 EO), alkyl phenol polyethylene glycol ether (丨 -50 EO) 'hydroxyethylated carbohydrates. Partial esters of fatty acid glycols' typical monostearic acid-diethylene glycol' PEG5 -PEG25 glyceryl stearate, such as PEG-5 glyceryl stearate 'PEG 15 glyceryl stearate or PEG 25 glyceryl stearate; hexadecyl octanoate; fatty acid alkanolamine and fatty acid di Alkanolamines' fatty acid compounds, alcohol amines, hydroxyethyl esters, and fatty acid amine oxides. Line i In addition, saturated and C8-C22 unsaturated fatty acid salts can be used. They are used as solubilizers, whether they are used individually, mixed with each other or with other interfacial active substances mentioned as component (c). Examples of these fatty acids are typically capric acid and dodecanoic acid , Myristic acid, hexadecanoic acid, stearic acid 'arachidic acid, yushuic acid, dodecenoic acid' myristic acid, octadecenoic acid, oleic acid, eicosanoic acid, and erucic acid, and Technical mixtures' are typically coconut fatty acids. These acids are available in the form of salts. Suitable cations are alkali metal cations, such as sodium and potassium cations, metal atoms, such as zinc and aluminum atoms, or nitrogen-containing organic compounds of sufficient basicity. , Typical amine or hydroxyethylamine. These salts can also be prepared in situ. _____________________________ Μ__ Wood and paper scales Ψ ί ί ί ΓΓί. Tick ((.NS) Λ4 is present (210X297 gong) 4 34 3 4 4 V. Description of the invention (p /) · In addition, a suitable solubilizer in this composition is a glycol , Preferably its alkylene group has 2 to 6 carbon atoms, typically ethylene glycol, 1,2- or ί, 3-propanediol, 1,3-, 1,4- or 2,3-butanediol , 1,5-pentanediol and 1,6-hexanediol, or monohydric alcohols such as methanol; ethanol or propanol: and acetone. The anionic, nonionic, zwitterionic, and amphoteric surface-active substances mentioned above can also be used. A mixture with one or more mono- and / or dibasic acids is used as a solubilizer for the antimicrobial agent. The 3c solution containing the antimicrobial agent (a) to rhenium is first honed, and 1) the biological agent is dispersed into fine Prepared by granulation, or by solubilizing or dispersing or dissolving a microbial agent in water without a honing process. It is preferred that the antimicrobial agent be dissolved in the surfactant before mixing, with or without a small amount of organic solvent, other ingredients or water. In a preferred method, the aqueous solution is heated above the melting point of the antimicrobial agent to assist the solubilization or dispersion process. The aqueous solution containing the antimicrobial agent in a dispersed or solubilized form prepared by this method can be diluted to almost any ratio. Preferably, the antimicrobial is added to the aqueous solution in an amount of 0.001 to 10% by weight of the fibrous material. Fibrous materials that can be treated with antimicrobial agents are materials containing materials such as silk, leather, sheep, and polyamides, and various materials such as nylon (including nylon-6, nylon-66), or polyurethane, polyester, and polyester Fibrous materials of acrylonitrile, polypropylene, polyethylene, and cellulose, such as natural cellulose fibers, such as cotton, linen, jute, and hemp, as well as viscose rayon and regenerated cellulose. It is understood that the polyester fiber materials that can be treated with antimicrobial agents include __________________________ \ 5___ wood paper 仏 scale H) 8 4 叱 枋 (2 \ ΟΧ29Ί ^ ~) i— · &quot; ------ ^ (¾ First read it back and note &quot; Matters' &quot;! _.: &Quot; ^ :). 4 343 4 4 A7 A7 B7 V. Description of the invention (\))-cellulose ester fibers, such as cellulose secondary acetic acid And cellulose triacetate fiber, which is more linear polyester fiber, which can be modified by acid, and is through terephthalic acid and ethylene glycol, or isophthalic acid or terephthalic acid and 14-bishydroxyl It is obtained by the condensation of methylcyclohexane, and a copolymer of terephthalic acid and isophthalic acid grade ethylene glycol. The linear polyester fiber substance (PES) used so far almost exclusively dominates the textile industry consisting of terephthalic acid and ethylene glycol. The fibrous material may also be a natural fiber such as cotton, wool or jute each other or a blend with a synthetic fiber material such as PES, nylon or polypropylene, or a blend of synthetic fiber materials with each other. Typical fiber blends of polyacrylonitrile-polyester, polyamide / polyester, polyester / cotton, polyester / viscose, and polyester / wool. Fabric fibrous materials can have different forms of appearance, preferably woven or woven fabrics or cloths such as knitted fabrics, woven nonwovens, blankets, clothing can also be packaged yarns, rewinds and the like, or finished products in any form Good for T-shirts, sportswear, running bras, sweaters, coats, women's underwear, shirts and socks. The fibers or fiber blends can be processed batchwise or continuously. The treatment of fibrous material is carried out in a continuous or batch process in an aqueous solution. In batch dyeing, the range of selectable solution ratios is I, typically from 1: 4 to 1: 100, preferably from 1: 5 to 1: 50. The processing temperature is not lower than 50 ° C, and usually not higher than M0 ° C. Best temperature Fan Yuan Department _ from. The concentration of the antimicrobial agent in the aqueous solution is sufficient for the agent to be drawn into the fiber cone. In particular, the antimicrobial concentration is preferably from 0.01 to 10% by weight based on the weight of the fiber or fabric material, and most preferably from 0.05 to _i ·% Of thunder. In the continuous processing method, the processing solution may include an auxiliary agent 1 £. 4 as necessary, and a description of the meaning of the paper;!: '内 内 R' ii · ;: :() Λ 4 / (2 I 0 X 2 9 (7 males) ---------- M ------ π -------..--{¾ Read the memorandums of the back first and then hit Jnv_4) A7 B7 r Y: 4 34 ^ 4-V. Description of the invention (丨 1!), Which is applied to yarn, fabric, and cloth, for example, by dip dyeing or rough dip dyeing, and is developed by _ heat fixation or HT steaming process. r The linear polyester fibers and cellulose fibers are preferably in a closed and high-pressure-resistant device 'at a temperature of &gt; 80 ° C, and preferably from 90 to 120. (: The range, as well as the processing at high temperature under normal or high pressure. Suitable closed devices include typical machines that are also used for dyeing processes, such as circular dyeing machines such as package yarn or ray dyeing machines, 'winches, jets or drums' Dyeing machine, sleeve dyeing machine, pad dyeing machine or jig dyeing machine. Cellulose secondary acetate is preferably processed in a temperature range of 80 to 85 ° C. The processing time is from 5 to 30, preferably 10 to 20 The fiber material treated by this method is characterized by a very uniform distribution of the antimicrobial agent on the entire fiber cross section. The method of the present invention is also combined with the dyeing method. A suitable dye is a disperse dye, which is only slightly soluble in water and metal. Compound dyes or acid dyes. Therefore they are present in the dyeing solution in the form of fine dispersions. They can belong to different dye grades, including acridinone's azo, quinone, humulin, hypochlorite; methyl, perinone , Naphthoquinone imine, quinoline, styryl or nitro dye.: R It is also possible to use a mixture of disperse dyes in the practice of the invention &gt; In the case of biological agents, the step may be I: first treating the fibrous material with these compounds, and then dyeing, or it is better to treat the fibrous material with an antimicrobial agent and a dye at the same time in the dyeing bath. However, the application of the antimicrobial agent is also May be affected by heat fixation after 5 'previously prepared staining. V ___ — 17____ Wood paper 仏 仏 m 屮 called imn () / vmL grid (2 丨 〇 / 2 叼 公 筇) 4 343 4 4 at ________ — B7 V. Description of the Invention (丨 f) * The treatment solution may also include tamparone L ^ l, such as dyeing aid, dispersant, carrier, wool protection agent, wetting agent and defoamer. (¾ 先Note from time to time a: δ- 亊 term again, _, this Π) | The treatment solution may also contain mineral acids, typically sulfuric acid or phosphoric acid, or organic acids for convenience, typically including aliphatic carboxylic acids such as formic acid, Acetic acid, oxalic acid, or citric acid and / or salts, such as ammonium acetate, ammonium sulfate, or sodium acetate. These acids are especially used to adjust the pH of the solution used in the practice of the invention to 4-5. First, the fibrous material is passed in 20-80 ° C dyeing bath, which contains antimicrobials, preferably dyes and Other adjuvants, and has been adjusted to pH 4.5-5.5. Then raise the temperature to 80-125 ° C for more than 20 to 40 minutes, and then preferably perform another treatment in the temperature range of 80 to 125 ° C for 10 to 100 Minutes, preferably 20 minutes and 80 minutes. The sample is completed by cooling the treatment solution to 50 to 80 ° C. If necessary, the dye is washed away with water. If necessary, it is reduced and washed with a basic vehicle in a conventional manner. The treated sample is then washed again and dried. When the reducing dye is used to dye the cellulose component, the finished product is first treated with bisulfite at pH 6-12.5, then treated with an oxidizing agent, and finally washed. A long-lasting effect is obtained by a microorganism to complete the fabric material. The fabric material completed by the method of the present invention has the advantages of inhibiting microorganisms, reducing the risk of contamination, reducing odor, increasing freshness, and improving sanitary conditions. In the following examples, percentages are expressed by weight. The amounts of dyes and anti-biological agents are mainly pure substances. Example 1: Preparation of anti-micro-bovine formulations In a suitable container that has been previously added with 200 g of quartz sand, winter paper comes out (('NS) grid (; MoX297 public dream) B7 4 3434 4 V. Invention Explanation (1 is) 7.0 g of compound of formula (101)

OH (Triclosan),, 21.0 g of naphthalenesulfonic acid / formaldehyde condensation product and 112.0 g of water. The mixture was then homogenized with a calender for 24 hours. The quartz sand is then filtered off and the formulation is ready for use. Example 2: Mixing the formulation Put 50 ml of the preparation prepared in Example 1 into a suitable container and dilute to 1000 ml with water, together with about 500 g of fabric material made of polyethylene terephthalate . The container was then sealed and placed in a bath at 120 ° C for 1-5 hours. The treated fabric is then removed from the formulation and rinsed thoroughly with water. Example 3: Determination of the concentration of Trilosan in fabrics The concentration of Tridosan in treated fabrics is measured by dissolving an appropriate amount of such fabric material in dichloroacetic acid, followed by an appropriate separation / extraction step, followed by HPLC analysis. The concentration was found to be 0.26% of the total weight of the fabric.眚 Example 4: Extraction of treated fabrics In order to determine whether Triclosan has been incorporated into the fabric's molecular structure or absorbed on the surface, extraction experiments must be performed. Therefore, using Triclosan 19 _____ —— — ~~ ^ · *-· * · **. 一 — _-. _ ___ ______ Mu Zhi Da 屮 Κΐϋ 忧 4 i rNS) ^ 柏柏 （2! () X 297 Public #) (please refer to it in the back, please refer to it; # .; δ matters again) • T,-'4 343 4 4 A7 B7 V. Description of the invention (q)-a good solvent, the appropriate amount of hexane extraction after treatment Fabric for 60 minutes. Concentrations of Triclosan and the extracts in the extracted fabrics were analyzed by HPLC

I. It was found that the Triclosan concentration in the fiber hardly changed, but the amount of Triclosan in the extract was almost negligible. These results indicate that Triclosan is incorporated into the PET fibers that form the fabric. Example 5: Determining the anti-microbovine effect of warp fiber The antimicrobial activity of the sample has been tested by a migration test according to the agar diffusion test. Sample: Polyvinyl acetate sample LA 45 ^ Microbovine evaluation ‘· Determine the bacteriostatic activity according to the bacterial growth inhibition test (modified test method CG 147). Principle: Cut a 20 mm diameter sample plate in a sterilized environment, and then apply the solidified bacteria-containing solution (obtained from overnight culture) to make a dilution of 1. · 100 (Staphylococcus aureus) and 1: 1000 (E. coli). And add 3.5 ml to 500 ml agar). Test blue orchid: Staphylococcus aureus ATCC9144 E. coli ATCC11229 Nutritional vehicle: casein soy meal Chen Agar (double-layer agar: 15 ml bacteria-free bottom and 6 ml bacteria-free upper layer) Incubation: 18-24 hours at 37 ° C (I read the back first; I '^ f, ft, then fill in this order—M., \ = T 20 4 ο μ · 3 4 4 A7 B7 V. Description of the invention (#) Table 1: Microbial samples J. Ceratocystis aureus ATCC 9144 ATCC 11229 ZI1 VR ZI VR2 Polyester sample with Triclosan 9/9 4/4 2/2 4/4 ~ 0 = vigorous growth (inactive) 4 = no growth (good activity) Inhibition area, expressed in millimeters Vinson rating of template growth (I first called read back and vi.-JLAi-events ItJA ,; '.. 人 -π]

1T Example 6: Exercise 1-a. Dissolve 5 g of SLS (sodium lauryl sulfate, Henkel) in 100 ml of water 'and then add 1 g of Trilosan with stirring. The preferred solution is heated to 60 ° C to aid solubilization / dispersion. Small · η h \\ .1 Hi b. Add 5 ml of the formulation to 195 ml of water. A sample of polyester fabric was then added to the diluted formulation and the mixture was heated to 130. (: Hold for 60 minutes. After that, the fabric was rinsed, and the Tridosan content in the fabric was found to be 0.47%. Example 7: 2.5 ml of the preparation prepared in Example 6a was added to 195 ml of water 21 wood paper it ruler玟 ”1, |. KH! ((('NS) sigh (2 10 X 29 7 commons &lt; v A7 B7 4 34 3 4 4 5. Description of the invention (/ |)-in. Then 10 grams of cotton A blend of (40%) and polyester (60%) fabric was added to the diluted formulation, and the mixture was heated to 130 ° C for 60 minutes.

I (1 «first«] Please do it in the back .... /!-Italian matter and then work.: Λ beat) After washing the fabric, the Triclosan content in the fabric was found to be 0.42% in polyester. Example 8: Determination of the antimicrobial activity of Triclosan-treated 2 polyester samples The dyeing method of Triclosan-treated 2 polyester samples was rinsed 20 times (15 each time) in 2500 ppm hypochlorite (the resulting pH 11) minute). The antimicrobial effect of these samples was determined by the agar diffusion test for one gram-positive and two gram-negative bacteria according to method CG 147. PES samples containing Tdclosan showed excellent antimicrobial effects against Gram-positive Staphylococcus aureus, Gram-negative E. coli, and Proteus even after 20 washes. Microbiological evaluation The bacteriostatic activity was measured according to a bacterial growth inhibition test (Agar Diffusion Test, CG 147). Sample Sample I: PES / cotton blend (60:40) containing 0.25% Tnclosan Sample 2: PES / cotton blend after 20 rinses. Test bacteria: Nutritional vehicle: Staphylococcus aureus ATCC9144 Escherichia coli NCTC 8196 Proteus ATCC 13315 Cool protein cultivar CAS0 · Jia 2 《^^ 屮 丨 4 丨 《Heart Therapy Tablet (.. (Male) B7 4 343 4 4 5. Explanation of the invention (&gt;) * Incubation: 24 hours at 37 ° C (28 ° for Proteus) Principle:

To prepare an agar plate, pour 15 ml of sterilized agar medium into a shallow petri dish. After the agar has solidified, distribute 6 ml of bacterial-containing agar evenly over the bottom agar layer. To prepare bacterial-containing agar at 47 ° C. (Next, 3.5 ml of 1: 100 (Staphylococcus aureus) and 1: 1000 (E. coli and Proteus) were diluted in an overnight bacterial culture mixed with 500 ml of molten agar β. After the upper layer was solidified, the fabric sample (20 mm The diameter sample plate) is applied in the middle of the inoculation plate (one sample on each agar plate). Each test substance is tested twice. ---------. M ------ 1T ---- --On, .I. (Please read the ί-δ matters first, and then less, ..Λ 丌) „Then inoculate all the plates. After measuring the inhibition area around the incubation fabric template and estimating the growth under the template. Results obtained The series are in Table 2: Table 2: Microbial aureus ATCC 9144 E. coli NCTC 8196 Proteus ATCC 13315 Sample ZI VR ZI VR 71 VR Sample 1 Blend of PES / cotton and 0.25% Irgasan DP300 10/10 4/4 5/5 4/4 6/6 4/4 Sample 2 PES / cotton blend after 20 treatments with 2500 chlorates 5/5 4/4 2/2 4/4. 0/0 4/4 ___ _________23 Wood and paper scale description 屮 丨 (NS) ~! Specifications (_ 2y7 公 #) A7 B7 4 343 4 4 5. Description of the invention (&gt; |) · All samples have been tested twice. Two The results are listed in Table 2. Legend 丨 ZΙ = Inhibition area around the fabric template, expressed in millimeters VR = Vincent grade, which indicates growth under the template. 0 = Growth under the template (no activity) 4 = No growth (excellent activity) ) LJ Vinson et al, J. Pharm. Sci. 50, 827-830, 1961 The results clearly show that the PES / cotton blend also exhibits excellent antimicrobial activity after treatment. At 2500 ppm hypochlorite The good activity after 20 washes was noticeable. Example 9 6 g of Tridosan was dissolved in 4 g of polypropylene (solution A) 0.5 g of sodium lauryl sulfate was dissolved in 200 g of water (solution B). Then 90 mg of solution A was added to solution B which had been heated to 6 (^ (:). The resulting mixture was a clear solution (solution C) 'in which Tdciosan had been dissolved. 10 grams of polyester fiber was added to solution C , And heated to 60 ° C for 60 minutes. Then the PES fiber was washed.

The concentration of Triclosan in the treated PES fibers was 0.48%. Example 10 Ten grams of Triclosan was dissolved in a mixture containing 10 grams of isopropanol and 20 grams of propylene glycol. 50 grams of sodium lauryl sulfate, 5 grams of sodium cumene sulfonate, and 5 grams of water were added to the solution. 'The resulting mixture was a clear solution. Example 11 5 grams of the formulation prepared in Example 10 was added to 200 grams of water. ________24__ ΐ &lt; 'NS) (210X297 gong) — A7 B7 4 3434 4 V. Description of the invention (&gt; ι) · The solution obtained is a turbid but stable emulsion. Add 10 grams of nylon 66 fiber to this mixture, then the antimicrobial treatment can be performed at 95 ° C for 60 minutes. After the treatment, the nylon 66 fiber contains 0.5% Triclosan. Example 12: Mixing the Hangwei cattle material into the resistant fiber in the simultaneous dyeing method This example adds the antimicrobial formulation and the dyes of nylon 6 and nylon 66 fibers, that is, the treatment is The fiber dyeing is performed together. The amount of the antimicrobial formulation of Example 6 added was 1 g. The processing period is 60 minutes. Triclosan concentrations were analyzed using the conditions described in Example 3. The solution ratio used in this experiment was 1:10, so 20 grams of fiber were in a 200 ml water bath. The dyes used in this example are:

Lanaset Green B®: 1.0% owf

Lanaset Blue 2R®: 0.8% owf

Lanaset Bordeaux® B: 0.2% owf

Erionyl Yellow ⑥ VIII: 0.6% owf The results show that the addition of dye does not affect the mixing of the antimicrobial agent into the fiber. This method is advantageous because antimicrobials can be used with dyeing. Therefore, the additional processing cost of mixing the desired antimicrobial agent into the fiber can be ruled out. Rich Example η: In the continuation method of the dye, Hang Wei cattle agent is mixed into the nylon blanket Continuous method for dyeing, which involves unstained felts with dyes dispersed / dissolved in an aqueous bath ________________________25______ Wood paper imitation scale 芘 S (CNS) grid (21 () X: 97 ^^) 1¾] Reading the back νί-General matters Jiang Ye ,,: .4 饤) Ding-.¾ Line-V '. ^^ .. ^ JU J ff &lt; &quot; κ .nlli- 4 3 ^ 3 4 4 A7 B7 meaning:}

il A 5. Description of the invention-Dip dyeing, then steam fixation at 100 ° C for 2-10 minutes, then spin-drying, rinsing, spin-drying and drying. In this example, the same antimicrobial formulation as described in Example 6 was mixed into the dyeing bath. The dyes used in this embodiment are:

Tectilon® Yellow 3R 200% 1.13% owf

Tectilon® Red 23 200% 0.464% owf

Tectilon® Blue 4R-0 200% 0.46% owf Adjuvant: 1 g / L Solvitose® OFA 3 g / L Irgapadol® PN 3 g / L ammonium acetate Add 11.5 g / L of the formulation described in Example 6 to this In the formulation. The choice of bath for blankets is 450%. The blanket was pre-moistened with Tinovetin® at 1 g / l at 60 ° C. In this example, two samples are prepared. One was obtained at a fixed time of 5 minutes, and the other was obtained at a fixed time of 10 minutes. The finished felt was analyzed using the procedure described in Example 3 for analyzing Triclosan concentration. The Tddosan concentration fixed to the carpet was found to be about 0.4% in both.例 Example 14: In the continuous method with dyes, the anti-microbial agent is mixed into the nylon felt. Most of the nylon felts are dyed in a continuous method. This method involves dispersing / dissolving the undyed felt with the dispersed The dyes in the aqueous bath are 26 d. -T ^ ,; t Wood paper ruler political commentary (CNS) 8 4 specifications (2I0X 297 male) 4 34 34 4 a? __ B7 V. Description of the invention ( &gt; ^) · Dip, then steam fix at 100 ° C for 2-10 minutes, then spin dry, rinse, spin dry and dry. In this embodiment, the embodiment 6

The same antimicrobial formulation as described in I was mixed into the dye bath. The dyes used in this embodiment are:

Tectilon® Yellow 3R 200% 1.13% owf

Tectilon® Red 23 200% 0.464% owf

Tectilon® Blue 4R-0 200% 0.46% owf Adjuvant: 1 g / L Solvitose® OFA 3 g / L Irgapadol® PN 3 g / L ammonium acetate Add 11.5 g / L of the formulation described in Example 6 to this In the formulation. The choice of bath for blankets is 450%. The blankets were pre-moistened with Tiiiovetin® Ju at 1 g / L at 60 ° C. 'In this example, two samples were prepared. One was obtained at a fixed time of 5 minutes, and the other was obtained at a fixed time of 10 minutes. The finished felt was analyzed using the procedure described in Example 3 for analyzing triclosan concentration. The Triclosan concentration fixed to the carpet was found to be about 0.4% in both. Example 15: 10 g of 4,4'-dichloro-2'-hydroxy-diphenyl ether was dissolved in a mixture containing 10 g of isopropanol and 20 g of propylene glycol. 50 grams of sodium lauryl sulfate and 5 grams of sodium cumenesulfonate and 5 grams of water were added to the mixture. The resulting preparation is Cheng _______________________________27_____ Wood paper ft scale 4 屮 ㈨ (r + N; S) Λ4ΑΙ 柁 (]) 〇y 297 male 筇) --------- :) 11 ------ tr ------ f {Read me first and then note *-氺 item, then go on .-- 'Dong Π). A7 B7 4 34 3 4 4 V. Description of the invention Γ / f) 淸 solution. Example: 0.5 g of the formulation prepared in Example 15 was used to process nylon 66 fibers using the procedure described in Example 11. The treated fiber contained 0.5% of 4,4'-dichloro-2'-hydroxy-diphenyl ether. __ _______28 The wooden roar A eight narrative ii: inside the line: 彳 (OS) 'Λ4 叱 格 i 21〇y 297 public bomb) --- n If ί I η [I-士 r ^-1 _ _ _ _ Γ. ......... -I ----- -¾. Fi), '-. {Please read first and note: δψterm then t. .Νπ)

Claims (1)

, · Ν ·· 8 8 8 8 ABCD Benefits' l A method of mixing an antimicrobial agent into a fiber, fabric or cloth, comprising passing the fiber into an aqueous solution containing an antimicrobial agent to treat the substance, and the antimicrobial agent is selected from: (a) a compound of the formula: (〇H) m \ OH where X is oxygen, sulfur, or -ch2-, Y is chloro or bromo, Z is S02H, NO2, or G-C4 alkyl, and r is 0 To 3, 0 is 0 to 3, P is 0 or 1, m is 0 or 1, and η is 0 or 1; and .r or 0 has at least one yin; acetol derivative; (c) ^ alcohol; (d) chlorohexidine and its derivatives; (e) C12-Cu alkyl betaine and Cs-Cu fatty acid amine alkyl betaine ⑴ amphoteric surfactant; Ministry of Economic Affairs ^.! Έ 财 ， ϊ-ΐ.'π :: Printed by the industrial consumer cooperatives The fullness of the clothing paper is in accordance with the Chinese National Standard (CMS) A4 specification (21 OX mm) Λ 8 Β8 4 343 4 4__〇 «_ — I 6. The scope of patent application Γ; (g) Trihalomediphenyl gland; (h) quaternary and polyquaternary compounds; and (i) azole compounds. 2. The method according to item 1 of the scope of patent application, wherein the anti-microbiological agent ⑻ is a compound of formula (1), wherein 1 X is oxygen, sulfur or -ch2-, and Y is chloro or bromo, 'm is 0, n is 0 or 1, 0 is 1 or 2, r is 1 or 2, and P is 0. 3. The method according to item 1 of the scope of patent application, wherein the antimicrobial agent (a) is a compound of the formula: (ci) n where X is -0- or -ch2-; ^ is 1 to 3; and η is 1 or 2. 4 · The method according to item 1 of the scope of patent application, wherein the antimicrobial agent (a) is a compound of the following formula: (&quot; First ':' 4 read back 6 of the pit matters and then fill out-this page) '' Avoid Chinese National Standard (CNS) Λ4 specification (210X297 male thin) B8 CS D8, patent application scope C! C! 0H 〇, (3) CI 5 · The method according to item 1 of the scope of patent application, wherein the antimicrobial agent (a) is a compound of the formula: (4) 0H 〇 ci 6 · The method according to item 1 of the scope of patent application, wherein the antimicrobial agent (b) is a compound of the formula: ⑸ OH Where R! Is hydrogen, hydroxy, alkyl, chloro, nitro, phenyl or benzyl R2 is hydrogen, cap, OC5 alkyl or halogen R; is hydrogen, Ci-Ce alkyl, hydroxyl, chloroammonium salt Form sulfonic acid, K is hydrogen or methyl, and R5 is hydrogen or nitro. Nitro or alkali metal salt or read 竒: .υ of note-'F and then fill out this S), \ ί ° This paper is fully compliant with Chinese National Standards (CNS) Α4 specifications (:: 10 × 297 mm) ~ 'Applicable patent scope 7 · The method according to item 1 of the patent application scope, wherein the antimicrobial agent (c) is a compound of the formula: Wherein Ri, R2, R3, L and 1 ^ 5 are independently hydrogen or chloro. 8 · The method according to item 1 of the scope of patent application, wherein the antimicrobial agent (g) is a compound of the following formula: Shi Xian 阃 read back.? ;; Note the ¥ item before filling this page) Set the total wealth of the Ministry of Economic Affairs 4. Exchange: 3; printed by the Industrial Cooperative Bone Cooperative where Hal is chloro or molybdenum, &gt; η and m are 1 or 2, and n + m is 3. 9 · The method according to item 1 of the scope of patent application, wherein the antimicrobial agent is applied in an aqueous formulation in a diluted, soluble, emulsified or dispersed form. Microbial agents are dissolved or dispersed by anionic, non-ionic or zwitterionic and zwitterionic interfacial active substances. 4 This paper is suitable for Chinese National Standards (CNS) Α4 specifications Ø 210X29 · / mm) 4 34 3 4 4 Γ &quot; —! 6. Scope of patent application | 1 1. According to the method of item 10 of the scope of patent application, Wherein the surfactant is sodium cumene sulfonate or sodium lauryl sulfate. (Please read the following note-1 ?! and then fill out this page) 1 2 · According to the method of claim 9 in the scope of patent application, the anti-biological agent is dissolved with a monohydric alcohol or a dihydric alcohol. 1 3 'The method according to item 9 of the scope of the patent application' wherein the antimicrobial agent is dissolved with a mixture of an anion, a non-ion, a zwitterion, an amphoteric surfactant, and one or more monohydric alcohols and / or dihydric alcohols. 1 4. The method according to item 1 of the patent application park, wherein the antimicrobial agent is added to the water-soluble solution in an amount of 0.001 to 10% by weight of the fiber substance. 1 5 · The method according to item 1 of the patent application range, wherein the method is performed at a temperature range from 80 ° C to 135 ° C. 16. The method according to item 1 of the scope of patent application 'wherein the antimicrobial agent contained in the aqueous solution is honed into fine particles before being mixed' and then dispersed, or the antimicrobial agent is solubilized or dispersed or dissolved in In water without any honing procedures. -1 7. The method according to item 16 of the scope of patent application, wherein the antimicrobial agent is dissolved in a small amount of organic solvent, other ingredients and water before being mixed into the surfactant. 1 8. The method according to item 16 of the scope of the patent application, wherein the dissolved, dispersed or solubilized antimicrobial agent is heated above its melting point. 19. The method according to item 1 of the scope of patent application, which is used for the treatment of textile materials. 20. The method according to item 19 of the scope of patent application, in which the substance 5 paper and paper are fully compliant with Chinese National Standard (CNS) A4 specifications (2 〖0x: tJ7 public therapy) Λ 8 Β8 4 343 4 4 The patent scope is selected from silk, leather, wool, polyamide, polyurethane, polyester, polyacrylonitrile and cellulose-containing fiber materials. 2 1 + The method according to item 19 of the application, wherein the fibrous substance is a blend of natural fibers with each other or with a synthetic fibrous substance, or a blend of synthetic fiber substances with each other. (Please read first.-Notes on the back of the matter before filling out this page) Order _ Ministry of Economic Affairs «.; Choi .. tayM Industrial Consumer Co., Ltd. Printed on paper standards applicable to China National Standard (CNS) A &lt; t specifications (210X297mm), · ν ·· 8 8 8 8 ABCD Benefits' l A method of mixing an antimicrobial agent into a fiber, fabric or cloth, comprising passing the fiber into an aqueous solution containing an antimicrobial agent to treat the substance, and the antimicrobial agent is selected from: (a) a compound of the formula: (〇H) m \ OH where X is oxygen, sulfur, or -ch2-, Y is chloro or bromo, Z is S02H, NO2, or G-C4 alkyl, and r is 0 To 3, 0 is 0 to 3, P is 0 or 1, m is 0 or 1, and η is 0 or 1; and .r or 0 has at least one yin; acetol derivative; (c) ^ alcohol; (d) chlorohexidine and its derivatives; (e) C12-Cu alkyl betaine and Cs-Cu fatty acid amine alkyl betaine ⑴ amphoteric surfactant; Ministry of Economic Affairs ^.! Έ 财 ， ϊ-ΐ.'π :: Printed by the industrial consumer cooperatives Clothing paper full GM China National Standard (CMS) A4 specification (21 OX mm)