KR20140137009A - Dyeing and printing of fabrics including partially aromatic polyamides - Google Patents

Abstract

Pretreatment applied dyes or printing or combinations thereof; And articles exhibiting flame retardant or flame retardant (FR) properties, including fabrics receiving post-treatment applied FR additives. The fabric comprises a basic yarn comprising a gas-phase action fiber and a partially aromatic polyamide fiber.

Description

[0001] DYEING AND PRINTING OF FABRICS INCLUDING PARTIALLY AROMATIC POLYAMIDES [0002]

The present invention relates to a process for dyeing fabrics comprising a flame retardant / flame retardant (FR) fabric comprising fibers exhibiting vapor phase action such as flame retardant / flame retardant (FR) treated cellulosic fibers and partially aromatic polyamide fibers And finishing.

Flame retardant and flame retardant (FR) fabrics are important in both military and non-military environments. Firefighters, racer drivers, and petrochemical workers are just a few of the non-military groups that enjoy the added protection benefits of flame retardant fabrics. However, the real advantage of today's flame retardant fabrics is related to the military. Along with the tough conditions for the military to carry out operations, the emergence of modern weapons other than the conventional has created a more difficult environment. Specifically, the use of an improvised explosive device ("IED") to detain multiple soldiers makes crucial individual protection important.

In addition to ballistic fabrics and armor, flame retardant fabrics play a significant role in protecting the military from the IED. The IED consists of a number of materials (eg, high-explosive packing, flammable liquid, lactic acid, etc.), some acting as projectiles and others acting as the soot during the explosion. Therefore, military fabrics must have various structures to handle various threats from the IED.

There are basically two types of flame retardant fabrics used in protective apparel: (1) fabrics made from flame retardant organic fibers (e.g., aramid, flame retardant rayon, polybenzimidazole, modacryl, etc.); And (2) a flame retardant fabric made from conventional materials (e.g., cotton) that have been post-treated to impart flame retardancy. Nomex® and Kevlar® aromatic polyamides are the most common types of flame retardant synthetic fibers. They are prepared by solution spinning meta-or para-aromatic polyamide polymers into fibers. Aromatic polyamides do not melt in extreme heat and are inherently flame retardant, but must be solution emissive. Unfortunately, Nomex® and Kevlar® are not very comfortable, difficult to manufacture, and costly.

Another fiber used in the protective garment is modacrylic which is a 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. Commercial examples include PROTEX® C and PROTEX® M fibers manufactured by Kaneka. With an approximate 1: 1 blend ratio, modacrylic fibers are known to impart flame retardancy 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 may become flame retardant by introducing a phosphorus-nitrogen additive during fiber spinning or fabric finishing. Mechanisms for flame retarding performance of both modacrylic and flame retardant cellulose are those that are derived from fibers that dilute, cool, chemically neutralize (vapor phase), and form an intense char barrier (condensation phase) It depends on the gas.

Post treatment flame retardants are applied to fabrics, which can be classified into two basic categories: (1) durable flame retardants; And (2) a non-durable flame retardant. In the case of protective clothing, since the treatment must withstand the washing, only the durability treatment is selected. For the most part, durable flame retardant chemistry today relies on phosphorous FR agonists and chemicals or resins to fix FR agonists on the fibers.

U.S. Provisional Patent Application Serial No. 61 / 530,434 and PCT Patent Application No. PCT / US11 / 52557, filed on September 21, 2011, disclose flame retardant fabrics comprising partially aromatic polyamide fibers. These fabrics can also include cellulosic fibers and can provide the protection required for FR fabrics and garments.

U. S. Patent No. 6,132, 476 discloses the dyeing of FR fabrics and garments, but when these fabrics contain certain inherently flame retardant fibers, such as aromatic polyamides, with fibers such as FR rayon, . The reason is that the high temperatures required for aromatic polyamide dyeing result in the exhaustion of FR agonist in FR rayon and make the fabric more susceptible to further depletion of FR additives during subsequent washing. Specific dyeing processes and conditions are required to avoid this concern.

There is a continuing need for fabrics that provide the FR properties necessary to avoid the risk of degradation of the FR properties of the fabric during dyeing and / or subsequent washing. Ideally, this novel process provides flexibility in selecting dyeing and / or printing while providing and maintaining desirable and / or required flame retardant or flame retardant properties.

One side providing a dyed and / or printed article exhibiting flame retardancy or flame retardancy including a basic yarn; Wherein the base yarns comprise fibers different from the flame retardant or flame retardant fibers comprising flame retardant or flame retardant (FR) fibers having significant gas phase action, such as modacrylic or FR cellulosic fibers, and partially aromatic polyamide fibers; Wherein the partially aromatic polyamide polymer free of FR additives is melt-spun into fibers. That is, the partially aromatic polyamide fibers exclude FR additives, which are incorporated into the fiber composition. The article may be yarn. However, the article may also be a fabric or garment comprising flame retardant yarn.

Another aspect provides an article that exhibits flame retardant or flame retardant (FR) properties, including (a) a fabric comprising pretreated applied dye or print or a combination thereof, and (b) Wherein the fabric comprises a basic yarn comprising a gas-phase action fiber and a partially aromatic polyamide fiber. The pretreatment is selected from the group consisting of dyes, prints, or combinations thereof, and is present in the garment prior to the addition of a post treatment comprising an FR additive. That is, there is almost no limitation in the dyeing process which can be used because the FR is not an issue since the FR is treated after the article is dyed. However, where printing is required, the printing can be applied before and after the application of the FR treatment, since it does not interfere with the FR treatment in such a way that the printing process can be a high temperature dyeing.

Further aspects are articles exhibiting flame retardancy or flame retardancy including (a) a fabric comprising a pretreatment consisting of dyeing, printing and combinations thereof, and (b) a post-treatment or flame retarding treatment comprising flame retardancy or flame retardancy, And a basic yarn comprising cotton fibers and partially aromatic polyamide fibers.

Methods for producing articles exhibiting flame retardant or flame retardant properties include the following sequential processes: (a) fabrication of fabrics comprising basic yarns comprising fibers having a gas phase action and partially aromatic polyamide fibers; (b) providing a pretreatment selected from the group consisting of dyeing, printing, and combinations thereof; And (c) post-treatment including flame retardant or flame retardant (FR) treatment. An optional subsequent process for printing can be introduced after the post-treatment application of the FR additive.

The terms "flame retardancy", "flame retardancy" and "FR" have subtle differences in the art. The difference in the use of these terms relates to describing a fabric that can resist combustion, burn at a slower rate, or be self-extinguishing under conditions such as a vertical flame test. For the purposes of the present invention, the terms "flame retardant" and "flame retardant" are used interchangeably and refer to any fabric do.

The term "gas phase" for fibers useful in the present invention is intended to include fibers that dilute, cool, or chemically neutralize a combustible gas. The mechanism for flame retarding performance of both modacrylic and flame retardant cellulose is dependent on the gas released from the fiber (condensed phase action) which dilutes, cools or chemically neutralizes (combusts) the gas and forms do.

The articles, particularly yarns, fabrics and garments, exhibit flame retardant and / or flame retardant properties. Such yarns include one or more fibers that are partially aromatic polyamides. Yarns comprising partially aromatic fibers are referred to in the claims as "base yarns ". The term "basic yarn" is not intended to set any relative weight percent of yarn compared to other yarns that may be present in the article, but instead is used to distinguish the yarn from other yarns. The base yarns should include partially aromatic fibers, such as FR cellulose fibers, modacryl fibers, and mixtures thereof, excluding spun-in FR additives bonded to FR fibers.

Unexpectedly, it has been found that MXD6 polyamide fibers can be dyed using some types of dyes for pretreated dyes. This allows the dyeer / printer / finisher to have additional flexibility in choosing the best and most compatible dye chemistry for performance and cost. A broader range of dyes and pigment choices makes it easier for dyeers to meet stringent military requirements for IR reflection of the camouflage fabric. Minimizing IR reflections is important to prevent the wearer from being seen through IR night vision goggles.

The article comprises a pretreatment, such as a dye or a print, or both. The dyes may be selected from the group consisting of acid dyes, cationic dyes, disperse dyes, vat dyes and combinations thereof. Where the dye is included, the article may be dyed with a union shade. Although the post-treatment step includes FR treatment, a second FR treatment that occurs during pre-treatment dyeing or printing can also be provided.

Vertical flammability tests indicate that dyeing can actually support flame retardancy of the MXD6 fabric. Also, the morphology of the MXD6 fibers can allow the FR component (e.g., cyclic phosphinate ester) to be added in the fabric dyeing.

The partially aromatic fibers may be prepared in the presence or absence of a non-halogen flame retardant additive. Spin-in non-halogen flame retarding additives may include: condensates of melamines (including melam, melem and melon), reactants of melamine and phosphoric acid (melamine phosphate, melamine pyrophosphate, and melamine polyphosphate (MPP) (Including melamine polyphosphate, melamine polyphosphate), melamine cyanurate (MC), zinc diethylphosphinate (DEPZn), aluminum diethylphosphinate (including melamine polyphosphate, DEPAl), calcium diethylphosphinate, magnesium diethylphosphinate, bisphenol-A bis (diphenylphosphinate) (BPADP), resorcinol bis (2,6-designylphosphate) (RDX) (Diphenyl phosphate) (RDP), phosphorus oxynitride, zinc borate, zinc oxide, zinc stannate, zinc hydroxystate, zinc sulfide, zinc phosphate, Magnesium stearate, ammonium octamolybdate, melamine morpholybdate, melamine octamolybdate, barium metaborate, ferrocene, boron phosphate, boron borate, magnesium phosphate, magnesium carbonate, zinc carbonate, zinc carbonate, zinc stearate, magnesium stearate, A melamine salt of 3-amino-1,2,4-triazole-5-thiol, a ureasol salt of potassium, zinc and iron, a magnesium salt of magnesium chloride, Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Mo, (SiTA), phosphotungstic acid, melamine salts of tungstic acid, linear, branched or cyclic phosphates or phosphates, such as oxides of Sn, Sb, Ba, W and Bi, polyhedral oligomeric silsesquioxanes, Phonates, spirobisphosphonates, spirobisphosphates and nanoparticles, I pray carbon nanotubes and nano-clay (including but not limited to, montmorillonite, halloysite, and laponite).

When the flame retardant additive is present in the partially aromatic polyamide fiber, the flame retardant additive is present in an amount from about 1% to about 25% w / w, which ranges from about 5% to about 20% w / w, from about 5% to about 10% , And about 10%. The average particle size of the flame retardant additive is less than about 3 micrometers, which includes less than about 2 micrometers, and less than about 1 micrometer.

The particle size of the flame retardant additive can be produced by a milling process that includes air-jet milling of each component or a co-milling blend of the components to reduce the particle size. Other wet or dry milling techniques known in the art (e.g., media milling) can also be used to reduce the additive particle size for fiber spinning. If appropriate, the milling may involve the injection of a liquid milling aid into the mill, possibly at any suitable point in the milling process, possibly under pressure. The liquid adjuvant is added to stabilize the flame retardant system and / or prevent flocculation. Additional components to assist in particle wetting and / or prevent re-agglomeration can also be added at any suitable point during milling of the flame retardant additive, blending of the flame retardant additive and polymer, and / or fiber spinning process.

The flame retardant may be blended with the polymeric material in an extruder. An alternative method involves dispersing the flame retardant composition into the polymer at a higher concentration than desired for the final polyamide fiber product and forming a masterbatch. The masterbatch can be ground or pelletized and the resulting microparticles dry blended with additional polyamide resin, which blend is used in a fiber spinning process. Yet another alternative involves adding some or all of the components of the flame retardant additive to the polymer at a suitable point in the polymerization process.

In one aspect, the partially aromatic fibers exclude spun-in FR additives. The partially aromatic polyamide may comprise a polymer or copolymer comprising 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 polyamides may also include or consist solely of MXD6 including aromatic diamines and non-aromatic diacids. Other partially aromatic polyamides may be based on aromatic diacids such as terephthalic acid (polyamide 6T), or isophthalic acid (polyamide 6I) or a blend thereof (polyamide 6T / 6I). The melting or working temperature of the partially aromatic polyamide is about 260 ° C, 280 ° C, 300 ° C, 320 ° C, and 340 ° C in the range of about 240 ° C for MXD6 to about 355 ° C for polyamideimide . Nylon 6 and Nylon 6,6 have melting temperatures of about 220 ° C and 260 ° C, respectively. The lower the melting temperature, the easier it is to process the polyamide polymer into fibers. The following is a list of common partially aromatic polymers and certain comparative non-aromatic and related melt temperatures.

The partially aromatic polyamide may also comprise a copolymer or a mixture of a plurality of partial aromatic amides. For example, MXD6 may be blended with nylon 6 / 6T prior to forming the fibers. Further, the partially aromatic polymer may be blended with a copolymer or mixture of aliphatic polyamides or a plurality of aliphatic polyamides. For example, MXD6 can be blended with nylon 6,6 before forming fibers. The partially aromatic fibers may comprise at least about 20% by weight of one or more aliphatic polyamides of the fibers.

The partially aromatic fibers may be staple fibers or continuous filament yarns. The partially aromatic fibers may also be contained in non-woven fabrics such as spun bond, melt blown or combinations thereof. The filament cross section may be of any shape, including circular, triangular, star-shaped, square, oval, bi-lobal, tri-lobal or flat. In addition, the filament can be textured using a known texturing method. As discussed above, the partially aromatic polyamide spun into fibers may also comprise additional partially aromatic or aliphatic polymers. When spinning such fibers, a mixture of more than one polyamide polymer may be blended prior to spinning into yarn, or may be blended with one or more partially aromatic polyamide polymers or additional partial aromatic polyamide polymers or aliphatic polymers with side Multi-filament yarns containing two-component forms such as side-by-side or core-sheath configurations can be made.

The partially aromatic fibers will be blended with FR fibers having significant gas phase action, such as modacrylic or FR cellulosic fibers to form basic yarns. The yarn comprises only partially aromatic fibers and FR fibers, and may alternatively be other fibers that are FR or non-FR fibers. The useful amount of the partially aromatic fibers varies. A suitable amount of partially aromatic fibers is from about 5% to about 75% by weight of the base yarn; From about 5% to about 60% by weight of the yarn; And from about 25% to about 50% by weight of the yarn. The blended yarn may be prepared by any suitable method. For example, the yarn may be a blended staple yarn. The blended staple yarn may be an intimate blend in which the partially aromatic fibers and the FR fibers are uniformly blended throughout the yarn. Alternatively, the yarn may be, among other things, a single twisted yarn or a ply twisted yarn, a biped (including single and double sheaths), or a core-spun yarn.

The base yarn should contain one or more FR fibers, such as modacrylic or FR cellulosic fibers, and combinations thereof, which have a considerable vapor phase action. The FR fibers may also be FR cellulose added to the FR cellulose during fiber fabrication. Alternatively, the FR treatment can be applied to articles containing untreated cellulose fibers. Examples of suitable cellulosic fibers include cotton, rayon or lyocell. An article comprising FR cellulose is intended to include those processed such that components such as yarn are introduced into the article. Articles containing FR cellulose also include those that have been treated after binding cellulose to the yarn, and those after which the yarn is made into a fabric or garment. As used herein, cellulose includes, but is not limited to, acetate, cotton, rayon, lyocell, and combinations thereof. In the base yarn, one or more cellulosic fibers may be bonded to each other and / or to modacrylics. The amount of FR fibers having a considerable vapor phase action may vary. A suitable amount of such fibers is from about 25% to about 75% by weight of the base yarn; Greater than 25 wt% to about 75 wt% of the yarn; From about 40% to about 60% by weight of the yarn; And from about 50% to about 75% by weight of the yarn.

Regardless of whether the FR fibers of the basic yarn are FR processed prior to the pretreatment step or have additives, the post-treatment applied FR additives are introduced into the article, fabric or garment after dyeing. The post-treatment flame retardant includes (1) a durable flame retardant, and (2) a non-durable flame retardant. In the case of protective clothing, the treatment is required to endure the washing, so that the durability treatment is more preferable. Post-Treatment A suitable example of FR treatment of applied FR additives includes phosphorus-based FR agonists and durable flame retardant chemistry that relies on chemicals or resins to fix FR agonists to the fibers.

One suitable process for FR post-treatment is the " PROBAN "process. "Pro-van" is the trade name of a finishing process in which a cotton-rich fabric is immersed in a water-soluble crosslinkable phosphorous-containing resin and cured with ammonia gas or liquid. The process was first patented by Hooker Chemical of the United States and Albright & Wilson of the United Kingdom. The process uses a tetrakis- (hydroxymethyl) phosphonium salt, wherein the salt component may be sulfate (THPS) or chlorate (THPC). Due to concerns about some by-products, the system used today is THPS with an ammonia gas curing chamber. The advantage of this process is that the FR component is a highly stable phosphine oxide structure. The THPC-urea condensation product is water-soluble until crosslinked by ammonia treatment. At that point it penetrates well into cotton fibers and is insoluble. Excellent durability in washing (up to 100 industrial wash cycles).

The basic yarn may also include other FR fibers well known in the art. Typically, they will be blended in small amounts such as from 0 to about 50%, based on the weight of the yarn. Other suitable amounts include greater than 0% by weight of the base yarn, such as greater than about 5% by weight, greater than about 10% by weight, and not greater than about 30% by weight. Examples include, but are not limited to, FR polyester, FR nylon, m-aramid, p-aramid, novoloid, melamine, poly (p- phenylenebenzobisoxazole) (PBO), polybenzimidazole (PBI) Amide (PSA), partially oxidized polyacrylonitrile (PAN), and combinations thereof.

The amount of partially aromatic fibers in the base yarn will depend on whether any FR fibers and / or other fibers (FR or non-FR) are also included in the yarn. For example, a partially aromatic polyamide fiber may be present in the basic yarn in an amount of from about 5% to about 75% by weight of the basic yarn, alternatively a partially aromatic polyamide fiber may be present in the basic yarn in an amount of from about 5% To about 60% by weight of the composition. Other suitable ranges are those in which the minimum amount of partially aromatic fibers is about 25%, for example the amount of partially aromatic fibers is from about 25% to about 75% by weight of the basic yarn or from about 25% to about 60% by weight of the basic yarn. The partially aromatic polyamide may also be present in an amount of from about 40% to about 60% or about 50% by weight of the base yarn. The type of FR fibers that accompany the partially aromatic fibers will contribute to the required weight percent of each component based on the total weight of the base yarn. When the base yarn is included in the fabric, the fabric is self-extinguishing in a vertical flammability test (ASTM D6416). Specifically, one side of the article is a fabric that can have an after-flame time of less than about 10 seconds in a vertical flammability test.

Additional fibers that may be included in the base yarn (depending on the fiber) in the form of staples or filaments of both flame retardancy and non-flammability are useful in forming other yarns, fabrics, and garments. Additional fibers include, but are not limited to, cellulose (whether FR or not) such as cotton, rayon or lyocell, para-aramid, meta-aramid, modacrylic, melamine, poly (p- phenylenebenzobisoxazole) (PBI) and polysulfone amide (PSA), oxidized acrylic, partially oxidized acrylic (including partially oxidized polyacrylonitrile), novoloid, wool, flax, hemp, dog, nylon ), Polyester (whether or not FR), antistatic fibers, and combinations thereof. Certain fibers, such as para-aramid, PBI, or PBO, are effective in maintaining strength after flame exposure and reducing the fabric char length after flammability testing when used in blended yarns and fabrics.

One side of the article may further comprise one or more additional yarns different in composition from the basic yarn. By "different in composition" it is meant that the additional yarn is different from the basic yarn in one or more of various aspects such as different aspects, such as different fiber compositions, different amounts of the same fibers, different fiber cross-sections, different additives, different colors, . The article may further comprise two or more additional yarns of different composition from one another and of a different composition from the basic yarn. Further, the additional yarn may be an FR yarn; Or non-FR yarn.

Fabrics made from basic yarns may also be fabricated using additional yarns such as cellulose (including FR or not), para-aramid, meta-aramid, modacrylic, melamine, poly (p- Polyoxyethylene (PBO), polybenzimidazole (PBI), or polysulfone amide (PSA), oxidized acrylic, partially oxidized acrylic (including partially oxidized polyacrylonitrile), novoloid, wool, Flax, hemp, dog, nylon (FR or not), polyester (FR or not), antistatic fibers, and combinations thereof.

The fabric comprising non-FR cellulose can be treated with additional flame retardant additives and, if desired, a finish. Exemplary methods for treating surfaces are found in the document 'Fabric Flame Retardant Treatment' (2003) by Cotton Incorporated, Cary, North Carolina, which is incorporated herein by reference in its entirety. The fabric may be a woven, knitted, and non-woven fabric. Nonwoven fabrics include those made from carded webs, wet-lay or spunbond / meltblown processes.

The fibers, yarns and fabrics may also contain additional components such as UV stabilizers, antibacterial agents, bleaches, optical brighteners, antioxidants, pigments, dyes, antifouling agents, anti-staining agents, nanoparticles and water repellents. UV stabilizers, antimicrobial agents, optical brighteners, antioxidants, nanoparticles and pigments may be added to the flame retardant polymer prior to melt-spinning or added as a post-treatment after fiber formation. Dyes, antifouling agents, anti-staining agents, nanoparticles and water repellent agents may be added as post treatment after fiber and / or fabric formation. Fabrics made of the disclosed flame retardant fibers may also have coatings or laminated films applied for wear resistance or for control of liquid / vapor permeation.

Justice:

After flame means "continuous burning of material after ignition source is removed". [Source: ASTM D6413-11 Standard Test Method for Flame Retardancy of Textiles (Vertical Method)]

The length of the char is: "the distance from the edge of the fabric directly exposed to the flame to the farthest position of the visible fabric damage after the application of a specific tearing force". [Source: ASTM D6413-11 Standard Test Method for Flame Retardancy of Textiles (Vertical Method)]

It refers to "a sufficient amount to form a continuous stream or flow of liquid short of the pressure": off down (drip) is. [Source: National Fire Protection Association (NFPA) Standard 2112, 2007 edition, Standard for Flame Retardant Clothing to Protect Industrial Workforce against Sudden Fire).

Melting means: 'the reaction of a substance to heat, which leads to evidence of flow or falling down'. [Source: National Fire Protection Association (NFPA) Standard 2112, 2007 edition, Standard for Flame Retardant Clothing to Protect Industrial Workforce against Sudden Fire).

Self-extinguishing means that after the ignition source is removed, the material is not continuously burned or the flame is stopped before the specimen is completely exhausted. ASTM D6413-11 Tested by standard test method (vertical method) for flame retardancy of textile.

The features and advantages of the present invention are more fully apparent from the following examples, which are provided for purposes of illustration and are not intended to limit the invention in any way.

Example

Test Methods:

Flame retardancy was determined by the standard test method (vertical test) for flame retardancy of ASTM D-6413-11 textile.

Color fastness to laundering : American Society of Textile Chemist and Colorists (AATCC) Test Method 61, wherein the color conversion to a multi-fiber test strip represents dye loss of the test fabric, Contamination of the multi-fiber test strip is shown in the table of the examples. The color loss or sorption is graded with Gray Scale (1-5), where 5 is a negligible change and 1 is a large change.

Color measurement : After dyeing, the color is measured using a Macbeth Color Eye 7000A spectrophotometer, which measures the visible light reflection of the sample against brightness, whiteness, and yellowness.

The interpretation of the measurements is as follows:

보다 높은 L값은 보다 밝은 쉐이드를 지칭한다

A higher L value refers to a lighter shade

보다 높은 K/S 값은 보다 어두운 쉐이드를 지칭한다

A higher K / S value refers to a darker shade

a-값: 적색도를 나타내며, a-값이 높을수록 보다 적색이다. 낮을수록 보다 녹색이다.

a-value: indicates the degree of redness, and the higher the a-value, the more red. The lower is the greener.

b-값: 황색도를 나타내며, b-값이 높을수록 보다 황색이고, 낮을수록 보다 청색이다.

b-value: indicates yellowness. The higher the b-value, the more yellowish the lower the lower the b-value.

Vertical flammability : ASTM D-6413 'Standard Test Method for Flame Retardancy of Textiles (Vertical Test)'

[For all embodiments: Several classes of dyes are used to compare the staining characteristics of MXD6 and nylon 66 fibers. The fiber samples were pre-scoured at 160 15 for 15 minutes using 1 g / l soda ash and 1 g / l Domoscour LFE-810.

Example Set 1: Fibers were individually dyed using milling acid dyes with and without leveling agent. The fibers were stained at 212 60 for 60 minutes.

conclusion : Without leveling agent milling  When an acid dye is used, MXD6  Fiber N66 It is dyed more darkly.

Example Set 2: Competitive dyeing . The fibers were dispersed at pH = 9.0 and dispersed at pH = 9.0. Acid Blue 122 Acid (MBB) dyes at pH = 5.8 and Acid Blue 45 (ABB) dyes at pH = 5.8 and pH 7.0 with or without anionic leveling agent at pH = And stained in the same bath. The fibers were stained at 212 60 for 60 minutes.

conclusion:

1. Anthraquinone milling  Blue B ( ABB  Type amine Horse short  Sensitive dye), MXD6 is stained 80% brighter than the control N-66.

2. Without leveling agent milling  blue BL ( MBB  Type structure sensitive dyes), 20% brighter than the control dye. Including leveling agent N66 ≪ / RTI >

Example Set 3: Dyeing with cationic dyes . The fibers were stained in a separate bath using one of two dye formulations:

Blue : 60 minutes at 212 째 F 1% Astrazon Blue F2RL 200%, 2 g / l Laurotex A-25, pH = 4.5, 0.5% Domoskar LFE-810

Red : Maxilon Red GRL 200%, 2 g / l Laurotex A-25, pH = 4.5, 0.5% Domoskar LFE-810

conclusion: MXD6 Than nylon 66 Cationic  Dyes are dyed more darkly. However, dyes do not lose color when washed as acid dyes.

Example Set 4: Dyeing with an acid dye . The fibers were dyed in separate baths using one of the acid dye formulations:

Navy (pre- metallized ) : 3% Lanaset Navy 2R + 0.2% Lanaset Orange RN, pH = 5.0, 0.25% Albegal B, 2 g /; Laurotex A-25, 212 F for 60 minutes.

Red : 2% Erionyl Red 3G + 0.5% Polar Red 3BN 140%, pH = 5.0, 0.25% Albegal B, 2 g /; Laurotex A-25, 212 F for 60 minutes.

Dark green : 2% Nylon Turq. GLM + 0.5% Supernol Navy R + 1% Telon Yellow A-3gL. pH = 5.0, 0.25% Albegal B, 2 g /; Laurotex A-25, 212 F for 60 minutes.

After dyeing, dye was attached using 3% Nylofixan MF2N at pH = 4.5, 170 20 for 20 minutes.

conclusion : MXD6  Total acid dyes of nylon Dyeing power is  It is weaker than Nylon 66, but it is excellent.

Example Set 5: Blend dyeing of MXD6 and cellulose fibers . The fabric containing both fibers was stained using a two-step process of reactive dye for cellulose fibers and acid dye for MXD6 fibers.

Pre-refining / bleaching:

1 g / l at 200 ° F for 20 min. Domoskar LFE-810 + 1.5 g / l Soda Ash + 2 g / l Albone 35 + 0.25 g / l Versene 30A. rinsing

Cellulose dyeing with reactive dye:

Set the bass to 80 2 with 2 g / l Laurotex A-25.

Dye is added.

0.56% Novacron Olive C

0.041% Novacron Brown NC

0.08% Novacron Navy FN-BN

Continue for 5 minutes. Add 50 g / l salt and proceed for 5 minutes. Raise to 140 ° F at 3 ° F / min.

Add 15 g / l soda ash.

45 minutes.

Drain at 200 ° F using a 1 g / l homescrewer LFE 810 for 15 minutes - rinse - soap removal.

Drop - Rinse -

As an acidic dye MXD6  dyeing:

Set the bass to 2 g / l Laurotex A-25 + 0.5% Albegal B

3 g / l MSP, pH = 5.5

Continue for 5 minutes. Acid dye is added.

0.22% Erionyl Yellow A-3G

0.032% Erionyl Red A-3g

0.16% Erionyl Navy A-R

Continue for 5 minutes. Raise to 212 ° F at 3 ° F / min. 45 minutes.

Cooling - drainage - rinse.

Apply 2% Cibafix DGF at 170,, pH = 4.5 for 20 minutes.

conclusion : The process was carried out in a 50/50 MXD6 /cellulose Fabric  Excellent union dyeing is obtained.

While there have been described what are presently considered to be preferred embodiments of the invention, those skilled in the art will recognize that changes and modifications may be made thereto without departing from the scope of the invention, which makes all changes and modifications within the true scope of the invention .

Claims (22)

(a) a fabric comprising pretreatment applied dyes or prints or combinations thereof; And
(b) Post-treatment applied FR additives
Wherein the fabric exhibits a flame retardant or flame retardant (FR) nature comprising a basic yarn comprising a fiber having a gas phase action and a partially aromatic polyamide fiber. The article of claim 1, wherein the pretreatment comprises a dye selected from the group consisting of an acid dye, a cationic dye, a disperse dye, a bat dye, a reactive dye, and combinations thereof. The article of claim 1, wherein the fabric is stained with a union shade. 2. The article of claim 1, wherein the pretreatment further comprises a second FR treatment. The article of claim 1, wherein the partially aromatic polyamide is radiated as fibers without an FR additive. The article of claim 1, wherein the partially aromatic polyamide comprises a polymer or copolymer comprising monomers selected from the group consisting of aromatic diamine monomers, aliphatic diamine monomers, aromatic diacid monomers, aliphatic diacid monomers, and combinations thereof. 7. The article of claim 6, wherein the partially aromatic polyamide further comprises an aromatic diamine monomer and an aliphatic dianionic monomer. The article of claim 1, wherein the partially aromatic polyamide is MXD6. The article of claim 1, wherein the partially aromatic polyamide fibers comprise a form selected from the group consisting of staples, continuous filaments, and combinations thereof. 2. The article of claim 1, wherein the base yarn comprises twisted yarns, sum yarns, textured yarns, blended staple yarns, and combinations thereof. The article of claim 1, wherein the partially aromatic polyamide fibers are present in the base yarn in an amount from about 5% to about 75% by weight of the base yarn. The article of claim 1, wherein the fibers having a vapor phase action are selected from modacrylic fibers, cellulosic fibers, and combinations thereof. The method of claim 1 wherein said base yarn is selected from the group consisting of FR polyester, FR nylon, FR rayon, m-aramid, p-aramid, modacrylic, novoloid, melamine, poly (p- phenylenebenzobisoxazole) , Polybenzimidazole (PBI), polysulfoneamide (PSA), oxidized acrylic, partially oxidized acrylic, and combinations thereof. The article of claim 1, wherein the article is a fabric. The article of claim 1, wherein the article is a garment. The article of claim 1, further comprising one or more additional yarns that differ in composition from the basic yarn. (a) a fabric comprising a pretreatment consisting of dyeing, printing and combinations thereof; And
(b) post-treatment including flame retardant treatment or flame retardant treatment
Wherein the fabric exhibits flame retardant or flame retardant properties, including basic yarns comprising cotton fibers and partially aromatic polyamide fibers. (a) fabricating a fabric comprising a basic yarn comprising a gas-phase action fiber and a partially aromatic polyamide fiber;
(b) providing a pretreatment selected from the group consisting of dyeing, printing, and combinations thereof; And
(c) post-treatment step comprising flame retardant or flame retardant (FR) treatment
Of flame retardant or flame retardant properties, including sequential processes. 19. The method of claim 18, further comprising a second printing step subsequent to post-treatment comprising flame retardant or flame retardant treatment. 19. The method of claim 18, wherein the fibers having a gas phase action are cellulosic fibers. 21. The method of claim 20, wherein the cellulosic fibers comprise a face. 19. The method of claim 18, wherein the pretreatment further comprises a second FR treatment.