Classifications

• • 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
  • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
  • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
  • D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
  • D06M13/207—Substituted carboxylic acids, e.g. by hydroxy or keto groups; Anhydrides, halides or salts thereof
  • D06M13/21—Halogenated carboxylic acids; Anhydrides, halides or salts thereof
• • 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
  • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
  • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
  • D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
  • D06M13/192—Polycarboxylic acids; Anhydrides, halides or salts thereof
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S428/00—Stock material or miscellaneous articles
  • Y10S428/92—Fire or heat protection feature
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
  • Y10T428/2913—Rod, strand, filament or fiber
  • Y10T428/2933—Coated or with bond, impregnation or core

Definitions

• ABSTRACT Flame-resistant polyamide filaments are made by treating drawn polyamide filaments with an aqueous composition of a halogenated compound selected from the class consisting of chlorendic, tetrabromophthalic and tetrachlorophthalic acids and the anhydrides thereof.
• the present invention provides flame-resistant filaments of drawn aliphatic polyamides containing 2 to about 18 percent, preferably 6 to 10 percent, by weight, based on the weight of the filaments, of at least one halogenated compound selected from the class consisting of chlorendic acid, chlorendic anhydride, tetrabromophthalic acid, tetrabromophthalic anhydride, tetrachlorophthalic acid and tetrachlorophthalic anhydride.
• This invention also provides a process for producing flame-resistant filaments wherein filaments of a polyamide are treated with aqueous liquids containing these halogenated compounds. Preferably, treatment with the aqueous liquid is conducted at temperatures of at least 97C. and at a pH less than about 5.
• the filaments produced by the present invention contain from 2 to about 18 percent by weight of a halogenated compound of the aforementioned class.
• the compound is present in the filaments, presumably, in a salt form from combination with amine ends produced by polymer molecules and/or as a coordinated molecule, and can be substantially entirely extracted from the filaments.
• chlorendic acid can be extracted with aqueous solutions containing from 1 to 5 percent, by weight of a base such as ammonia, sodium carbonate or sodium hydroxide.
• the filaments of this invention show a significant reduction in burning propensity in comparison to untreated fibers.
• a superior rating, as determined by the Vertical Flame Test, is obtained when the halogenated compound content is at least 3 percent, by weight. At contents greater than about 6 percent, by weight, the
• filaments are rated self-extinguishing or nearly so when the combustion source is removed and filaments containing 6 to 10 percent of the halogenated compound are a preferred embodiment of this invention. While amounts greater than 10 percent by weight may be incorporated, the resistance of the filament to burning is not increased proportionally.
• halogenated compounds used in the practice of this invention are reactive towards the polyamides, degradative discoloration of the treated filaments can occur at elevated temperatures. However, at moderate temperatures, eg in the range of about l30l50C., or for short thermal exposure times at higher temperatures, e.g., on the order of 200C., filaments of this invention exhibit very little, if any, change in color. This is, of course, a distinct advantage over the use of the halogenated compounds in conjunction with molten polymer. In addition, since the halogenated compounds are applied to drawn filaments, the disadvantages attendant to the drawing of polyamide filaments containing foreign matter are avoided.
• the process of the present invention provides flameresistant filaments by treatment of drawn polyamide filaments with aqueous liquids containing the halogenated compounds.
• aqueous compositions containing the halogenated compound may be padded onto the filaments and the treated filaments subsequently heated to an elevated temperature such as by passing them over heated rolls or through hot-air ovens and the like. Suitable temperatures range from 97C. to about 140C. Elevated temperatures are used to increase the rate of absorption of the halogenated compound by the filaments and to facilitate removal of water.
• the treating liquid may or may not contain a dye.
• the polyamide filaments are treated in an aqueous bath that contains chlorendic acid and is maintained at an elevated temperature, e.g., at least about 97C. and preferably at 98C. to 100C. At temperatures below 97C., the solubility of chlorendic acid in water is so low it will not give an even strike on the fabric.
• the pH of the aqueous bath will not exceed 5 and for best results the pH should be between 2 and 4.
• the aqueous bath may be made acidic by the use of either organic or mineral acids such as, for example, acetic, formic, oxalic and phosphoric acids.
• organic or mineral acids such as, for example, acetic, formic, oxalic and phosphoric acids.
• the pH may be relatively high during the initial period of the treatment, the pH should be reduced to a value of 2 to 4 prior to completing the treatment. Low pH values promote bath exhaustion and high fiber up-take of halogenated compound.
• polyamide filaments are treated with chlorendic acid in the course of their manufacture.
• the chlorendic acid may be applied to continuous filaments, yarns, tows, and the like following the drawing step and prior to packaging by having the chlorendic acid present in lubricating finishes, post-draw baths or other treating media. If the filaments are to be converted to short fibers, e.g. staple fibers, the fibers may be treated after the cutting operation.
• the filaments may be treated after packaging.
• Package-dyeing techniques such as are known to those skilled in the art may be followed, it being understood, of course, that the high temperatures and low pH values required for this invention are to be incorporated in the treatment.
• the filaments may also be treated after they have been converted to fabric.
• the halogenated compound may be added to conventional baths such as dyebaths used in the processing of the fabrics or in a special bath as an addition to standard treatment.
• the treatment of the filaments may be before, after, during, or instead of, dyeing.
• the treatment may be applied to filaments in the form of nonwovens, knit or woven fabrics. Also, carpets, upholstery, artificial hair pieces, wig fibers and the like may be made more flame resistant by the practice of this invention.
• the amount of halogenated compound of the aforementioned class that is used in the bath may vary from about 1 percent to about 10 percent, by weight.
• substantial hydrolysis to the acid will occur and both acid and anhyhaving 320 filaments and an RV of 56.
• the yarn is drawn at a draw ratio of 3.0 to a denier per filament of 18.5.
• the yarn is knitted into fabric and dyed using the foltreating baths may contain small amounts of one or l i procedure, more of the following: an organic liquid, a wetting An aqueous dyebath is prepared wherein for each agent, a buffering agent, a whitener and a seque e ng 100 grams of fabric there is used 2 kilograms of water, agent. 25 ml. of a 1 percent solution of tetrasodium ethylene- Tl'le p ly mi useful in the Practice Of this invendiaminetetraacetate, 16 ml.
• 62055 is added to the bath, followed by the fabhexamethylene adipamide (66-nylon) is highly preric.
• the bath is then raised to the boil in 45-60 minutes ferred polyamide.
• ferred polyamide Among other useful polyamides and held at the boil for 30 minutes.
• a boiling solution there may be mentioned the polymer prepared from of 12 grams of chlorendic acid in 200 ml. of water is caprolactam (6-nylon) and the polymer made from then added, the pH adjusted, the bath boiled for an adbis(4-aminocyclohexyl)methane and dodecanedioic ditional 30 minutes and the pH measured. The dyed acid.
• Copolymers such as those from 66- and 6-nylon fabric is rinsed for 10 minutes in cold water and air may also be used. dried.
• the chlorendic acid content of the filaments is in the following examples illustrating the invention, determined and their flame resistance measured. Reall percentages are by weight based on the weight of the sults are shown in the Table.
• Relative viscosity is the ratio of absolute viscosities at 25C. of solution and solvent.
• the solvent is 90 percent, by weight, formic acid and 10 percent water and the solution is 8.4 percent, by weight, polyamide.
• the chlorendic acid content of filaments is determined by coulometric analysis of chloride using the method described in Cotlov et al., Journal of Laboratory and Clinical Medicine, 51, 461-468, 1958 and calculated as chlorendic acid.
• the weight the filaments gain from the treatment with the halogenated compound differs from the halogenated compound content as determined by analysis by no more than 2 percent.
• a measurement of weight gain can be taken as a meaningful indication of the halogenated compound content.
• the significance of this approximation can be augmented by flame performance wherein filaments showing a weight gain of at least 6 percent are flame resistant, i.e., they self-extinguish, frequently in a matter of seconds, e.g., less than seconds.
• a -ml. bath is prepared by adding to water at 60C. 0.025 gram of the product obtained by condensing 20 molecular proportions of ethylene oxide with one molecular proportion of a monofunctional 18- carbon, aliphatic alcohol, 0.050 gram of Acid Red 151 (C.I. 26900) and sufficient formic acid to give a pH of 3.
• a 25-gram swatch of the fabric is added, the temperature raised to 71C. in about 20 minutes, and 0.38 gram of a mixture of alpha and beta methylnaphthalenes added. After 10 minutes formic acid is added to return the pH of the bath to 3 and the bath heated to the boil. To the bath is added 0.25 gram of chlorendic acid.
• the fabric is then heat-set, free to relax, at 190C. for 60 seconds.
• the filaments are found to contain 6.2 percent chlorendic acid and, after a 3-second ignition, to selfextinguish in about 1.3 seconds* after burning about 2.5 inches (Average of four samples).
• EXAMPLE III minutes rinsed in cool water and dried.
• the dried fabric is then repadded with a paste which contains per 100 parts of paste, 7 parts of chlorendic anhydride, 5 parts thiodiglycol, 2 parts of a fatty amide, 2 parts of a nonionic surfactant, 55 parts of the purified natural gum ether, 5 parts of benzyl alcohol, 0.5 part of the sodium salt of a sulfonated alkyl benzene and 0.5 part of 2-ethylhexanol.
• the repadded fabric is steamed 12 minutes at 100C., scoured 3 minutes at 60C.
• EXAMPLE V quizzed to 5.5 with acetic acid.
• the temperature is raised to about 99C. in 45 minutes and a solution of 12 grams of tetrabromophthalic anhydride in grams of benzyl alcohol heated to 160C. is added.
• the bath is maintained at the boil for 60 minutes and the pH found to be 4.
• the treated fabric is then rinsed for 10 minutes at 21C., excess water removed and the fabric heated to about 150C. for 10 minutes.
• the weight gain for the fabric is 8.7 percent and, following a 12-second ignition, it burns only 14 seconds and 1.5 inches (3.8 centimeters).
• the pH of the bath is adjusted to 2.5 with 10 percent phosphoric acid.
• Fifty ml. of a solution containing 1 percent of Acid Blue 78 (C.I. 62105) and 100 grams of the fabric described in Example I is added.
• the bath is boiled for 30 minutes, a boiling solution of 12 grams of tetrachlorophthalic anhydride in 500 m1. of water added and the bath boiled for an additional 30 minutes.
• the pH is found to be 2.5.
• the fabric is rinsed for 10 minutes in cold water, excess water removed and the fabric dried in air.
• the weight gain for the fabric is 2.75 percent and the flame retardant content, calculated as tetrachlorophthalic acid, is 2.9 percent.
• the fabric burns 3 seconds and the burn length is 0.25 inch (0.6 centimeter).
• a process for imparting flame resistance to drawn polyamide filaments selected from the group consisting of poly(hexamethylene adipamide) and poly(methylene-di-1,4-cyclohexylene dodecanediamide) filaments comprising treating such filaments with an aqueous composition of a halogenated compound of the class consisting of chlorendic, tetrabromophthalic and tetrachlorophthalic acids and their anhydrides, said aqueous composition being at a temperature of at least 97C. and at a pH of less than about 5, and drying the filaments.
• polyamide is poly(methylene-di-l,4-cyclohexylene dodecane diamide).

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• Engineering & Computer Science (AREA)
• Textile Engineering (AREA)
• Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Applications Claiming Priority (1)

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Family Applications (1)

Country Status (7)

Cited By (3)

Citations (11)

Family Cites Families (1)

• 0
  • BE BE790109D patent/BE790109A/fr unknown
• 1971
  • 1971-10-15 US US00189753A patent/US3772067A/en not_active Expired - Lifetime
• 1972
  • 1972-10-13 GB GB4744072A patent/GB1384154A/en not_active Expired
  • 1972-10-13 NL NL7213902A patent/NL7213902A/xx unknown
  • 1972-10-13 DE DE2250352A patent/DE2250352A1/de active Pending
  • 1972-10-13 IT IT30493/72A patent/IT986858B/it active
  • 1972-10-13 FR FR7236335A patent/FR2156336B1/fr not_active Expired

Patent Citations (11)

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