WO2013148653A1 - Dyeing and printing of fabrics including partially aromatic polyamides - Google Patents

Dyeing and printing of fabrics including partially aromatic polyamides Download PDF

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Publication number
WO2013148653A1
WO2013148653A1 PCT/US2013/033841 US2013033841W WO2013148653A1 WO 2013148653 A1 WO2013148653 A1 WO 2013148653A1 US 2013033841 W US2013033841 W US 2013033841W WO 2013148653 A1 WO2013148653 A1 WO 2013148653A1
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WIPO (PCT)
Prior art keywords
fiber
article
treatment
yarn
partially aromatic
Prior art date
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PCT/US2013/033841
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English (en)
French (fr)
Inventor
Thomas Edward Schmitt
Kamleshkumar Chunilal Patel
Original Assignee
Invista Technologies S.À R.L.
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 Invista Technologies S.À R.L. filed Critical Invista Technologies S.À R.L.
Priority to IN2134MUN2014 priority Critical patent/IN2014MN02134A/en
Priority to KR1020147029592A priority patent/KR20140137009A/ko
Priority to CN201380027698.XA priority patent/CN104321485A/zh
Priority to US14/395,293 priority patent/US20150308041A1/en
Priority to EP13768029.4A priority patent/EP2831335A4/en
Publication of WO2013148653A1 publication Critical patent/WO2013148653A1/en

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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/34—Material containing ester groups
    • D06P3/52—Polyesters
    • D06P3/522—Polyesters using basic dyes
    • 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
    • D06M13/244—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 sulfur or phosphorus
    • D06M13/282—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 sulfur or phosphorus with compounds containing phosphorus
    • D06M13/285—Phosphines; Phosphine oxides; Phosphine sulfides; Phosphinic or phosphinous acids or derivatives 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
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/39—Aldehyde resins; Ketone resins; Polyacetals
    • D06M15/423—Amino-aldehyde resins
    • D06M15/43—Amino-aldehyde resins modified by phosphorus compounds
    • D06M15/431—Amino-aldehyde resins modified by phosphorus compounds by phosphines or phosphine oxides; by oxides or salts of the phosphonium radical
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/02—Material containing basic nitrogen
    • D06P3/04—Material containing basic nitrogen containing amide groups
    • D06P3/14—Wool
    • D06P3/16—Wool using acid dyes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/02—Material containing basic nitrogen
    • D06P3/04—Material containing basic nitrogen containing amide groups
    • D06P3/14—Wool
    • D06P3/18—Wool using basic dyes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/02—Material containing basic nitrogen
    • D06P3/04—Material containing basic nitrogen containing amide groups
    • D06P3/24—Polyamides; Polyurethanes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/02—Material containing basic nitrogen
    • D06P3/04—Material containing basic nitrogen containing amide groups
    • D06P3/24—Polyamides; Polyurethanes
    • D06P3/241—Polyamides; Polyurethanes using acid dyes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/02—Material containing basic nitrogen
    • D06P3/04—Material containing basic nitrogen containing amide groups
    • D06P3/24—Polyamides; Polyurethanes
    • D06P3/242—Polyamides; Polyurethanes using basic dyes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/02—Material containing basic nitrogen
    • D06P3/04—Material containing basic nitrogen containing amide groups
    • D06P3/24—Polyamides; Polyurethanes
    • D06P3/26—Polyamides; Polyurethanes using dispersed dyestuffs
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/58—Material containing hydroxyl groups
    • D06P3/60—Natural or regenerated cellulose
    • D06P3/6016—Natural or regenerated cellulose using basic dyes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/58—Material containing hydroxyl groups
    • D06P3/60—Natural or regenerated cellulose
    • D06P3/66—Natural or regenerated cellulose using reactive dyes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/82—Textiles which contain different kinds of fibres
    • D06P3/8204—Textiles which contain different kinds of fibres fibres of different chemical nature
    • D06P3/8209—Textiles which contain different kinds of fibres fibres of different chemical nature mixtures of fibres containing amide groups
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/82—Textiles which contain different kinds of fibres
    • D06P3/8204—Textiles which contain different kinds of fibres fibres of different chemical nature
    • D06P3/8214—Textiles which contain different kinds of fibres fibres of different chemical nature mixtures of fibres containing ester and amide groups
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/82—Textiles which contain different kinds of fibres
    • D06P3/8204—Textiles which contain different kinds of fibres fibres of different chemical nature
    • D06P3/8219—Textiles which contain different kinds of fibres fibres of different chemical nature mixtures of fibres containing hydroxyl and amide groups
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/82—Textiles which contain different kinds of fibres
    • D06P3/8204—Textiles which contain different kinds of fibres fibres of different chemical nature
    • D06P3/8271—Textiles which contain different kinds of fibres fibres of different chemical nature mixtures of fibres containing amide and nitrile groups
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
    • D06P5/02—After-treatment
    • 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
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/30—Flame or heat resistance, fire retardancy properties

Definitions

  • the invention relates to dyeing and finishing fabrics including flame resistant/ flame retardant (FR) fabrics that include partially aromatic polyamide fibers and a fiber exhibiting vapor phase action, such as cellulose fibers that have received FR treatment.
  • FR flame resistant/ flame retardant
  • lEDs are constructed of numerous materials (e.g. high- explosive charges, flammable liquids, shrapnel, etc.), some acting as projectiles and others acting as incendiaries upon detonation.
  • military fabrics must be of varied construction to handle the multitude of threats from an I ED.
  • flame retardant fabrics used in protective clothing: (1) Fabrics made from flame retardant organic fibers (e.g. aramid, flame retardant rayon, polybenzimidazole, modacrylic etc.); and (2) Flame retardant fabrics made from conventional materials (e.g. cotton) that have been post treated to impart flame retardancy.
  • Nomex® and Kevlar® aromatic polyamides are among the most common types of flame retardant synthetic fibers. These are made by solution spinning a meta- or para- aromatic polyamide polymer into fiber. Aromatic polyamides do not melt under extreme heat, are naturally flame retardant, but must be solution spun. Unfortunately, Nomex® and KEVLAR® are not very comfortable and are difficult and expensive to produce.
  • modacrylic is fiber comprising 30 to 70 parts by mass of acrylonitrile and 70 to 30 parts by mass of a monomer such as a halogen- containing vinylidene monomer and/or a halogen-containing vinyl monomer.
  • a monomer such as a halogen- containing vinylidene monomer and/or a halogen-containing vinyl monomer.
  • commercial examples include PROTEX® C and PROTEX® M fibers manufactured by Kaneka.
  • modacrylic fibers are known to impart flame resistance properties to fabrics comprising non-FR treated cellulosic fibers such as cotton and lyocell. Examples can be found in EP1498522 and WO2008027454.
  • Cellulose fibers such as acetate, rayon, lyocell, and cotton can be rendered flame resistant by incorporating phosphorus-nitrogen additives at fiber spinning or at fabric finishing.
  • the mechanisms for flame resistance performance of both modacrylic and flame resistant cellulose rely on gases emitted from the fibers which dilute, cool, or chemically neutralize flammable gases (vapor phase action) and which form intumescent char barriers (condensed phase action).
  • Post-treatment flame retardants are applied to fabrics and can be broken down into two basic categories: (1 ) Durable flame retardants; and (2) Non-durable flame retardants.
  • Durable flame retardants For protective clothing, the treatment must withstand laundering, so only durable treatments are selected.
  • durable flame retardant chemistry relies on phosphorus-based FR agents and chemicals or resins to fix the FR agents to the fibers.
  • U.S. Patent No. 6,132,476 discloses the dyeing of FR fabrics and garments, but acknowledges that when these fabrics include certain inherently flame resistant fiber such as aromatic polyamides in combination with fibers such as FR rayon, the dyeing process reduces the effectiveness of the FR properties. The reason is that the high temperatures required for dyeing aromatic polyamides cause depletion of the FR agents in the FR rayon and make the fabrics more susceptible to further depletion of the FR additive during subsequent laundering. Specific dyeing processes and conditions are required to avoid these concerns.
  • One aspect provides an article which has been dyed and/or printed exhibiting flame resistant or flame retardant property including a primary yarn; where the primary yarn includes a flame resistant or flame retardant (FR) fiber having significant vapor phase action such as modacrylic or FR cellulose fibers and a fiber different from said flame resistant or flame retardant fiber including a partially aromatic polyamide fiber; where the partially aromatic polyamide polymer without FR additives is melt spun into fiber.
  • FR flame resistant or flame retardant
  • the partially aromatic polyamide fiber excludes FR additives, which are integral to the fiber composition.
  • the article may be a yarn. However, the article may also be a fabric or a garment including the flame resistant yarn.
  • an article exhibiting flame resistant or flame retardant (FR) property including (a) a fabric including a pre-treatment applied dye or print or combinations thereof; and (b) a post-treatment applied FR additive; wherein the fabric includes a primary yarn comprising a fiber having vapor phase action and a partially aromatic polyamide fiber.
  • the pre- treatment is selected from the group consisting of a dye, a print, or combinations thereof and is present on the garment prior to the addition of the post-treatment which includes an FR additive.
  • the print may be applied before or after the application of the FR treatment because the printing process does not interfere with the FR treatment in the manner that high temperature dyeing may.
  • an article exhibiting flame resistant or flame retardant property including (a) a fabric including a pre-treatment consisting of dyeing, printing, and combinations thereof; and (b) a post-treatment including a flame resistant or flame resistant or flame retardant treatment; wherein said fabric includes a primary yarn including a cotton fiber and a partially aromatic polyamide fiber.
  • a method for preparing an article exhibiting flame resistant or flame retardant property including the following sequential process (a) preparing a fabric including primary yarn comprising a fiber having vapor phase action and a partially aromatic polyamide fiber; (b) providing a pre-treatment selected from the group consisting of dyeing, printing, and combinations thereof; and (c) a post-treatment including a flame resistant or flame resistant (FR) treatment.
  • An optional subsequent process for printing may be introduced following the post-treatment application of FR additive.
  • flame resistant has subtle differences in the art. The differences in the usage of the terms relate to describing fabrics which either resist burning, burn at a slower rate and are capable of self-extinguishing under conditions such as a vertical flame test.
  • flame resistant and “flame retardant” are used interchangeably and are meant to include any fabric that possesses one or more of the desired properties such as resistance to burning, slow burning, self-extinguishing, etc.
  • vapor phase action for fibers useful in the present invention is meant to include fibers which dilute, cool, or chemically neutralize flammable gases.
  • the mechanisms for flame resistance performance of both modacrylic and flame resistant cellulose rely on gases emitted from the fibers which dilute, cool, or chemically neutralize flammable gases (vapor phase action) and which form intumescent char barriers (condensed phase actions).
  • the articles specifically, yarns, fabrics and garments exhibit flame resistant and/or flame retardant properties.
  • the yarns include at least one fiber which is a partially aromatic polyamide.
  • the yarn including the partially aromatic fiber is referred to in the claims as a "primary yarn.”
  • the term "primary yarn” is not meant to establish any relative weight percent of yarn in comparison to other yarns that may be present in the article, but instead is used to distinguish the yarn from other yarns.
  • the primary yarn must include a partially aromatic fiber which excludes spun-in FR additives combined with a FR fiber such as a FR cellulose fiber, modacrylic fiber, and mixtures thereof.
  • MXD6 polyamide fibers are dye-able using several types of dyes for the pre-treatment applied dye. This enables the dyer/printer/finisher to have extra flexibility in choosing the best and most compatible dyeing chemistry for performance and cost. A wider range of dye and pigment selection permits the dyer to more easily meet stringent military requirements for the IR reflectance of camouflage fabrics. Minimizing IR reflectance is critical to prevent wearer from being seen via IR night vision goggles.
  • the articles including a pre-treatment such as a dye or a print or both.
  • the dye may be selected from the group consisting of acid dye, cationic dye, disperse dye, vat dye, and combinations thereof. Where a dye is included, the article may be dyed to a union shade. While the post-treatment step includes an FR treatment, a second FR treatment that occurs during the pre-treatment dyeing or printing may also be provided
  • MXD6 fibers may allow FR ingredients (such as cyclic phosphinate esters) to be added at fabric dyeing,
  • the partially aromatic fibers may be prepared in the presence or absence of non- halogen flame retardant additives.
  • the spun-in non-halogen flame retardant additives can include: condensation products of melamine (including melam, melem, and melon), reaction products of melamine with phosphoric acid (including melamine phosphate, melamine pyrophosphate, and melamine polyphosphate (MPP)), reaction products of condensation products of melamine with phosphoric acid (including melam polyphosphate, melem
  • polyphosphate polyphosphate, melon polyphosphate), melamine cyanurate (MC), zinc diethylphosphinate (DEPZn), aluminum diethylphosphinate (DEPAI), calcium diethylphosphinate, magnesium diethylphosphinate, bisphenol-A bis(diphenyphosphinate) (BPADP), resorcinol bis(2,6-dixylenyl phosphate) (RDX), resorcinol bis(diphenyl phosphate) (RDP), phosphorous oxynitride, zinc borate, zinc oxide, zinc stannate, zinc hydroxystannate, zinc sulfide, zinc phosphate, zinc silicate, zinc hydroxide, zinc carbonate, zinc stearate, magnesium stearate, ammonium octamolybdate, melamine molybdate, melamine octamolybdate, barium metaborate, ferrocene, boron
  • the flame retardant additive When present in the partially aromatic polyamide fiber, the flame retardant additive is present in an amount from about 1% to about 25% w/w, including from about 5% to about 20% w/w, about 5% to about 10%, and about 10%.
  • the mean particle size of the flame retardant additive is less than about 3 microns, including less than about 2 microns, and less than about 1 micron.
  • the particle size of the flame retardant additive may be prepared by a milling process which comprises air jet milling of each component, or of co-milling blends of components to reduce the particle size.
  • Other wet or dry milling techniques known in the art e.g. media milling
  • milling may involve the injection of liquid milling aids, possibly under pressure, into the mill at any suitable point in the milling process. These liquid aids are added to stabilize the flame retardant system and/or prevent agglomeration. Additional components to aid in particle wetting and/or prevent re-agglomeration may also be added at any suitable point during the milling of flame retardant additive, the blending of the flame retardant additive and polymer, and/or the fiber spinning process.
  • the flame retardant may be compounded with the polymeric material in an extruder.
  • An alternative method involves dispersing the flame retardant composition in polymer at a higher concentration than desired in the final polyamide fiber product, and forming a
  • the masterbatch may be ground or pelletized and the resulting particulate dry- blended with additional polyamide resin and this blend used in the fiber spinning process.
  • Yet another alternative method involves adding some or all components of the flame retardant additive to the polymer at a suitable point in the polymerization process.
  • the partially aromatic fibers exclude spun-in FR additives.
  • the partially aromatic polyamide may include polymers or copolymers including monomers selected from the group consisting of aromatic diamine monomers, aliphatic diamine monomers, aromatic diacid monomers, aliphatic diacid monomers and combinations thereof.
  • the partially aromatic polyamide can also include or exclusively be MXD6 which includes an aromatic diamine and non-aromatic diacid.
  • Other partially aromatic polyamides can be based upon an aromatic diacid such as terephthalic acid (polyamide 6T) or isophthalic acid (polyamide 6I) or blends thereof (polyamide 6T/6I).
  • the melting, or processing temperatures, of partially aromatic polyamides ranges from about 240°C (for MXD6) to about 355°C (for polyamideimide), including about 260°C, 280°C, 300°C, 320°C, and 340°C.
  • Nylon 6 and nylon 6,6 have melting temperatures of about 220°C and 260°C, respectively. The lower the melting temperature, the easier the polyamide polymer is to process into fiber.
  • the partially aromatic polyamides may also include co-polymers or mixtures of multiple partially aromatic amides.
  • MXD6 can be blended with Nylon 6/6T prior to forming a fiber.
  • partially aromatic polymers may be blended with an aliphatic polyamide or co-polymers or mixtures of multiple aliphatic polyamides.
  • MXD6 can be blended with Nylon 6,6 prior to forming a fiber.
  • the partially aromatic fiber may include up to about 20% by weight of the fiber of one or more aliphatic polyamides.
  • the partially aromatic fiber can be a staple fiber or continuous filament yarn.
  • the partially aromatic fiber can also be contained in a nonwoven fabric such as spun bond, melt blown, or a combination thereof.
  • the filament cross section can be any shape, including round, triangle, star, square, oval, bi-lobal, tri-lobal, or flat. Further, the filament can be textured using known texturing methods.
  • the partially aromatic polyamides spun into fibers can also include additional partially aromatic or aliphatic polymers.
  • a mixture of more than one polyamide polymer may be blended prior to spinning into yarn or a multi- filament yarn may be produced containing at least one partially aromatic polyamide polymer and an additional partially aromatic polyamide polymer or aliphatic polymer in a bicomponent form such as a side-by-side or core-sheath configuration.
  • the partially aromatic fiber will be combined with an FR fiber having significant vapor phase action such as modacrylic or FR cellulose fibers to form the primary yarn.
  • the yarn may include only the partially aromatic fiber and the FR fiber; alternatively other fibers which are FR or non-FR fibers may be included.
  • the useful amount of partially aromatic fiber varies. Suitable amounts of partially aromatic fiber include about 5% to about 75% by weight of the primary yarn; about 5% to about 60% by weight of the yarn; and about 25% to about 50% by weight of the yarn.
  • the combined yarn may be prepared by any suitable method.
  • the yarn may be a blended staple yarn.
  • the blended staple yarn may be an intimate blend in which the partially aromatic fiber and FR fiber are uniformly blended throughout the yarn.
  • the yarn may be a single or ply twisted yam, a covered yarn (including single and double covering) or a core-spun yarn, among others.
  • the primary yarn must include at least one FR fiber which is and has significant vapor phase action such as modacrylic or FR cellulose fibers, and combinations thereof.
  • the FR fiber may also be FR cellulose where an FR additive is added to the FR cellulose during fiber manufacturing.
  • an FR treatment may be applied to the article including an untreated cellulosic fiber.
  • suitable cellulosic fibers include cotton, rayon or lyocell.
  • Articles that include FR cellulose are meant to include those in which a constituent element, such as a yarn, is treated prior to incorporation into an article.
  • Articles that include FR cellulose are also meant to include those treated after combining the cellulose into a yarn, as well as those treated after the yarns have been made into fabric or garments.
  • cellulose includes, but is not limited to, acetate, cotton, rayon, lyocell, and combinations thereof.
  • one or more cellulosic fibers can be combined with each other and/or with modacrylic.
  • the amounts of FR fiber having significant vapor phase action may vary. Suitable amounts of this fiber include about 25% to about 75% by weight of the primary yarn; greater than 25% to about 75% by weight of the yarn; about 40% to about 60% by weight of the yarn; and about 50% to about 75% by weight of the yarn.
  • a post-treatment applied FR additive is introduced to article, fabric or garment, after dyeing.
  • Post-treatment flame retardants include: (1 ) Durable flame retardants; and (2) Non-durable flame retardants.
  • FR treatments for the post-treatment applied FR additive include durable flame retardant chemistry relying on phosphorus-based FR agents and chemicals or resins to fix the FR agents to the fibers.
  • PROBAN is the trade name for a finishing process in which a cotton-rich fabric is dipped in a water-soluble cross linkable phosphorus-containing resin and cured by ammonia gas or liquid.
  • the process was originally patented by Hooker Chemical in the US and Albright & Wilson in the UK.
  • This process uses tetrakis-(hydroxylmethyl) phosphonium salts wherein the salt component could be sulfate (THPS) or chlorate (THPC).
  • THPS sulfate
  • THPC chlorate
  • a benefit of the process is that the FR component is in a very stable phosphine oxide structure.
  • the THPC-urea precondensate is water soluble until it is cross linked by the ammonia treatment. At that point it is well-penetrated into the cotton fibers and insoluble. Wash durability is excellent (up to 100 industrial laundering cycles).
  • the primary yarn may also include other FR fibers which are well-known in the art. Typically, these will be combined in a minor amount such as from 0 to about 50% based on the weight of the yarn. Other suitable amounts include greater than 0 such as greater than about 5%, greater than about 10% and up to about 30% by weight of the primary yarn. Examples include, but are not limited to, FR polyester, FR nylon, m-aramid, p-aramid, novoloid, melamine, poly(p-phenylene benzobisoxazole (PBO), polybenzimidazole (PBI), polysulphonamide (PSA), partially oxidized polyacrylonitrile (PAN) and combinations thereof.
  • PBO poly(p-phenylene benzobisoxazole
  • PBI polybenzimidazole
  • PSA polysulphonamide
  • PAN partially oxidized polyacrylonitrile
  • the amount of the partially aromatic fiber in the primary yarn will depend on which FR fiber and/or other fibers (FR or non-FR) are also included in the yarn.
  • the partially aromatic polyamide fiber may be present in said primary yarn in an amount of about 5% to about 75% by weight of the primary yarn; alternatively the partially aromatic polyamide fiber may be present in said primary yarn in an amount of about 5% to about 60% by weight of the primary yarn.
  • Other suitable ranges include where the minimum amount of partially aromatic fiber is about 25%; such as where the amount of partially aromatic fiber is about 25% to about 75% by weight of the primary yarn or about 25% to about 60% by weight of the primary yarn.
  • the partially aromatic polyamide may also be present in an amount of about 40% to about 60% or about 50% by weight of the primary yarn.
  • the type of FR fiber that accompanies the partially aromatic fiber will contribute to the necessary weight percent of each component based on the total weight of the primary yarn.
  • the fabric self- extinguishes in a vertical flammability test (ASTM D6416).
  • ASTM D6416 a vertical flammability test
  • the article of one aspect is a fabric capable of having an after-flame time of less than about 10 seconds in a vertical flammability test.
  • Additional fibers which may be included within the primary yarn, in staple or filament form (depending on the fiber), both flame retardant and non-flame retardant, are useful for to form other yarns, fabrics and garments.
  • the additional fibers can include cellulose (whether FR or not) such as cotton, rayon or lyocell, para-aramid, meta-aramid, modacrylic, melamine, poly(p-phenylene benzobisoxazole) (PBO), polybenzimidazole (PBI), polysulphonamide (PSA), oxidized acrylic, partially oxidized acrylic (including partially oxidized polyacrylonitrile), novoloid, wool, flax, hemp, silk, nylon (whether FR or not), polyester (whether FR or not) , anti-static fibers, and combinations thereof.
  • Certain fibers, such as para-aramid, PBI, or PBO maintain strength after flame exposure and, when used in blended yarns and fabrics, are effective at reducing the fabric char length after flammability testing.
  • the article of one aspect may further include at least one additional yarn which is compositionally different from said primary yarn.
  • “Compositionally different” means that the additional yarn differs from the primary yarn in at least one of a variety of aspects such as including different fiber compositions, different amounts of the same fibers, different fiber cross- section, different additives, different colors, etc.
  • the article may further comprise at least two additional yarns which are compositionally different from each other and compositionally different from said primary yarn.
  • the additional yarn may be an FR yarn; or may be a non- FR yarn.
  • the fabrics made with the primary yarn can also include additional yarns such as cellulose (whether FR or not) including cotton, rayon or lyocell, para-aramid, meta-aramid, modacrylic, melamine, poly(p-phenylene benzobisoxazole) (PBO), polybenzimidazole (PBI), or polysulphonamide (PSA), oxidized acrylic, partially oxidized acrylic (including partially oxidized polyacrylonitrile), novoloid, wool, flax, hemp, silk, nylon (whether FR or not), polyester (whether FR or not) , anti-static fibers, and combinations thereof.
  • additional yarns such as cellulose (whether FR or not) including cotton, rayon or lyocell, para-aramid, meta-aramid, modacrylic, melamine, poly(p-phenylene benzobisoxazole) (PBO), polybenzimidazole (PBI), or polysulphonamide (PSA), oxidized acrylic, partially oxidized acrylic (including partially oxid
  • Fabrics comprising non-FR celluloses can be treated with additional flame retardant additives and finishes if necessary.
  • An exemplary method for treating cotton is found in the technical bulletin 'Fabric Flame Retardant Treatment' (2003) published by Cotton Incorporated, Cary, North Carolina, herein incorporated by reference in its entirety.
  • the fabrics can be woven, knit, and non-woven fabrics.
  • Non-woven fabrics include those made from carded webs, wet-lay, or spun bond/melt blown processes.
  • the fibers, yarns, and fabrics can also contain additional components such as: UV stabilizers, anti-microbial agents, bleaching agents, optical brighteners, anti-oxidants, pigments, dyes, soil repellants, stain repellants, nanoparticles, and water repellants.
  • UV stabilizers, antimicrobials agents, optical brighteners, anti-oxidants, nanoparticles, and pigments can be added to the flame retardant polymer prior to melt-spinning or added as a post-treatment after fiber formation.
  • Dyes, soil repellants, stain repellants, nanoparticles, and water repellants can be added as a post-treatment after fiber and/or fabric formation.
  • Fabrics made with the disclosed flame retardant fiber may also have a coating or laminated film applied for abrasion resistance or for control of liquid/vapor permeation.
  • Char length means: "The distance from the fabric edge, which is directly exposed to flame to the furthest of visible fabric damage, after a specified tearing force has been applied.”
  • Drip means: "A flow of liquid that lacks sufficient quantity or pressure to form a continuous stream.”
  • NFPA National Fire Protection Association
  • Self-Extinguishing means Material will have no persistent flaming after the ignition source is removed OR flaming shall stop before the specimen is totally consumed. When tested by ATSM D6413-11 Standard test Method for Flame Resistance of Textiles (Vertical Method).
  • Colorfastness to Laundering American Association of Textile Chemist and Colorists (AATCC) Test Method 61 wherein color transfer to a multi-fiber test strip indicates dye loss from test fabric and staining a multi-fiber test strip comprised on the fibers listed in the tables of Examples. Color loss or adsorption is rated on a Gray Scale (1-5) where 5 is negligible change and 1 is a large change.
  • Color Measurement After dyeing, color is read using a Macbeth Color Eye 7000A spectrophotometer which measures visible light spectral reflectance of the sample for brightness, whiteness, and yellowness,
  • Example Set 1 Fibers were dyed individually using milling acid dye with and without ajeveling agent. Fibers were dyed for 60 minutes at 212 °F.
  • Example Set 5 Dyeing blends of MXD6 and cellulose fibers. Fabric comprising both fibers were dyed using two step processes of a reactive dye for the cellulose fiber and an acid dye for the MXD6 fiber.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Woven Fabrics (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
PCT/US2013/033841 2012-03-27 2013-03-26 Dyeing and printing of fabrics including partially aromatic polyamides WO2013148653A1 (en)

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IN2134MUN2014 IN2014MN02134A (enrdf_load_stackoverflow) 2012-03-27 2013-03-26
KR1020147029592A KR20140137009A (ko) 2012-03-27 2013-03-26 부분 방향족 폴리아미드를 포함한 패브릭의 염색 및 날염
CN201380027698.XA CN104321485A (zh) 2012-03-27 2013-03-26 包括部分芳族聚酰胺的织物的染色和印刷
US14/395,293 US20150308041A1 (en) 2012-03-27 2013-03-26 Dyeing and printing of fabrics including partially aromatic polyamides
EP13768029.4A EP2831335A4 (en) 2012-03-27 2013-03-26 COLORING AND PRINTING OF FABRIC WITH PARTICULAR POLYAMIDES

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JPWO2022074965A1 (enrdf_load_stackoverflow) * 2020-10-08 2022-04-14

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CN109112858A (zh) * 2018-07-25 2019-01-01 安徽新生纺织有限公司 一种芳纶和锦纶混纺织物的染色方法
KR102140541B1 (ko) * 2020-01-06 2020-08-04 (주)태일잉크화학 인조모발용 모다아크릴에 사용되는 액상 안료 착색제 조성물 및 그 제조방법
KR102823269B1 (ko) * 2022-11-30 2025-06-20 (주)성광테크 아라미드 복합 원단의 제조방법, 아라미드 복합 원단 및 이를 포함하는 방호복

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KR20140137009A (ko) 2014-12-01
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TW201348535A (zh) 2013-12-01
IN2014MN02134A (enrdf_load_stackoverflow) 2015-08-21
CN104321485A (zh) 2015-01-28
US20150308041A1 (en) 2015-10-29

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