EP0177126A2 - Verfahren zum Einbringen von antimikrobiellen Agenzien in Fasern - Google Patents

Verfahren zum Einbringen von antimikrobiellen Agenzien in Fasern Download PDF

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Publication number
EP0177126A2
EP0177126A2 EP85305037A EP85305037A EP0177126A2 EP 0177126 A2 EP0177126 A2 EP 0177126A2 EP 85305037 A EP85305037 A EP 85305037A EP 85305037 A EP85305037 A EP 85305037A EP 0177126 A2 EP0177126 A2 EP 0177126A2
Authority
EP
European Patent Office
Prior art keywords
fiber
antimicrobial agent
ppm
oxybisphenoxarsine
medium
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP85305037A
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English (en)
French (fr)
Other versions
EP0177126A3 (de
Inventor
Thomas C. Mcentee
James Brophy
Lawrence J. Guilbault
Judith L. Koob
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ATK Launch Systems LLC
Original Assignee
Morton Thiokol Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Morton Thiokol Inc filed Critical Morton Thiokol Inc
Publication of EP0177126A2 publication Critical patent/EP0177126A2/de
Publication of EP0177126A3 publication Critical patent/EP0177126A3/de
Withdrawn legal-status Critical Current

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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic

Definitions

  • This invention generally pertains to a technique for incorporating antimicrobial agents into fibers following the melt spinning step in fiber manufacturing processes.
  • the process of the invention results in a fiber having an essentially homogeneous
  • Antimicrobial agents such as 10, 10'-oxybisphenoxarsine, (OBPA) are known to serve to provide protection against bacterial attack of thermoplastic fiber materials, such as Nylon 6.
  • OBPA also serves to reduce the occurrence of mildew and other undesirable growth on the fiber when in final product form such as carpeting.
  • OBPA has been incorporated into molten nylon so as to be included in as-spun fiber. This results in an essentially homogeneous distribution of the agent through the fiber cross-section.
  • United States Patent No. 3,345,341 is illustrative of such prior techniques.
  • melt incorporation is unsatisfactory for many antimicrobial agents such as bis (tri-n-butyl tin) oxide (TBTO), because the temperatures of the molten fiber material are sufficiently high to destroy the effectiveness of the agent.
  • TBTO bis (tri-n-butyl tin) oxide
  • solution dyeing in which the dye is incorporated into the melt along with the antimicrobial agent at the melt-spinning state.
  • nylon carpet containing melt incorporated OBPA is currently manufactured in this manner.
  • solution dyed carpeting is only available in a rather limited number of shades and, of course, can only be dyed by the fiber manufacturer. It would be desirable for the carpet manufacturers to be able to process undyed bulk fiber into carpeting by incorporating an antimicrobial agent homogeneously throughout the carpet fiber during or subsequent to the dyeing process. This procedure would provide greater latitude as to color selection and would provide greater flexibility for the overall manufacturing process. It is believed that the process of this invention overcomes the above mentioned problems in a highly advantageous and efficient manner by adding or exhausting the antimicrobial agent into the fiber only in the amount ultimately required during the dyeing step.
  • the invention involves a method of incorporating an antimicrobial agent into a fiber which includes treating a fiber which does not include the agent by passing such fiber into a liquid containing a sufficient concentration of the agent to cause the agent to be exhausted into the fiber.
  • the resultant product is characterized by having an essentially homogeneous distribution of the agent throughout the fiber cross-section.
  • the product exhibits increased durability in this form.
  • the product contains appreciable quantities of the antimicrobial agent in a form which has not been deteriorated by the heat of the temperatures encountered during melt spinning. Such deteriorated agent is usually in an oxidized form.
  • the product of the invention comprises a fiber containing an effective amount of an antimicrobial agent to provide protection against microbial attack of said fiber.
  • the antimicrobial agent is present in an essentially homogeneous cross-sectional distribution throughout said fiber and is further characterized by the presence of a greater amount of active antimicrobial agent than if an equal total amount of the agent had been incorporated into the fiber when the fiber was in the molten condition. This is because potential losses by volatilization and/or degradation from exposure to the vigorous melt-spinning conditions are avoided.
  • a particularly advantageous form of the product may include an antimicrobial agent that is unstable or volatile at the melting point of said, fiber.
  • Such agents include bis (tri-n-butyl tin) oxide (TBTO).
  • the concentration of antimicrobial agents in fibers can be easily controlled during the practice of the invention. Basically, the process involves treating a fiber by passing the fiber through an antimicrobial agent containing medium.
  • concentration of the agent in the medium will constitute the major control variable to achieve the result of the process.
  • time of passage and temperature of the fiber and medium are variables to consider when practicing the process of the invention. These variables are of a nature, however, that one skilled in the art could readily develop suitable parameters for various combinations of fiber, medium, and antimicrobial agent.
  • these hydrophobic, water-insoluble biocides approach an equilibrium apportionment between the fiber (solid phase) and the bath medium (liquid phase) which strongly favors the fiber phase.
  • This method distributes the biocide throughout the fiber, avoiding the disadvantages of a surface application.
  • the antimicrobial agent is compatible with the fiber and does not spew to its surface. The method also avoids the adverse processing conditions encountered when biocides are incorporated at the melt spinning step, thereby minimizing the possible formation of appreciable quantities of deteriorated antimicrobial agents or losses due to volatilization.
  • Fibers suitable for use in connection with the invention include synthetic, semisynthetic, or natural fibers or blends thereof. It is expected that this exhaustive method of biocide incorporation would also be useful with other biocides with similar hydrophobic/solubility properties and in treating other fiber compositions such as acrylics and polyesters.
  • Synthetic fibers include but are not limited to polyamides such as Nylon 6 -and Nylon 66, polyesters, polyacrylics, and modified cellulosics.
  • Suitable media for passage of the fiber include those which are capable of dissolving or dispersing the antimicrobial agent. Obviously the selection of such medium is dependent on the nature of the agent. Such property would be readily determined by one skilled in the art. It is preferred that the medium be a liquid. Normally an aqueous solution of the antimicrobial agent constitutes the preferred medium for reasons of economy and availability. Beck dye baths constitute a typical aqueous medium. Such dye baths typically comprise a continuous aqueous phase, surfactant, dye and pH adjusting agent. Other conventional dye baths such as continuous foam, kuester, dispersed, jet, etc. are also suitable.
  • the resultant product of the invention exhibits an essentially uniform distribution of antimicrobial agent across the cross-section of the fiber, ie; a substantially homogeneous distribution.
  • This product and its cross-sectional antimicrobial distribution-differs essentially from surface treated fibers as taught in United States Patent Numbers 3,966,659.
  • the inventive product contains a significantly higher proportion of active antimicrobial agent than a product having a uniform antimicrobial distribution that has been made by the prior art technique of melt incorporation.
  • the antimicrobial agent is preferably dissolved in an aqueous bath. Antimicrobials which do not readily form aqueous solutions are still suitable when a surfactant is used to assist in forming a bath to contact the fiber.
  • the concentration of antimicrobial agent in the bath is a function of the concentration of the antimicrobial agent required in the finished textile. Generally the bath contains from about 0.001% to 1% antimicrobial.
  • antimicrobial agents include but are not limited to those described below.
  • microbiocidal compounds examples include, but are not limited to, phenoxarsines (including bisphenoxarsines), phenarsazines (including bisphenarsazines), maleimides, isoindole dicarboximides, having a sulfur atom bonded to the nitrogen atom of the dicarboximide group, halogenated aryl alkanols and isothiazolinone compounds.
  • Organotin compounds are also specifically contemplated.
  • microbiocidal phenoxarsine and phenarsazine compounds useful in the compositions of this invention include compounds represented by the formulas:
  • phenoxarsines and phenarsazines include, but are not limited to, 10-chlorophenoxarsine; 10-iodophenoxarsine; 10-bromophenoxarsine; 4-methyl-10-chlorophenoxarsine; 2-tert-butyl-10-chlorophenoxarsine; 2-methyl-8, 10-dichlorophenoxarsine; 1, 3, 10-trichlorophenoxarsine; 2, 6, 10-trichlorophenoxarsine; 1, 2, 4, 10-thiocyanato phenoxarsine; and 10, 10'-thiobisphenoxarsine; 10, 10'-oxybisphenarazine 10,10'-thiobisphenarsazine; and 10,10'-oxybisphenoxarsine (OBPA).
  • 10-chlorophenoxarsine 10-iodophenoxarsine
  • 10-bromophenoxarsine 4-methyl-10-chlorophenoxarsine
  • microbiocidal maleimide compounds useful in the compositions of this invention are exemplified by a preferred maleimide, N-(2-methylnaphthyl) maleimide.
  • microbiocidal compounds useful in the practice of this invention which are isoindole dicarboximides having a sulfur atom bonded to the nitrogen atom of the dicarboximide group are compounds which contain at least one group having the structure:
  • the preferred isoindole discarboximides are the following:
  • halogenated aryl alkanols which can be used as microbiocidal compounds in accordance with this invention are exemplified by a preferred compound, 2, 4-dichlorobenzyl alcohol.
  • An example of a preferred isothiazolinone compound useful in the composition of this invention is 2-(n-octyl-4-isothiazolin-3-one).
  • the most preferred microbiocidal compounds are the bisphenoxarsines and bisphenarsazines having the formula: where Y is oxygen or sulfur and Z is oxygen or nitrogen. of these bisphenoxarsines and bisphenarsazines, the most preferred are 10, 10'-oxybisphenoxarsine; 10, 10 1- thiobisphenoxarsine; 10, 10'-oxybisphenarsazine; and 10, 10'-thiobisphenarsazine.
  • TBTO bis(tri-n-butyl tin) oxide
  • the invention may be practiced upon fibers at any stage of fabrication including but not limited to mono-filiments, bulked continuous filiment, staple, skein yarn, stack yarn, woven goods, greige goods, nonwoven scrim, needle- punched goods, knits, etc.
  • the practice of this invention includes but is not limited to the typical parameters set forth below.
  • the range of bath concentration levels includes 1 ppm to 120 ppm; with a preferred range from 15 ppm to 40 ppm. The 15 to 40 ppm range is preferred because the treated fiber will contain OBPA in the preferred range.
  • the range of OBPA concentration in the fiber includes 10 to 3300 ppm; with a preferred range from 250-500 ppm. The latter range is preferred because this level provides good antimicrobial protection.
  • the treatment time ranges from less than one minute to greater than 60 minutes; with a preferred range from 5 minutes to 30 minutes and the treatment temperature ranges from 20°C to 100°C; with a preferred range of 40 to 100°C. These respective preferred ranges were selected because they allow effective treatment within moderate handling time at temperatures efficient for OBPA uptake and commonly used for commercial dyeing. pH ranges from 4 to 7 and appears to have little or no effect upon the partitioning of the OBPA. This behavior suggests the non- interference of OBPA with terminal amino groups which are common sites for dye attachment in nylon fiber.
  • a simulated beck dye bath was prepared by adding 1 mL TRITON X-100 surfactant to 1 L tap water with stirring. The pH was adjusted to pH 4.0 or 7.0 with glacial acetic acid or ammonium hydroxide. Powdered OBPA (20-80 mg.) for the desired concentration was added with heating and stirring for one hour. The hot simulated dye bath was filtered through Whatman 2V paper and brought to the desired temperature. -Dilutions of this dye bath were made as desired.
  • the capped tubes were kept in constant temperature water baths without agitation at 40°C or 90°C and at ambient temperature for 25°C.
  • the final dye bath aliquots were removed for analysis at 30 minutes.
  • aliquots were removed at timed intervals of 0.5, 1.0, 2.0, 3.0, 5.0, 10, 15, 30 and 60 minutes. Only one aliquot (1-5 mL) was removed from each tube.
  • the yarn coil was removed with forceps and drained for 10 seconds.
  • the fiber coils were rinsed in fresh 50 mL portions of deionized water for 15 seconds, finger squeezed, and air-dried overnight at 45°C. All samples containing OBPA indicated antimicrobial activity.
  • the treatment bath samples were acid digested and analyzed for total arsenic by the SDDC method.
  • the arsenic depletion in the treatment baths was used to calculate the approximate fiber (yarn) concentration, as OBPA.
  • Some fiber samples were analyzed directly by the SDDC method.
  • Nylon 6 fibers were treated in an OBPA-containing surfactant bath for 30 minutes in the above described general manner.
  • a bath ratio (bath volume, mL: fiber weight, (g) of 20:1 was used.
  • a pH of 4 was used.
  • Other variables are listed below in Table 1.
  • the results of Trials A-C are shown in Figure 1.
  • Example II The trials of Example I were repeated with a pH of 7. The only other variables that were different are listed below in Table 2.
  • Example I The trials of Example I were repeated. The only other variables that were different are listed below in Table 3. The results of trials G-I are shown in Figure 3.
  • Bis (tri-n-butyl tin) oxide 30.2 mg of 98% (TBTO) was added to 500 mL tap water containing 0.5 mL TRITON X-100.
  • the bath concentration was about 50-60 ppm TBTO. The bath was stirred and heated to boiling.
  • Nylon yarn was loosely tied into 4 1.0-g hanks.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Biochemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Microbiology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Textile Engineering (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Artificial Filaments (AREA)
  • Coloring (AREA)
EP85305037A 1984-10-03 1985-07-15 Verfahren zum Einbringen von antimikrobiellen Agenzien in Fasern Withdrawn EP0177126A3 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US65711784A 1984-10-03 1984-10-03
US657117 1984-10-03

Publications (2)

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EP0177126A2 true EP0177126A2 (de) 1986-04-09
EP0177126A3 EP0177126A3 (de) 1987-09-16

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EP85305037A Withdrawn EP0177126A3 (de) 1984-10-03 1985-07-15 Verfahren zum Einbringen von antimikrobiellen Agenzien in Fasern

Country Status (7)

Country Link
EP (1) EP0177126A3 (de)
JP (1) JPS61108774A (de)
KR (1) KR890000244B1 (de)
BR (1) BR8504851A (de)
CA (1) CA1236954A (de)
ES (1) ES8702541A1 (de)
IL (1) IL75582A0 (de)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0332397A3 (en) * 1988-03-08 1989-11-23 Basf Corporation Fiber-containing yarn possessing antimicrobial activity
EP0852148A1 (de) 1991-04-04 1998-07-08 Sion Narrow-Weaving Produkte mit antimikrobiologischer Wirkung

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101403527B1 (ko) 2012-09-24 2014-06-09 주식회사 지클로 항균성 셀룰로오스 섬유의 제조방법 및 이로부터 제조되는 섬유

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE940827C (de) * 1954-04-13 1956-03-29 Bayer Ag Verfahren zur Herstellung von organischen Arsenverbindungen
US3043648A (en) * 1955-12-09 1962-07-10 Sandoz Ltd Process for the fast dyeing of natural and artificial polyamide fibers with water-soluble metal-containing azo dyestuffs
GB932654A (en) * 1960-03-25 1963-07-31 Dow Chemical Co Phenoxarsine compositions for the control of the growth of plants, fungi, and microbes
DE1594897A1 (de) * 1966-10-07 1969-09-18 Albright & Wilson Mfg Ltd Verfahren zur Erhaltung faeulnisverhindernder Substanzen auf den Einfluss von Atmosphaerilien ausgesetzten Oberflaechen
DE2313687C3 (de) * 1973-03-20 1975-08-28 Hoechst Ag, 6000 Frankfurt In Wasser lösliche oder dispergierbare Konzentrate von Triphenylzinnverbindungen und ihre Verwendung zur Verhinderung des Insektenbefalls und der Verrottung von Fasermaterialien oder Pelzen
US4408996A (en) * 1981-10-09 1983-10-11 Burlington Industries, Inc. Process for dyeing absorbent microbiocidal fabric and product so produced

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0332397A3 (en) * 1988-03-08 1989-11-23 Basf Corporation Fiber-containing yarn possessing antimicrobial activity
EP0852148A1 (de) 1991-04-04 1998-07-08 Sion Narrow-Weaving Produkte mit antimikrobiologischer Wirkung

Also Published As

Publication number Publication date
BR8504851A (pt) 1986-07-22
ES8702541A1 (es) 1986-12-16
JPS61108774A (ja) 1986-05-27
KR890000244B1 (ko) 1989-03-11
KR860003381A (ko) 1986-05-23
CA1236954A (en) 1988-05-24
IL75582A0 (en) 1985-10-31
ES546640A0 (es) 1986-12-16
EP0177126A3 (de) 1987-09-16

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Inventor name: MCENTEE, THOMAS C.