US3772067A - A process for imparting flame resistance to drawn polyamide filaments - Google Patents

A process for imparting flame resistance to drawn polyamide filaments Download PDF

Info

Publication number
US3772067A
US3772067A US00189753A US3772067DA US3772067A US 3772067 A US3772067 A US 3772067A US 00189753 A US00189753 A US 00189753A US 3772067D A US3772067D A US 3772067DA US 3772067 A US3772067 A US 3772067A
Authority
US
United States
Prior art keywords
filaments
percent
acid
halogenated compound
fabric
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.)
Expired - Lifetime
Application number
US00189753A
Other languages
English (en)
Inventor
T Alderson
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.)
EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
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 EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Application granted granted Critical
Publication of US3772067A publication Critical patent/US3772067A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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).

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
US00189753A 1971-10-15 1971-10-15 A process for imparting flame resistance to drawn polyamide filaments Expired - Lifetime US3772067A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US18975371A 1971-10-15 1971-10-15

Publications (1)

Publication Number Publication Date
US3772067A true US3772067A (en) 1973-11-13

Family

ID=22698626

Family Applications (1)

Application Number Title Priority Date Filing Date
US00189753A Expired - Lifetime US3772067A (en) 1971-10-15 1971-10-15 A process for imparting flame resistance to drawn polyamide filaments

Country Status (7)

Country Link
US (1) US3772067A (enrdf_load_stackoverflow)
BE (1) BE790109A (enrdf_load_stackoverflow)
DE (1) DE2250352A1 (enrdf_load_stackoverflow)
FR (1) FR2156336B1 (enrdf_load_stackoverflow)
GB (1) GB1384154A (enrdf_load_stackoverflow)
IT (1) IT986858B (enrdf_load_stackoverflow)
NL (1) NL7213902A (enrdf_load_stackoverflow)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3903221A (en) * 1974-05-08 1975-09-02 Du Pont Process and product
US5114786A (en) * 1990-06-25 1992-05-19 Apex Chemical Corp. Flame retardant polyamide fabrics
US20080293326A1 (en) * 2007-05-22 2008-11-27 The Pilot Ink Co., Ltd. Hair for toys
CN116731310A (zh) * 2023-06-27 2023-09-12 河南工业大学 一种卤代苯酐接枝尼龙的制备方法

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3285995A (en) * 1963-05-22 1966-11-15 Michigan Chem Corp Process of preparing self-extinguishing resinous polyesters based upon tetrabromophthalic anhydride
US3312565A (en) * 1962-03-14 1967-04-04 Eric T Rayner Flammable base with fire-retardant protective coating
US3350334A (en) * 1962-12-31 1967-10-31 North American Aviation Inc Castor oil-hexachloroendomethylenetetrahydrophthalic anhydride reaction product
US3418267A (en) * 1965-09-01 1968-12-24 Du Pont Flame-resistant polyamides and process thereof
US3437682A (en) * 1966-04-11 1969-04-08 Ashland Oil Inc Halogenated polyfunctional carboxylic ester
US3445482A (en) * 1965-08-12 1969-05-20 Universal Oil Prod Co Bis(polyhalocycloalkene)dicarboxylic acids and derivatives thereof
US3465006A (en) * 1968-11-08 1969-09-02 Universal Oil Prod Co Polyhalo - substituted polyhydromethanonaphthalenedicarboxylic acids or anhydrides thereof
US3519597A (en) * 1964-02-17 1970-07-07 Hooker Chemical Corp Adducts of hexahalocyclopentadiene with alkadienes as fire-retardant additives for polymers
US3538189A (en) * 1964-08-06 1970-11-03 Hooker Chemical Corp Fire retardant polyesters from acyldiphosphonic acids and polyhalobicyclic diacids
US3547876A (en) * 1968-07-01 1970-12-15 American Cyanamid Co Synergistic flame-retardant compositions
US3642525A (en) * 1968-08-08 1972-02-15 Ventron Instr Corp Fire-resistant fibers and fabric

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1234292A (enrdf_load_stackoverflow) * 1968-03-29 1971-06-03

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3312565A (en) * 1962-03-14 1967-04-04 Eric T Rayner Flammable base with fire-retardant protective coating
US3350334A (en) * 1962-12-31 1967-10-31 North American Aviation Inc Castor oil-hexachloroendomethylenetetrahydrophthalic anhydride reaction product
US3285995A (en) * 1963-05-22 1966-11-15 Michigan Chem Corp Process of preparing self-extinguishing resinous polyesters based upon tetrabromophthalic anhydride
US3519597A (en) * 1964-02-17 1970-07-07 Hooker Chemical Corp Adducts of hexahalocyclopentadiene with alkadienes as fire-retardant additives for polymers
US3538189A (en) * 1964-08-06 1970-11-03 Hooker Chemical Corp Fire retardant polyesters from acyldiphosphonic acids and polyhalobicyclic diacids
US3445482A (en) * 1965-08-12 1969-05-20 Universal Oil Prod Co Bis(polyhalocycloalkene)dicarboxylic acids and derivatives thereof
US3418267A (en) * 1965-09-01 1968-12-24 Du Pont Flame-resistant polyamides and process thereof
US3437682A (en) * 1966-04-11 1969-04-08 Ashland Oil Inc Halogenated polyfunctional carboxylic ester
US3547876A (en) * 1968-07-01 1970-12-15 American Cyanamid Co Synergistic flame-retardant compositions
US3642525A (en) * 1968-08-08 1972-02-15 Ventron Instr Corp Fire-resistant fibers and fabric
US3465006A (en) * 1968-11-08 1969-09-02 Universal Oil Prod Co Polyhalo - substituted polyhydromethanonaphthalenedicarboxylic acids or anhydrides thereof

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3903221A (en) * 1974-05-08 1975-09-02 Du Pont Process and product
US5114786A (en) * 1990-06-25 1992-05-19 Apex Chemical Corp. Flame retardant polyamide fabrics
US20080293326A1 (en) * 2007-05-22 2008-11-27 The Pilot Ink Co., Ltd. Hair for toys
EP2006004A3 (en) * 2007-05-22 2009-01-07 The Pilot Ink Co., Ltd. Hair for toys
CN116731310A (zh) * 2023-06-27 2023-09-12 河南工业大学 一种卤代苯酐接枝尼龙的制备方法

Also Published As

Publication number Publication date
FR2156336A1 (enrdf_load_stackoverflow) 1973-05-25
DE2250352A1 (de) 1973-04-19
GB1384154A (en) 1975-02-19
FR2156336B1 (enrdf_load_stackoverflow) 1976-05-21
NL7213902A (enrdf_load_stackoverflow) 1973-04-17
IT986858B (it) 1975-01-30
BE790109A (fr) 1973-02-01

Similar Documents

Publication Publication Date Title
US2510777A (en) Polyamide treated with a hypophosphorous acid compound
EP0212948B1 (en) Aromatic polyamide fibers and process for stabilizing such fibers
US4755335A (en) Method of improving impregnation of poly (meta-phenylene isophthalamide) fibers
US5468554A (en) Dyed antistain nylon with cationic dye modifier
CN1036670C (zh) 织物处理方法
US4120914A (en) Aromatic polyamide fiber blend for protective clothing
US5155178A (en) Antistain block copolymer compositions of modified nylon copolymers and high carbon nylons
EP0661397A2 (en) Process for the manufacture of a stain resistant melt colored carpet
US5242733A (en) Carpets and fabrics of antistain block copolymer compositions of modified nylon copolymers and high carbon nylons
US3772067A (en) A process for imparting flame resistance to drawn polyamide filaments
US4112016A (en) Polyamide fiber
US4014829A (en) Flame resistant fiber blends
US4061810A (en) Flame-retardant carpet and composition for preparing the same
US5114786A (en) Flame retardant polyamide fabrics
US2201741A (en) Polymeric materials
EP0228224B1 (en) Aromatic polyamide fibers and processes for making such fibers
US2424284A (en) Fixation of finely divided substances
US5330834A (en) Dye-retarded nylon 6/6,6 block copolymer fibers
US3779705A (en) Process for dyeing fibers or fabrics of aromatic polyamides
US3190718A (en) Process of heat treating a tow of polyester filaments while under tension to modify the properties thereof
US3436250A (en) Method for retaining flame and soil resistances to fabrics
EP0901534B1 (en) Process for dyeing cationic-dyeable modified polyamide fibers with acid dyes
US3233961A (en) Process for dyeing cellulose acetate having an acetyl value of at least 59% in the presence of hydroxyalkylamine-fatty acid condensation products
US2540726A (en) Treatment of a heat set, oriented nylon fabric with formaldehyde
US4008345A (en) Process for fire-proofing treatment of shaped articles of aromatic polyamides