TW201348535A - Dyeing and printing of fabrics including partially aromatic polyamides - Google Patents

Abstract

An article exhibiting flame resistant or flame retardant (FR) property including a fabric that has received a pre-treatment applied dye or print or combinations thereof; and a post-treatment applied FR additive. The fabric includes a primary yarn including a fiber having vapor phase action and a partially aromatic polyamide fiber.

Description

Contains dyeing and printing of partially aromatic polyamide fabrics

The present invention relates to dyed and finished fabrics comprising flame resistant/flame retardant (FR) fabrics comprising partially aromatic polyamide fibers and fibers exhibiting a gas phase effect, such as cellulose fibers that have been subjected to FR treatment.

Flame retardant and flame resistant (FR) fibers are critical in both military and non-military environments. Firefighters, racers and petrochemical workers are only a few non-military groups that benefit from the added protection of flame retardant fabrics. However, the real benefit of current flame retardant fabrics is military. In addition to the ruthless environment in which the military must operate, the advent of modern warfare is a more sinister environment. In particular, the use of a simple explosive device ("IED") to deactivate a group of soldiers makes individual military protection extremely important.

In addition to ballistic fabrics and body armor, flame retardant fabrics play a key role in protecting soldiers from IED. IEDs are constructed from a variety of materials (eg, high-energy explosive charges, flammable liquids, shrapnel, etc.), some used as projectiles and others used as incendiary bombs during an explosion. Therefore, military fabrics must have multiple structures to handle the multiple threats of IED.

There are basically two types of flame retardant fabrics for protective clothing: (1) fabrics made of flame retardant organic fibers (eg aromatic polyamines, flame retardant oximes, polybenzimidazoles, modified polyacrylonitriles) Fibers, etc.; and (2) flame-retardant fabrics made of conventional materials (such as cotton) that have been post-treated to impart flame retardancy. Nomex® and Kevlar® aromatic polyamines are among the most common Type of flame retardant synthetic fiber. These polyamines are made by spinning an inter-aromatic polyamine or a solution of an aromatic polyamine polymer into a fiber. Aromatic polyamines which are not melted under extreme heating are natural flame retardants, but solution spinning is necessary. Unfortunately, Nomex® and KEVLAR® are not very comfortable and difficult to produce and costly.

Another fiber for the protective garment is a modified polyacrylonitrile 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 content. Fiber of halogen ethylene monomer). Commercial examples include PROTEX® C and PROTEX® M fibers manufactured by Kaneka. At a blend ratio of about 1:1, it is known that modified polyacrylonitrile fibers impart flame resistance properties to fabrics including cellulosic fibers that are not FR treated, such as cotton and soluble cellulose. Examples can be found in EP1498522 and WO2008027454.

Cellulose fibers such as acetate, hydrazine, soluble cellulose, and cotton can impart flame resistance by incorporating a phosphorus-nitrogen additive during fiber spinning or fabric conditioning. The mechanism of the flame resistance of modified polyacrylonitrile fibers and flame resistant cellulose relies on the gas emitted by the fiber, which dilutes, cools or chemically neutralizes the combustible gas (gas phase action) and forms an enlarged scorch barrier (condensation phase).

Post-treatment flame retardants are applied to fabrics and can be divided into two basic categories: (1) durable flame retardants; and (2) non-durable flame retardants. For protective clothing, the treatment must withstand washing, so only durable treatment is chosen. Currently, most commonly, durable flame retardant chemicals rely on phosphorus-based FR agents and chemicals or resins that fix FR agents to fibers.

The flame retardant fibers, which partially contain aromatic polyamide fibers, are disclosed in U.S. Provisional Patent Application Serial No. 61/530,434, filed on Sep. 21, 2011, and the PCT Patent Application No. PCT/US11/52557. These fibers may also contain cellulosic fibers and provide the protection needed for FR fabrics and garments.

U.S. Patent No. 6,132,476 discloses the dyeing of FR fabrics and garments, but recognizes that when such fabrics comprise a combination of specific inherent flame retardant fibers (such as aromatic polyamides) and fibers (such as FR®), the dyeing process reduces FR. The validity of the feature. The reason is dyeing aromaticity The high temperatures required for polyamido cause the FR agent in the FR(R) to be depleted and make the fabric easier to further deplete the FR additive during subsequent washing. Specific dyeing processes and conditions are required to avoid these problems.

There is currently a need to provide fabrics with the necessary FR characteristics to avoid the problem of reducing the FR characteristics of the fabric during dyeing and/or subsequent laundering. Ideally, these new methods provide flexibility in selecting dyeing and/or printing processes while providing and maintaining desired and/or desired flame or flame retardant properties.

An aspect provides an article that has been dyed and/or printed and exhibits flame or flame retardant properties, comprising a primary yarn; wherein the primary yarn comprises a flame resistant or flame retardant (FR) fiber having an important gas phase effect, such as modified poly Acrylonitrile fibers or FR cellulose fibers, and fibers other than the flame resistant or flame retardant fibers, comprise partially aromatic polyamide fibers; wherein a portion of the aromatic polyamine polymer without the FR additive is melt spun into the fibers. In other words, the partially aromatic polyamide fibers exclude the FR additive, which is a component necessary for constituting the entire fiber composition. The item can be a yarn. However, the article may also be a fabric or garment comprising a flame resistant yarn.

Another aspect provides an article exhibiting flame resistant or flame retardant (FR) properties comprising (a) a fabric comprising a pretreatment applied dye or print or a combination thereof; and (b) a post treatment applied FR additive; wherein the fabric comprises The main yarn includes a gas phase-acting fiber and a partially aromatic polyamide fiber. The pretreatment is selected from the group consisting of dyeing, printing, or a combination thereof and is present on the garment prior to treatment after the addition of the FR additive is added. In other words, there is almost no limit to the dyeing process which can be used as the FR depletion, which is not a problem because the article is subjected to FR treatment after dyeing. However, when printing is required, printing can be applied before or after the application of the FR treatment because the printing process does not interfere with the FR treatment in a manner that may be present in high temperature dyeing.

In another aspect, an article exhibiting flame resistance or flame retardant properties, comprising (a) comprising a pretreated fabric comprising dyeing, printing, and combinations thereof; and (b) comprising a post-combustion or flame retardant treatment; wherein the fabric comprises a primary yarn comprising cotton fibers and partially aromatic polyamide fibers.

A method of preparing an article exhibiting flame retardant or flame retardant properties, comprising the following continuous processing: (a) preparing a fabric comprising a primary yarn comprising a gas having a gas phase effect and a partially aromatic polyamide fiber; (b) providing a pretreatment selected from the group consisting of: dyeing, printing, and combinations thereof; and (c) treating after treatment with a flame or flame retardant (FR) treatment. Subsequent printing processing, as the case may be, may be introduced after the application of the FR additive after the application.

The terms "flame resistant", "flame retardant" and "FR" have subtle differences in this technology. The differences in the use of these terms relate to any of the descriptions of fabrics that resist combustion under conditions such as upright burn testing, burn at a lower rate, and are self-extinguishing. For the purposes of the present invention, the terms "flame-resistant" and "flame retardant" are used interchangeably and are intended to include any fabric having one or more desired characteristics, such as resistance to combustion, slow burning, self-extinguishing, and the like.

The term "gas phase action" as used in the context of the present invention is intended to include fibers which dilute, cool or chemically neutralize combustible gases. The mechanism of the flame resistance of modified polyacrylonitrile fibers and flame resistant cellulose relies on the gas emitted by the fiber, which dilutes, cools or chemically neutralizes the combustible gas (gas phase action) and forms an enlarged scorch barrier (condensation phase).

Articles (specifically, yarns, fabrics, and garments) exhibit flame and/or flame retardant properties. The yarn comprises at least one fiber that is a partially aromatic polyamine. Yarns containing partially aromatic fibers are referred to as "primary yarns" in the scope of the patent application. The term "primary yarn" is not intended to establish any relative weight percentage of the yarn (as compared to other yarns that may be present in the article), but rather to distinguish the yarn from other yarns. The main yarn must contain a part of the fragrance Combination of fibers (except for spun FR additives) with FR fibers such as FR cellulosic fibers, modified polyacrylonitrile fibers, and mixtures thereof.

Surprisingly, it has been found that MXD6 polyamine fibers can be dyed using several types of dyes used as pretreatment applied dyes. This allows the dyeing machine/printer/dresser to have exceptional flexibility in selecting the dye chemistry that is optimal for performance and cost. A wide range of dye and pigment options allow the dyeing machine to more easily meet the stringent military needs for IR reflectivity of camouflage fabrics. The minimum IR reflectance is critical to prevent the wearer from being found by IR night vision glasses.

The items include pretreatments such as dyeing or printing or both. The dye may be selected from the group consisting of acid dyes, cationic dyes, disperse dyes, anthraquinone dyes, and combinations thereof. If a dye is included, the article can be dyed to a uniform hue. Although the post-processing step includes FR processing, a second FR treatment that occurs during pre-treatment staining or printing may also be provided.

Upright burning tests have shown that dyes can actually contribute to the flame resistance of MXD6 fabrics. In addition, the morphology of the MXD6 fibers can allow for the addition of FR components such as cyclic phosphonites when the fabric is dyed.

Part of the aromatic fiber can be prepared in the presence or absence of a non-halogen flame retardant additive. The spinning non-halogen flame retardant additive may comprise: a condensation product of melamine (containing melam, melem and melon), a reaction product of melamine and phosphoric acid (including melamine phosphate, Reaction product of melamine pyrophosphate and melamine polyphosphate (MPP), melamine condensation product and phosphoric acid (including melam polyphosphate, melidamine polyphosphate, cyanuric polyphosphate), melamine cyanurate (MC), two Zinc ethanephosphonate (DEPZn), aluminum dihydrogenphosphinate (DEPAI), calcium diethanephosphonate, magnesium dihydrogenphosphonate, bisphenol A bis(diphenylphosphinate) (BPADP), Resorcinol bis(2,6-di(dimethylphenyl)phosphate) (RDX), resorcinol bis(diphenyl phosphate) (RDP), phosphorus oxynitride, zinc borate, zinc oxide, tin Zinc acid, zinc hydroxystannate, zinc sulfide, zinc phosphate, zinc antimonate, zinc hydroxide, zinc carbonate, zinc stearate, magnesium stearate, ammonium octamolybdate, melamine molybdate Amine, melamine octamolybdate, bismuth metaborate, ferrocene, boron phosphate, boron borate, magnesium hydroxide, magnesium borate, aluminum hydroxide, alumina trihydrate, melamine salt of glycoluril and 3-amino-1, 2,4-triazole-5-thiol, potassium, zinc and iron urezo salt, 1,2-ethanediyl-4-4'-bis-triazolyl-3,5-dione, polyfluorene Oxide, Mg, Al, Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Mo, Sn, Sb, Ba, W and Bi oxides, polyhedral oligomeric polysesquioxanes, bismuth Tungstic acid (SiTA), phosphotungstic acid, melamine salt of tungstic acid, linear, branched or cyclic phosphate or phosphonate, spiro bisphosphonate, spiro bisphosphonate and nano particles, such as carbon nanotubes Tubes and nano-clay (including but not limited to those based on montmorillonite, halloysite and laponite).

When present in a portion of the aromatic polyamide fibers, the flame retardant additive comprises from about 1% to about 25% by weight, from about 5% to about 20% by weight, from about 5% to about 10% by weight, and about It is present in an amount of 10% by weight. The flame retardant additive has an average particle size of less than about 3 [mu]m, and comprises less than about 2 [mu]m and less than about 1 [mu]m.

The particle size of the flame retardant additive can be prepared by a milling process that includes jet milling or co-milling component blends of the various components to reduce particle size. Other wet or dry milling techniques known in the art, such as media milling, can also be used to reduce the particle size of the additive used for fiber spinning. If appropriate, grinding can involve injecting a liquid grinding aid into the mill at any suitable point of the grinding process, possibly under pressure. These liquid auxiliaries are added to stabilize the flame retardant system and/or to prevent coalescence. Other components that aid in wetting and/or preventing re-agglomeration of the particles may also be added at any suitable point during the grinding of the flame retardant additive, blending of the flame retardant additive with the polymer, and/or during the fiber spinning process.

The flame retardant can be mixed with the polymeric material in an extruder. An alternative method involves dispersing the flame retardant composition in the polymer at a concentration that is higher than the desired concentration in the final polyamide fiber product and forming a parent mixture. The parent mixture can be milled or granulated and the resulting microparticles are dry blended with additional polyamide resin and this blend is used in the fiber spinning process. Another alternative involves adding some or all of the flame retardant additives to the polymer at suitable points in the polymerization process. Component.

In one aspect, some of the aromatic fibers exclude the spun FR additive. The partially aromatic polyamine may comprise a polymer or copolymer comprising a monomer selected from the group consisting of aromatic diamine monomers, aliphatic diamine monomers, aromatic diacid monomers, aliphatic diacids Monomers and combinations thereof. Part of the aromatic polyamine can also comprise or be wholly MXD6, which comprises an aromatic diamine and a non-aromatic diacid. Other partially aromatic polyamines can be based on aromatic diacids such as terephthalic acid (polyamine 6T) or isophthalic acid (polyamine 6I) or blends thereof (polyamine 6T/6I). The melting or processing temperature of the partially aromatic polyamine is in the range of about 240 ° C (for MXD6) to about 355 ° C (for polyamidimine), including about 260 ° C, 280 ° C, 300 ° C, 320 ° C and 340 °C. The melting temperatures of nylon 6 (Nylon 6) and nylon 6,6 are about 220 ° C and 260 ° C, respectively. The lower the melting temperature, the easier the polyamide polymer is processed into fibers. Below is a list of common partially aromatic polymers and certain comparative non-aromatic hydrocarbons and their associated melting temperatures.

Part of the aromatic polyamine can also comprise a copolymer or mixture of a plurality of partially aromatic decylamines. For example, MXD6 can be blended with nylon 6/6T prior to fiber formation. Further, a partially aromatic polymer may be blended with a copolymer or mixture of an aliphatic polyamine or a plurality of aliphatic polyamines. For example, MXD6 can be blended with nylon 6,6 prior to fiber formation. Part of the aromatic fiber may comprise up to about 20% by weight of one or more of the aliphatic polyamine fibers.

Part of the aromatic fiber may be a staple fiber or a continuous filament yarn. Part of the aromatic fibers may also be included in the nonwoven fabric, such as spunbond, meltblown, or combinations thereof. The filament cross section can be any shape including a circle, a triangle, a star, a square, an ellipse, a bilobal, a trilobal or a plane. In addition, the filaments can be textured using known texturing methods. As discussed above, the partially aromatic polyamines that are spun into fibers also contain other partially aromatic or aliphatic polymers. When the fibers are woven, a mixture of more than one polyammonium polymer may be blended prior to spinning into a yarn or may result in the inclusion of at least one partially aromatic polyamine polymer and an additional portion of the aromatic polyamide polymer. Or a plurality of filament yarns of a two-component form of an aliphatic polymer, such as a side-by-side or core-sheath configuration.

The combination of a portion of the aromatic fibers with FR fibers having a significant gas phase effect, such as modified polyacrylonitrile fibers or FR cellulose fibers, can form the primary yarn. The yarn may comprise only a portion of the aromatic fibers and FR fibers; or may comprise other fibers that are FR or non-FR fibers. The amount of some aromatic fibers may vary. Suitable amounts of the partially aromatic fibers comprise from about 5% by weight to about 75% by weight of the primary yarn; from about 5% by weight to about 60% by weight of the yarn; and from about 25% by weight to about 50% by weight of the yarn. The combined yarn can be prepared by any suitable method. For example, the yarn can be a blended staple yarn. The blended staple fiber yarns can be precision blended, with some of the aromatic fibers and FR fibers uniformly blended throughout the yarn. Alternatively, the yarn may in particular be a single strand or a plied yarn, a covered yarn (including single and double quilts) or a cored yarn.

The primary yarn must contain at least one FR fiber that is and has a significant gas phase effect, such as modified polyacrylonitrile fibers or FR cellulose fibers, and combinations thereof. The FR fibers can also be FR cellulose wherein FR additives are added to the FR cellulose during fiber manufacture. Alternatively, FR treatment can be applied to articles containing untreated cellulosic fibers. Examples of suitable cellulosic fibers include cotton, yarn or dissolved cellulose. Articles comprising FR cellulose are intended to contain constituent elements, such as yarns, that are treated prior to incorporation into the article. Articles comprising FR cellulose are also intended to include those after the cellulose has been incorporated into the yarn, and after the yarn has been formed into a fabric or garment. As used herein, cellulose includes, but is not limited to, B Acid esters, cotton, enamel, dissolved cellulose, and combinations thereof. In the primary yarn, one or more cellulosic fibers may be combined with one another and/or with modified polyacrylonitrile fibers. The amount of FR fibers having an important gas phase effect can vary. Suitable amounts of the fibers comprise from about 25% to about 75% by weight of the primary yarn; from greater than 25% to about 75% by weight of the yarn; from about 40% to about 60% by weight of the yarn; and from about 50% to about 75 wt% yarn.

Regardless of whether the FR fibers of the primary yarn are subjected to FR treatment or additives prior to the pretreatment step, post-treatment applied FR additives are introduced into the article, fabric or garment after dyeing. The post-treatment flame retardant comprises: (1) a durable flame retardant; and (2) a non-durable flame retardant. For protective clothing, the treatment must withstand washing, so durable treatment is more desirable. Suitable examples of FR treatments for post-treatment applied FR additives include durable flame retardant chemicals that rely on phosphorus-based FR agents and chemicals or resins that fix FR agents to the fibers.

One suitable method for post-FR processing is the "PROBAN" method. "PROBAN" is the trade name of the finishing process in which cotton-rich fibers are immersed in a water-soluble crosslinkable phosphorus-containing resin and cured by ammonia gas or liquid. The method was originally patented by Hooker Chemical in the United States and Albright and Wilson in the United Kingdom. This method uses a ruthenium-(hydroxymethyl) phosphonium salt wherein the salt component can be sulfate (THPS) or chlorate (THPC). THPS with an ammonia gas curing chamber is currently in use because of concerns about the presence of some by-products. The benefit of this method is that the FR component is a very stable phosphine oxide structure. The THPC-urea precondensate is water soluble prior to its crosslinking by ammonia treatment. At this time, it penetrated well into the cotton fiber and was insoluble. Excellent washing durability (up to 100 industrial washing cycles).

The primary yarn may also comprise other FR fibers well known in the art. Typically, such materials will be combined in small amounts, such as from 0 to about 50% by weight of the yarn. Other suitable amounts include greater than zero, 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, inter-aromatic polyamine, p-aromatic polyamine, phenolic, melamine, poly(p-phenylene benzobisoxazole) (PBO), poly Benzimidazole (PBI), polysulfonamide (PSA), partially oxidized polyacrylonitrile (PAN) and its group Hehe.

The amount of partially aromatic fibers in the primary yarn will depend on which FR fibers and/or other fibers (FR or non-FR) are also included in the yarn. For example, a portion of the aromatic polyamide fibers may be present in the primary yarn in an amount from about 5% by weight to about 75% by weight of the primary yarn; or a portion of the aromatic polyamide fibers may be about 5 of the primary yarn. An amount of from about 5% by weight to about 60% by weight is present in the primary yarn. Other suitable ranges include a minimum of a portion of the aromatic fibers of about 25%; such as a portion of the aromatic fibers being from about 25% to about 75% by weight of the primary yarn or from about 25% to about 5% by weight of the primary yarn. 60% by weight. Part of the aromatic polyamine can also be present in an amount from about 40% to about 60% or about 50% by weight of the primary yarn. The type of FR fiber present with the partially aromatic fibers will contribute to the necessary weight percentage of each component based on the total weight of the primary yarn. When the main yarn is included in the fabric, the fabric is self-extinguishing in the upright burning test (ASTM D6416). In particular, one aspect of the article is a fabric that enables a smoldering time in the upright burn test to be less than about 10 seconds.

Other fibers which may be included in the staple yarn or in the form of filaments (depending on the fiber) and which are flame retardant and not flame retardant are suitable for forming other yarns, fabrics and garments. Other fibers may comprise cellulose such as cotton, strontium or dissolved cellulose (with or without FR), aromatic aromatic polyamides, inter-aromatic polyamines, modified polyacrylonitrile fibers, melamine, poly(pairs) Phenylbenzobisoxazole) (PBO), polybenzimidazole (PBI), polysulfonamide (PSA), oxidized acrylic acid, partially oxidized acrylic acid (including partially oxidized polyacrylonitrile), phenolic, wool, flax, marijuana , silk, crepe (with or without FR), polyester (with or without FR), antistatic fibers, and combinations thereof. Certain fibers such as aromatic polyamides, PBI or PBO maintain strength after flame exposure and, when used in blending yarns and fabrics, effectively reduce the burnt length of the fabric after the burn test.

An aspect of the article may additionally comprise at least one additional yarn that is compositionally different from the primary yarn. "Different in composition" means that the difference between the extra yarn and the main yarn is At least one of a plurality of aspects, such as comprising different fiber compositions, different amounts of the same fibers, different fiber cross-sections, different additives, different colors, and the like. The article may additionally comprise at least two additional yarns that differ in composition from each other and that differ in composition from the primary yarn. Also, the additional yarn may be an FR yarn; or may be a non-FR yarn.

Fabrics made from primary yarns may also contain additional yarns, such as cellulose containing cotton, alfalfa or dissolved cellulose (with or without FR), aromatic polyamides, inter-aromatic polyamines, Polyacrylonitrile fiber, melamine, poly(p-phenylene benzobisoxazole) (PBO), polybenzimidazole (PBI) or polysulfonamide (PSA), oxidized acrylic acid, partially oxidized acrylic acid (including partial oxidation) Polyacrylonitrile), phenolic, wool, linen, hemp, silk, crepe (with or without FR), polyester (with or without FR), antistatic fibers, and combinations thereof.

Fabrics comprising non-FR cellulose can be treated with additional flame retardant additives and trimmed as necessary. An exemplary method of treating cotton is found in the technical bulletin "Fabric Flame Retardant Treatment" (2003), published by Cotton Incorporated, Cary, North Carolina, which is incorporated herein by reference in its entirety. The fabric can be a woven, knitted, and non-woven fabric. Non-woven fabrics are made from carded fabrics, wet laid or spunbond/meltblown processes.

Fibers, yarns and fabrics may also contain other components such as: UV stabilizers, antimicrobials, bleaches, optical brighteners, antioxidants, pigments, dyes, soil repellents, colorants, nanoparticles and Water repellent. A UV stabilizer, an antimicrobial agent, an optical brightener, an antioxidant, a nanoparticle, and a pigment may be added to the flame retardant polymer prior to melt spinning or may be added after the fiber formation. Dyes, soil repellents, color repellents, nanoparticles, and water repellents may be added after the formation of the fibers and/or fabrics. Fabrics made using the disclosed flame retardant fibers may also have a coating or laminate film applied for abrasion resistance or controlled liquid/vapor permeation.

definition:

The smoldering means: "The material continues to burn after the ignition source is removed." [Source: ATSM D6413-11 Standard test Method for Flame Resistance of Textiles (Vertical Method) ]

The burnt length means: "After applying a specific tear force, directly expose the edge of the fabric of the flame to the farthest distance from the visible fabric damage." [Source: ATSM D6413-11 Standard test Method for Flame Resistance of Textiles (Vertical Method) ]

The drip means: "There is a lack of sufficient amount or pressure to form a continuous flow of liquid." [Source: National Fire Protection Association (NFPA) Standard 2112, 2007 Edition, Standard on Flame-Resistant Garments for Protection of Industrial Personnel Against Flash Fire ] .

Melting means that the material produces a distinct flow or a thermal reaction of droplets. [Source: National Fire Protection Association (NFPA) Standard 2112, 2007 Edition, Standard on Flame-Resistant Garments for Protection of Industrial Personnel Against Flash Fire ].

Self-extinguishing means that the material does not continue to burn after removal of the ignition source or the combustion stops before the sample is completely consumed. When tested by the ATSM D6413-11 Standard test Method for Flame Resistance of Textiles (Vertical Method) .

The features and advantages of the present invention are fully described by the following examples, which are provided for illustrative purposes and are not to be construed as limiting the invention in any manner.

Instance

testing method:

The flame retardancy was measured in accordance with ASTM D-6413-11 Standard Test Method for Flame Resistance of Textiles (Vertical Test) .

Washfastness: The American Association of Textile Chemist and Colorists (AATCC) Test Method 61, in which the color transfer to the multi-fiber test strip indicates the dye loss of the test fabric and will be listed in the table of examples. The multi-fiber test strips included on the fibers were dyed. The color loss or adsorption is rated according to the gray scale (1-5), where 5 is a negligible change and 1 is a large change.

Color Measurement: After staining, the color was read using a Macbeth Color Eye 7000A spectrophotometer, which measures the visible spectrum reflectance of the sample for brightness, whiteness, and yellow.

The interpretation of the reading is as follows:

. Higher L values indicate lighter tones

. Higher K/S values indicate darker tones

. a value: indicates red, and the higher the a value, the more red. The lower the greener.

. b value: indicates yellow. The higher the b value, the more yellow, the lower the blue.

Upright burning: ASTM D6413 "Standard Test Method for Flame Resistance of Textiles (Vertical Test)"

[For all examples: the dyeing characteristics of MXD6 and nylon 66 fibers were compared using several classes of dyes. At 160 °F, the fiber samples were pre-flushed with 1 g/l soda ash and 1 g/l Domoscour LFE-810 for 15 minutes. ]

Example Configuration 1: Fibers were individually dyed using a grinding acid dye with or without a leveling agent. The fibers were dyed at 212 °F for 60 minutes.

Compare stained color eye readings

Conclusion: MXD6 fibers are darker than N66 when using a ground acid dye without a leveling agent.

Example configuration 2: Compare staining . The fibers were used in the same bath with disperse blue 3 dye (pH = 9.0) and acid blue 45 (ABB) dye (pH = 5.8) and acid blue 122 grinding acid (MBB) with and without an anionic leveling agent (pH = 5.7). The dye (pH = 5.0) was dyed. The fibers were dyed at 212 °F for 60 minutes.

Color eye readings for multiple dye categories

in conclusion:

1. Using 蒽醌 Grinding Blue B (ABB type amine end group sensitive colorant), MXD6 staining was 80% lighter than the control group N-66.

2. Grinding blue BL (MBB type structure sensitive colorant) without a leveling agent was used, and the staining was 20% lighter than the control group. The dyeing is similar to N66 with a leveling agent.

Example configuration 3: Dyeing with cationic dyes . The fibers are dyed in each bath using one of two dyeing formulas:

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

Red : 1% at 212°F Maxilon Red GRL 200%, 2g/l Laurotex A-25, pH=4.5, 0.5% Domoscour LFE-810 lasts 60 minutes

Color eye readings for cationic dye tones

Cationic dye color and washability

Conclusion: MXD6 dyed with cationic dye is darker than nylon 66. However, dyeing is not as washable as acid dyes.

Example configuration 4: Dyeing with an acid dye. The fibers are dyed in each bath using one of two acid dyeing formulas:

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

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

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

After dyeing, fixed staining with 3% Nylofixan MF2N at 170 °F, pH=4.5 It lasts for 20 minutes.

Color eye readings for acid dyes

Acid dye color and washability

Conclusion: All acid dyes of MXD6嫘萦 have good dyeing ability, but weaker than nylon 66.

Example configuration 5: Dyeing blend of MXD6 with cellulosic fibers. A fabric comprising two fibers is dyed using a two-step process of reactive dyes of cellulosic fibers and acid dyes of MXD6 fibers.

Pre-scouring/bleaching:

1 g/l Domoscour LFE-810 + 1.5 g/l soda ash + 2 g/l Albone 35 + 0.25 g/l Versene 30A at 200 °F for 20 minutes. rinse.

Use reactive dyes to dye cellulose:

The bath was placed at 2 °/l laurotex A-25 at 80 °F.

Add dye.

0.56% Novacron Olive C

0.041% Novacron Brown NC

0.08% Novacron Navy FN-BN

Operate for 5 minutes. 50 g/l of salt was added and the operation was carried out for 5 minutes. Increase to 140 °F, 3 °F / min.

Add 15g/l soda ash.

45 minutes of operation

Drain-flush - Wash with soap and use 1 g/l Domoscour LFE 810 at 200 °F for 15 minutes.

Drip - rinse -

Dyeing MXD6 with acid dye:

The bath was configured with 2 g/l Laurotex A-25 + 0.5% ALbegal B.

3g/l MSP, ph=5.5

Operate for 5 minutes. Add acid dye.

0.22% Erionyl Yellow A-3G

0.032% Erionyl Red A-3g

0.16% Erionyl Navy A-R

Operate for 5 minutes. Increase to 212 °F, 3 °F / min. Operate for 45 minutes.

Cooling - draining - flushing.

2% Cibafix DGF was applied at 170 °F, pH = 4.5 for 20 minutes.

Conclusion: The above method produced good uniform dyeing of 50/50 MXD6 cellulose fibers.

Although the embodiments have been described in the foregoing as a preferred embodiment of the present invention, those skilled in the art will appreciate that changes and modifications may be made without departing from the spirit of the invention. Contains all such changes and modifications.

Claims (22)

An article exhibiting flame retardant or flame retardant (FR) characteristics, comprising: (a) a fabric comprising a pretreatment applied dye or print or a combination thereof; and (b) a post treatment applied FR additive; wherein the fabric comprises a primary Yarn, the main 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 acid dyes, cationic dyes, disperse dyes, anthraquinone dyes, reactive dyes, and combinations thereof. The article of claim 1 wherein the fabric is dyed to a uniform hue. The item of claim 1, wherein the pre-processing additionally includes a second FR process. The article of claim 1 wherein the portion of the aromatic polyamine is spun into fibers having no FR additive. The article of claim 1, wherein the partially aromatic polyamine comprises a polymer or copolymer comprising a monomer selected from the group consisting of aromatic diamine monomers, aliphatic diamine monomers, aromatic two Acid monomers, aliphatic diacid monomers, and combinations thereof. The article of claim 6 wherein the portion of the aromatic polyamine further comprises an aromatic diamine monomer and an aliphatic diacid monomer. The article of claim 1 wherein the portion of the aromatic polyamine is MXD6. The article of claim 1 wherein the portion of the aromatic polyamide fibers comprises a form selected from the group consisting of: cuts, continuous filaments, and combinations thereof. The article of claim 1 wherein the primary yarn comprises a single strand of twisted yarn, a plied twisted yarn, a textured yarn, a blended staple yarn, and combinations thereof. The article of claim 1 wherein the portion of the aromatic polyamide fiber is present in the primary yarn in an amount from about 5% by weight to about 75% by weight of the primary yarn. The article of claim 1, wherein the fiber having a gas phase effect is selected from the group consisting of modified polyacrylonitrile fibers, cellulose fibers, and combinations thereof. The article of claim 1 wherein the primary yarn additionally comprises other fibers selected from the group consisting of FR polyester, FR nylon, FR, meta-aromatic polyamine, para-aromatic polyfluorene Amine, modified polyacrylonitrile fiber, phenolic aldehyde, melamine, poly(p-phenylene benzobisoxazole (PBO), polybenzimidazole (PBI), polysulfonamide (PSA), oxidized acrylic acid, partially oxidized acrylic acid And their combinations. The item of claim 1, wherein the item is a fabric. The item of claim 1, wherein the item is clothing. The article of claim 1 additionally comprising at least one other yarn that differs in composition from the primary yarn. An article exhibiting flame retardant or flame retardant properties, comprising: (a) a fabric comprising a pretreatment consisting of dyeing, printing, and combinations thereof; and (b) comprising a post-combustion treatment or a flame retardant treatment; wherein the fabric comprises Main yarns including cotton fibers and partially aromatic polyamide fibers. A method of preparing an article exhibiting flame retardant or flame retardant properties, comprising the following continuous processing: (a) preparing a fabric comprising a primary yarn comprising a gas having a gas phase effect and a partially aromatic polyamide fiber; (b) providing a pretreatment selected from the group consisting of dyeing, printing, and combinations thereof; and (c) treating after treatment with a flame or flame retardant (FR) treatment. The method of claim 18, which additionally comprises a second printing step after the treatment comprising the flame resistant or flame retardant treatment. The method of claim 18, wherein the gas having a gas phase effect is a cellulose fiber. The method of claim 20, wherein the cellulosic fibers comprise cotton. The method of claim 18, wherein the pre-processing additionally includes a second FR process.