WO2015179616A1 - Polymères ayant des propriétés de surface modifiées et procédés de fabrication de ceux-ci - Google Patents

Polymères ayant des propriétés de surface modifiées et procédés de fabrication de ceux-ci Download PDF

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Publication number
WO2015179616A1
WO2015179616A1 PCT/US2015/031935 US2015031935W WO2015179616A1 WO 2015179616 A1 WO2015179616 A1 WO 2015179616A1 US 2015031935 W US2015031935 W US 2015031935W WO 2015179616 A1 WO2015179616 A1 WO 2015179616A1
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WIPO (PCT)
Prior art keywords
fiber
additive
thermoplastic
reactive
thermoplastic fiber
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PCT/US2015/031935
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English (en)
Inventor
Natalie M. GIBSON
Mansour K. Abdulbaki
Isaac K. Iverson
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Invista North America S.A.R.L.
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Application filed by Invista North America S.A.R.L. filed Critical Invista North America S.A.R.L.
Priority to JP2016568927A priority Critical patent/JP6839983B2/ja
Priority to AU2015264103A priority patent/AU2015264103B2/en
Priority to CA2949532A priority patent/CA2949532A1/fr
Priority to CN201580039911.8A priority patent/CN107001792A/zh
Priority to EP15795331.6A priority patent/EP3145996A4/fr
Priority to US15/312,322 priority patent/US20170081783A1/en
Publication of WO2015179616A1 publication Critical patent/WO2015179616A1/fr

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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/60—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides

Definitions

  • the present disclosure relates to compositions of additive-modified polymers wherein the additive or additives provide a modified and/or reactive surface on substrates produced from the additive-modified polymers.
  • the substrate is a fiber or molded part and the additive is a polyol.
  • the additive or additives enhance association of selected molecules to the fiber or molded part and/or enhance soil resistance of the fiber or molded part.
  • Fibers formed from natural and synthetic fibers are often treated to impart properties that are beneficial for industrial and residential use. These properties include stain resistance, dye permanence and soil resistance. When topical chemistry is used to provide these properties, additional equipment, chemicals and processes are involved. This can add significant cost and time to a fiber manufacturing process. Therefore, there is a need for fibers that have modified or reactive surfaces to allow for targeted covalent attachment or improved non-covalent association of topical treatments and/or modified surfaces to improve soil resistance and/or release.
  • U.S. Patent 6,623,853 discloses a method of copolymerizing polyethylene glycol and branching agent into polyethylene terephthalate to achieve a composition that can be spun into fibers with superior wicking, dyeability and tactile properties.
  • U.S. Patent 5,135,697 and 5,272,246 disclose the incorporation into polyethylene terephthalate (PET) of 175 to 700 ppm of pentaerythritol and 1.3 to 3.1 wt. percent adipic acid to improve the atmospheric dye rating to 112.
  • PET polyethylene terephthalate
  • Patent 6,284,864 discloses copolymer fibers of polyethylene terephthalate prepared fiOm terephthalic acid, or its ester equivalent; at least two dicarboxylic acids, or their anhydride or ester equivalents; and pentaerythritol with improved dyeability and dye retention properties.
  • these references only teach improved dyeability on polyester fibers and do not teach a modified or reactive surface to improve fiber properties or to allow for targeted covalent attachment of topical treatments.
  • Some polymeric fibers such as cationic ("cat-dye") nylon fiber that are topically treated to be stain resistant, bleed following stain-blocking treatment due to the required acidic process parameters. Therefore, there is also a need for improved synthetic fibers, such as nylon fibers and solution-dyed nylon fibers, which have improved dye uptake and/or dye fastness.
  • 2013/0228728 Al also discloses addition of polyhydric alcohols such as monopentaerythritol or pentaerythritol (MPE), dipentaerythiitol (DPE), tripentaeiythritol (TPE), and combinations thereof, for use in imparting flame retardance to molded polyamides and to help retain tensile strength, elongation, and impact resistance after being exposed to high heats for extended periods of time.
  • MPE monopentaerythritol or pentaerythritol
  • DPE dipentaerythiitol
  • TPE tripentaeiythritol
  • Patent 8,304,513 discloses soil resistant polyester polymers, particularly poly (trimethylene terephthalate) comprising fluorovinylether functionalized aromatic repeat units.
  • U.S. Patent 8,697,831 discloses soil resistant polyamides, particularly nylon 6,6 and nylon 6 comprising fiuoroether functionalized aromatic repeat units.
  • thermoplastic polymers, fibers and molded products with modified and/or reactive surface properties are disclosed. Also disclosed are articles of manufacture and methods of making the polymers, fibers and molded parts.
  • an aspect of the present invention relates to a thermoplastic polymer with a modified and/or reactive surface.
  • the thermoplastic polymer is produced by incorporating an additive which yields a modified and/or reactive surface with a polymer during the polymer melt state.
  • the additive is a polyol that yields reactive hydroxyl groups on the surface of a substrate produced from the polymer.
  • thermoplastic fiber or molded part comprises a thermoplastic polymer and an additive present in the thermoplastic fiber or molded part which yields modified and/or reactive groups on the surface of the fiber or molded part.
  • the additive is a polyol that yields reactive hydroxyl groups on the surface of the fiber or molded part.
  • thermoplastic fiber or molded part comprising a thermoplastic polymer, an additive present in the thermoplastic fiber which yields modified and/or reactive groups on the surface of the fiber or molded part, and a selected molecule such as a topical treatment and/or dye attached to the modified and/or reactive groups.
  • Another aspect of the present invention relates to a method for manufacturing a thermoplastic fiber or molded part with a modified and/or reactive surface.
  • the method comprises incoiporating an additive which yields a modified and/or reactive surface with a polymer during the polymer melt state.
  • the additive is a polyol that yields reactive hydroxyl groups on the surface of the polymer, fiber or molded part.
  • Another aspect of the present invention relates to an article of manufacture, at least a portion of which comprises a thermoplastic polymer having a modified and/or reactive surface produced by incorporating an additive which yields modified and/or reactive groups on the surface of a substrate produced from the polymer.
  • the additive is a polyol that yields reactive hydroxyl groups on the surface of a substrate produced from the polymer.
  • Another aspect of the present invention relates to an article of manufacture, at least a portion of which comprises a thermoplastic fiber comprising a thermoplastic polymer and an additive present in the thermoplastic liber that yields modified and/or reactive groups on the surface of the fiber.
  • the additive is a polyol that yields reactive hydroxyl groups on the surface of the fiber.
  • thermoplastic fiber comprising a thermoplastic polymer, an additive present in the thermoplastic fiber which yields modified and/or reactive groups on the surface of the fiber, and a selected molecule such as a topical treatment and/or dye attached to or bound to the modified and/or reactive groups present on the fiber surface.
  • thermoplastic fiber or molded part comprising a thermoplastic polymer and an additive incorporated with the thermoplastic polymer for enhanced soil resistance.
  • thermoplastic fiber comprising a thermoplastic polymer, a stain resistant additive capable of disabling acid dye sites of the thermoplastic polymer and an additive incorporated with the thermoplastic polymer for enhanced soil resistance.
  • Yet another aspect of the present invention relates to a method for enhancing soil resistance of a thermoplastic fiber or molded part.
  • the method comprises incorporating an additive which yields a modified and/or reactive surface with a polymer during the polymer melt state.
  • the additive is a polyol that yields reactive hydroxyl groups on the surface of the fiber or molded part.
  • Yet another aspect of the present invention relates to a method for enhancing stain and soil resistance of a thermoplastic fiber, said method comprising incorporating a stain blocking additive capable of disabling acid dye sites and an additive which yields a modified and/or reactive surface with a thermoplastic polymer during the polymer melt state.
  • Figure 1 A and IB are SEM images of nylon 6,6 fibers with 5% DPE ( Figure 1 A) and pure nylon 6,6 ( Figure IB).
  • Figure 2 displays images of cross-sections and modification ratios (MR) of fibers spun from nylon 6,6 and various polyols.
  • Figure 3 A is an image of control and caipet made from nylon 6,6 fiber with 1.5% DPE after dying and rinsing using Procion® Red MX-5B dye.
  • Figure 3B is a plot of chromameter data for the samples shown in Figure 3 A showing the a* values (average of three measurements.) for the carpets with and without DPE using Procion® Red MX-5B dye.
  • Figure 4 is a plot of chromameter data for carpets with and without DPE dyed at room temperature using Procion® Red MX-5B dye
  • Figure 5A is an image of control and carpet made from nylon 6,6 fiber with 1.5% DPE after dying and rinsing using Remazol® Brilliant Orange dye.
  • Figure 5B is a plot of chromameter data for the samples shown in Figure 5 A showing the a* values (average of three measurements.) for the carpets with and without DPE Remazol® Brilliant Orange dye.
  • Figure 6 is a plot of chromameter data for carpets with and without DPE dyed at room temperature using Remazol® Brilliant Orange dye
  • Figure7 is a plot of soiling data obtained from ASTM D6540 testing of un-pigmented, cationic-dyeable nylon 6,6 cut-pile carpet without any additional topical chemistry with and without an attempted pre-extraction of un-anchored surface constituents.
  • No change in the hot water extraction (HWE) vs. unwashed data demonstrates a degree of durability of the additive present at the surface.
  • Figure 8 is an image of the soiled and cleaned cut-pile carpets from which the data in Figure 7 was collected.
  • Figure 9 consolidates the data points from the HWE and unwashed readings of Figure 7, further demonstrating the grouping of the data points regardless of attempted extraction.
  • Figure 10 is a plot of additional soiling data per ASTM D6540 on cut-pile carpets with 0%, 1%, and 2 % by weight of DPE in the thermoplastic fiber.
  • Figure 11 is a plot of soiling data from cut-pile carpet with and without an attempted pre- extraction of unbound surface constituents by HWE where the carpet was treated with a topical fluorochemical-containing anti-soiling treatment and shows that it was not as well-bound to the surface of the 2% DPE fibers as it was to the standard nylon fibers.
  • Figure 12 is a plot of soiling data per ASTM D6540 on stain resistant, loop-pile carpets with 0%, topical anti-soil treatment with 200 ppm of fluorine, and 0.53 % and 0.77% by weight of DPE in the thermoplastic fiber.
  • Figure 13 is a plot of soiling data per ASTM D6540 on stain resistant, loop-pile carpets with topical anti-soil treatment with 200 ppm of fluorine, and 0.53 % and 0.77% by weight of DPE in the thermoplastic fiber.
  • thermoplastic polymers having modified and/or reactive surfaces, themioplastic polymeric fibers or molded parts comprising an additive present in the thermoplastic polymer which yields modified and/or reactive groups on the surface of the fiber or molded part for attachment to a topical treatment and/or dye and/or to modify surface properties, methods for production of these thermoplastic polymers, fibers or molded parts and articles of manufacture, at least a portion of which comprises these thermoplastic polymers fibers or molded parts.
  • Embodiments of the current invention also do not require high heat exposure for extended periods in order to realize the claimed benefits, thus providing an advantage in processing time and reduced manufacturing complexity.
  • thermoplastic polymers useful in the present invention include polyamides, polyethylenes, polypropylenes, and combinations thereof.
  • the thermoplastic polymer is a polyamide such as, but not limited to nylon 6,6; nylon 6; nylon 4,6; nylon 6,12; nylon 6,10; nylon 6T; nylon 61; nylon 9T; nylon DT; nylon DI; nylon D6; and nylon 7; and/or combinations thereof.
  • a polyamide such as, but not limited to nylon 6,6; nylon 6; nylon 4,6; nylon 6,12; nylon 6,10; nylon 6T; nylon 61; nylon 9T; nylon DT; nylon DI; nylon D6; and nylon 7; and/or combinations thereof.
  • the thermoplastic polymer is nylon 6,6.
  • Additives useful in the present invention when present in the thermoplastic polymer yield modified and/or reactive groups on the surface of any substrate produced from the polymer following extrusion.
  • modified and/or reactive group or “modified and/or reactive surface” for purposes of the present invention, it is meant one or more functional chemical groups yielded by an additive which are incorporated and/or embedded and/or imparted on, in or at the surface of a polymer substrate.
  • one or, more functional chemical groups yielded by an additive are capable of chemically or physically reacting, binding or attaching to, or associating with a molecule selected to modify properties of the polymer substrate and/or its surface.
  • non-covalent bonding, attachment or association includes dipole-dipole, ion-dipole, or hydrogen bonding interaction.
  • a polyol additive during the polymer melt state yields reactive hydroxyl groups on the surface of the fiber or molded part.
  • additives useful in the present invention include, but are not limited to, polyols including, but not limited to, pentaerythiitol (MPE), dipentaerythritol (DPE),
  • TPE tripentaerythritol
  • sugar alcohols such as disclosed by US 2010/0029819 Al, teachings of which are incorporated herein, including, but not limited to glycerol, trimethylolpropane, 2,3-di-(2'-hydroxyethyl)-cyclohexan-l-ol, hexane-l,2,6-triol, 1,1,1 -tris-(hydroxymethyl)ethane, 3 -(2'-hydroxyethoxy) -propane- 1 ,2diol, 3 -(2'- hydroxypropoxy)-propane-l,2-diol, 2-(2 !
  • the amount of additive included may vary depending upon the desired texture and/or strength of the substrate as well as the surface property to be modified.
  • the additive included ranges from about 0.01wt% to about 10wt%. In another nonlimiting embodiment, the additive included ranges from about 0.05 wt% to about 5wt%. In another nonlimiting embodiment, the additive included ranges from about 0.05wt% to about 3wt%. In another nonlimiting embodiment the additive is present below about 2wt%. In another nonlimiting embodiment, the additive is present below lwt%.
  • the additive included is in an amount greater than about
  • the additive included is in an amount greater than about 350 ppm.
  • at least a portion of the additive is present on the surface of the thermoplastic fiber or molded part.
  • Figure 1 shows SEM images of nylon 6,6 fibers with 5% DPE (Figure 1A) and pure nylon 6,6 ( Figure IB). As can be seen in Figure 1A, there is addiitve present on the surface of the thermoplastic fiber.
  • thermoplastic fibers When incorporated into thermoplastic fibers, the hydroxyl groups found at the surface of the fiber can be exploited by a chemical or physical reaction or association with various topical treatments for enhanced topical durability and reactive dyes for improved aesthetics. Such color cannot be as readily achieved with pure polymers such as nylon 6,6 alone.
  • the hydroxyl groups present on the surface can be covalently reacted or non-covalently bound with an array of molecules, including but not limited to topical stain blockers, soil resistant treatments, reactive dyes including both homo- and hetero-functional reactive dye,
  • the additive modifies the surface of the
  • thermoplastic fiber to impart enhanced soil resistance Example 4 shows that thermoplastic fibers with the additive present display built in soil resistance.
  • the additive is incorporated in the range of less than about 2% by weight.
  • thermoplastic fiber with built in stain and soil resistance could be formed from embodiments of the current invention.
  • the thermoplastic fiber has improved stain resistance and the additive modifies the surface of the fiber to impart enhanced soil resistance.
  • a stain blocking additive capable of disabling acid dye sites is incorporated in the thermoplastic polymer.
  • the stain blocking additive may be added directly into the polymer melt or via a masterbatch.
  • the stain blocking additive is already present in the thermoplastic polymer prior to the addition of the additive which yields a modified and/or reactive surface on the thermoplastic fiber.
  • Suitable built-in stain blocking additives include those that are known to disable acid dye sites.
  • acid dyes sites refer to amine end groups or amide linkages which react or associate with acid dyes which result in staining.
  • Stain blocking additives react or associate with these acid dye sites to prevent the acid dye sites from reacting or associating with acid dyes.
  • Suitable stain blocking additives for use in polyamides are discussed in US Pat. No. 5,155,178, herein incorporated by reference.
  • Suitable stain blocking additives include, but are not limited to aromatic sulfonates and alkali metal salts thereof, such as 5-sulfoisophthalic acid, sodium salt and dimethyl-5-sulfoisophthalate, sodium salt.
  • the stain blocking additive is 5-sulfoisophthalic acid, sodium salt (SSIPA). In one nonlimiting embodiment, the stain blocking additive is present in a range from about 1 to 10 percent by weight. In another nonlimiting embodiment, the stain blocking additive is present in a range from about 1 to 5 percent by weight.
  • thermoplastic fibers of the present invention with improved stain resistance and enhanced soil resistance may be useful for many applications.
  • One application would be in broadloom carpet and carpet tile.
  • the thermoplastic fibers of the present invention with improved stain resistance and enhanced soil resistance may also be textured to form BCF fiber and utilized in broadloom carpet or carpet tile.
  • thermoplastic fibers comprising a stain blocking additive and an additive which imparts soil resistance is disclosed, wherein the thermoplastic fiber is a bulk continuous filament (BCF) fiber.
  • BCF bulk continuous filament
  • the thermoplastic fibers of the present invention with improved stain resistance and enhanced soil resistance may also be solution dyed fibers, wherein pigments known in the art are incorporated in the fiber.
  • thermoplastic fibers comprising a stain blocking additive and an additive which imparts soil resistance
  • thermoplastic fiber is a bulk continuous filament (BCF) and solution dyed fiber
  • thermoplastic fibers comprising a stain blocking additive and an additive which imparts soil resistance
  • thermoplastic fiber is a bulk continuous filament (BCF) and solution dyed nylon (SDN) fiber.
  • the additives described herein may also be incorporated into molded thermoplastics.
  • the hydroxyl groups found on the surface of the molded parts are also expected to react with dyes as well as other topical agents such as, but not limited to, flame retardants, and to increase hydrophilicity of the molded parts.
  • the present invention also relates to thermoplastic fibers and molded parts comprising a thennoplastic polymer, an additive present in the thennoplastic polymer which imparts reactive groups at the surface of the fiber or molded part, and a topical treatment and/or dye attached to the reactive group.
  • thermoplastic polymer contains no further additional reinforcing materials.
  • thermoplastic fibers further comprise an additional reinforcing material or materials.
  • additional reinforcing materials which can be used in the fibers of the present invention include, but are in no way limited to, carbon, glass, and/or silicate particles of various morphologies.
  • thermoplastics polymers of this invention examples include, but are not limited to, TiC% pigments, dye enhancing additives, sulfonated oligomers, lubricants and process modifiers.
  • the present invention also provides methods for manufacturing a thermoplastic polymer with a modified and/or reactive surface.
  • an additive which yields a modified and/or reactive surface is incorporated with a polymer during the polymer melt state.
  • the additive is a polyol.
  • reactive hydroxyl groups are imparted on the surface.
  • Standard thermoplastic polymer processing conditions can be used.
  • the additive may be added directly into the polymer melt or via a masterbatch.
  • the present invention also provides methods for enhancing soil resistance of a thermoplastic fiber, said method comprising incorporating an additive which yields a modified and/or reactive surface with a thermoplastic polymer during the polymer melt state.
  • the additive is a polyol.
  • reactive hydroxyl groups are imparted on the surface.
  • Standard thennoplastic polymer processing conditions can be used.
  • the additive may be added directly into the polymer melt or via a masterbatch.
  • the present invention also provides methods for enhancing stain and soil resistance of a thermoplastic fiber, said method comprising incorporating a stain blocking additive capable of disabling acid dye sites and an additive which yields a modified and/or reactive surface with a thermoplastic polymer during the polymer melt state.
  • the additive is a polyol.
  • reactive hydroxyl groups are imparted on the surface.
  • Standard thermoplastic polymer processing conditions can be used.
  • the additive and stain blocking additive may be added directly into the polymer melt or via a masterbatch.
  • the stain blocking additive is already present in the thermoplastic polymer prior the polymer melt state and prior to the addition of the additive which yields a modified and/or reactive surface on the thermoplastic fiber.
  • thermoplastic polymer with a modified and/or reactive surface produced by incorporating an additive which yields a modified and/or reactive surface
  • thermoplastic polymeric fiber or molded part comprising a thermoplastic polymer and an additive present in the thermoplastic fiber which imparts modified or reactive groups the surface of the fiber or molded part
  • thermoplastic polymer, an additive incorporated with the polymer which yields modified and/or reactive groups on the surface of the fiber or molded part, and a topical treatment and/or dye attached to the reactive group is a polyol.
  • the additive yields or imparts hydroxyl groups and/or hydroxy!
  • Non-limiting examples of such articles of manufacture include, but are not limited to, carpeting, bathmats, area rags, upholstery, drapery, linens, towels, clothing, footwear, membranes, food and storage containers, equipment and automotive parts.
  • carpets prepared from fibers in accordance with the present invention exhibit greater uptake of reactive dyes and the potential to have targeted covalent attachment of chemical moieties and greater uptake of reactive dyes, thereby deepening the color and improving aesthetic properties.
  • articles of manufacture comprising the fibers of the present invention are expected to exhibit increased hydrophilicity, increased moisture absorption, wick- ability and/or wettability, as well as increased topical durability when reacted with tailored surface treatments, thus making them useful in applications such as, but not limited to, bathmats, towels, robes, linens, clothing, medical textiles and personal care items.
  • drawing of the fibers aligns or exposes the groups to the surface and/or that the material is blooming to the surface during quenching and thus with a lower denier fiber, there is a greater likelihood that the material can migrate before being fully quenched.
  • Nylon 6,6 fibers comprising pentaerythritol were easily processed and spun into filaments.
  • Nylon 6,6 fibers comprising TPE behaved very similarly to DPE. When exposed to the same cotton dye, pentaerythritol also showed preferential dye uptake over the control.
  • thermoplastic polymer [0065] The following section provides further illustration of thermoplastic polymer
  • compositions, articles of manufacture and processes of the present invention comprised nylon 6,6 and either MPE, DPE or TPE.
  • Compositions, examined in these nonlimiting examples comprised nylon 6,6 and either MPE, DPE or TPE.
  • MPE polyethylene
  • DPE polyethylene
  • TPE thermoplastic polymers and additives which are expected to exhibit similar behaviors to those described herein for nylon 6,6 and MPE, DPE or TPE in accordance with the teachings herein.
  • these working examples are illustrative only and are not intended to limit the scope of the invention in any way.
  • Samples used for the following examples were made using nylon 6,6 with an RV of 45.3 when tested using an adaptation of ASTM D789 and 20.95 amine end groups (AEG) when tested by potentionietric titration technique.
  • the MPE used is commercially available from Perstop under the trade name CharmoreTM PM 15.
  • the DPE used is commercially available from
  • a masterbatch comprising dipentaerythritol additive and nylon 6,6 was used. In initial experiments, the masterbatch contained 30% DPE. In subsequent experiments, a masterbatch containing 40% DPE was used. The masterbatch was mixed with nylon 6,6 polymer in various concentrations ranging from 0-5 wt.% actives as shown in Table 1 below. The mixtures were spun using trilobal spinnerets with a 920 denier aim. SEMs of the control and Sample 4 as seen in Figure 1 show how the surface roughens when DPE is added.
  • the mixture was melted and recirculated at 15 rpm for 5 minutes at 265°C.
  • the spinneret temperature was set to 260°C as the fiber was extruded.
  • MPE could be processed and strung up on a tube at 5% actives, but TPE at 5% had the same problems as DPE. Maximum TPE concentrations were not determined.
  • Reactive fibers were produced by the direct addition of polyol powders to nylon 6,6; thereby bypassing the masterbatching process and removing any acid dye carrier polymer.
  • Polyol powders which included monopentaerythritol (MPE), dipentaerythritol (DPE) and
  • TPE tripentaerythrital
  • the polyol powders were then coated onto nylon 6,6 pellets and pigment pellets using a portable cement mixer. Powders were added in the ratios depicted in Table 2. After coating, the blends were placed in the hopper and melt spun with a 920 denier aim (or 4.25 dpi) using a 108 filament trilobal spinneret. After spinning, cross- sections and modification ratios (MR) of the fibers were obtained and are shown in Figure 2. Fibers were then processed into yams and tufted into carpets for follow up experiments. Figure 2 shows the Cross-sections and modification ratios (MR) of fibers spun from Table 2.
  • Example 15 The control and 1.5% DPE carpet (Sample 15) from Example 2 were cut into 6 in. x 6 in. squares and dyed using Procion® Red MX-5B reactive dye. The dyeing procedure took place using the following technique:
  • Figure 3 A shows damp carpets directly after dyeing and rinsing (control carpet, left; 1.5% DPE carpet, right).
  • Figure 3A shows the a*values (average of three measurements) for carpets with and without DPE using Procion® Red MX-5B dye.
  • Example 15 the control and 1.5% DPE carpet (Sample 15) from Example 2 were dyed at room temperature by adding the samples to the reserved dye baths from Example 3. The caipets were again cut into 6 in. x 6 in. squares, then directly submerged in the pre-prepared Procion® Red MX- 5B dye bath. Carpets were allowed to sit in the bath at room temperature for 4 hours. After dyeing carpets were thoroughly rinsed until the water ran clear. The carpets were then dried in an oven until all moisture was removed. To test the durability of the dye, HWE was completed in the same manner as Example 3. The a* values of the three measurements were averaged and reported in Figure 4. Figure 4 shows the a*values (average of 3 measurements) for carpets with and without DPE dyed at room
  • Example 15 The control and 1.5% DPE carpet (Sample 15) from Example 2 were cut into 6 in. x 6 in. squares and dyed using Remazol® Reactive Orange Dye (Brilliant Orange 3R).
  • the dye bath was prepared by stirring in 70 grams of NaCl to 2000 ml of DI H20, until dissolved. Carpets were placed into the salt bath for 10 minutes then removed and wrung out. To the salt water, 1.0 gram of dye was added, followed by the addition of 5.3 grams of sodium bicarbonate. Carpet samples were placed back in the beaker for an additional 10 minutes then an additional 16 grams of sodium bicarbonate was added. The temperature of the bath was increased to 50°C ⁇ 5°C and left for sit for 4 hours.
  • Example 15 the control and 1.5% DPE carpet (Sample 15) from Example 2 were dyed at room temperature by adding the samples to the reserved dye bath from Examples 5.
  • the carpets were again cut into 6 in. x 6 in. squares, then directly submerged in the pre-prepared Remazol® Reactive Orange Dye (Brilliant Orange 3R).dye bath. Carpets were allowed to sit in the bath at room temperature for 4 hours. After dyeing carpets were thoroughly rinsed until the water ran clear. The carpets were then dried in an oven until all moisture was removed.
  • HWE was completed in the same manner as Example 3.
  • the a* values of the three measurements were averaged and reported in Figure 6.
  • Figure 6 shows the a* values (average of 3 measurements) for carpets with and without DPE dyed at room temperature using Remazol® Brilliant Orange dye.
  • a concentrated polymer masterbatch of DPE in nylon 6,6 was added to a melt extruder with nylon 6,6 flake and melt spun at a ratio such as to give a 2wt% loading of DPE actives in the resultant nylon 6,6 fibers.
  • the fibers were processed in a standard way recognizable to those skilled in the field of BCF spinning and caipet manufacture. Cut-pile carpets were then tufted and finished for dyeing.
  • the 95% by weight of the nylon used to produce the fibers was of a stain-resistant nylon that resists acid dyeing and anionic staiiring.
  • nylon 6,6 used as a carrier in the polymer additive concentrate was not of a stain resistant formulation leaving 3wt% of the material in the final form potentially able to accept an acidic dye. As expected, it was found that the carpet was not dyeable with standard acidic dyes, was not pigmented, and so had a white color for testing.
  • Drum soiling data is recorded as Delta E ( ⁇ ) and measured according to ASTM D6540, where a lower ⁇ indicates a smaller difference in the color of the caipet before and after being soiled and vacuumed-clean.
  • ⁇ the relative soiling performance of variously-treated samples may be determined.
  • the test simulates the soiling of carpet in residential or commercial environments to a traffic count level of about 100,000 to 300,000.
  • soiling tests can be conducted on up to six carpet samples simultaneously using a drum.
  • the base color of the sample (using the L, a, b color space) is measured using the hand held color measurement instrument sold by Minolta Corporation as "Chromameter" model CR-310 (at Camden).
  • This measurement output is in the form L*, a* and b* values and describes a color value in color space. This is the original color value.
  • the carpet sample is mounted on a thin plastic sheet and placed in the drum. Two hundred fifty grams (250 g) of dirty Zytel 101 nylon beads (by DuPont Canada, Mississauga, Ontario) are placed on the sample. The dirty beads are prepared by mixing ten grams (10 g) of AATCC TM-122 synthetic caipet soil (by Manufacturer Textile Innovators Corp. Windsor, N.C.) with one thousand grams (1000 g) of new Nylon Zytel 101 beads. One thousand grams (1000 g) of 3 /s-inch diameter steel ball bearings are added into the drum.
  • the drum is run for 30 minutes with direction reversal and the sample removed, After removal, the carpet is cleaned with a vacuum cleaner and the chromameter is used again to measure the color of the carpet after cleaning.
  • the difference between the color measurements of each carpet (before and after soiling and cleaning) is the total color difference, ⁇ *, and is based on L*, a*, and b* color differences in color space, known to those skilled in the field where
  • AE* V((AL*) 2 * ( ⁇ *) 2 * ( ⁇ * ) 2 )
  • Example 8 Surface presence of hydroxyls and reduced adhesion of incompatible topical treatments
  • a concentrated polymer masterbatch of DPE in nylon 6,6, was added to a melt extruder with nylon 6,6 flake and melt spun at a ratio such as to give a 2wt% loading of DPE in the resultant nylon 6,6 fibers.
  • the fibers were processed in a standard way recognizable to those skilled in the field of BCF spinning and carpet manufacture. Cut-pile catpets were then tufted and finished for dyeing.
  • the 95% by weight of the nylon used to produce the fibers was of a stain-resistant nylon that resists acid dyeing and anionic staining.
  • the nylon 6,6 used as a carrier in the polymer additive concentrate was not of a stain resistant formulation leaving 3wt% of the material in the final form potentially able to accept an acidic dye.
  • the carpet was not dyeable with standard acidic dyes, was not pigmented, and so had a white color for testing.
  • the caipets were treated with a topical anti-soiling treatment that has a fluorochemical component as a minority ingredient. Soiling of the carpet with and without an attempted pre-extraction of unbound surface constituents by hot water extraction showed that the fluorochemical anti-soiling treatment was not as well-bound to the surface of the 2% DPE fibers as it was to the standard nylon fibers (see Figure 11).
  • a concentrated polymer masterbatch of DPE (40%) in nylon 6,6 was added to a melt extruder with nylon 6,6 flake and melt spun at different ratios such as to give a 0.53 wt% and 0.77 wt% loading of DPE in the resultant nylon 6,6 fibers.
  • the fibers were processed in a standard way recognizable to those skilled in the field of BCF spinning and carpet manufacture. Loop-pile carpets were then tufted and finished.
  • the 95% by weight of the nylon used to produce the fibers was of a stain-resistant nylon that resists acid dyeing and anionic staining.
  • the fibers were of a rounded square cross section with 4 continuous voids along the length of the fiber.

Abstract

L'invention concerne des fibres thermoplastiques présentant un additif qui permet d'obtenir des groupes modifiés et/ou réactifs à la surface des fibres. L'invention concerne également des procédés de fabrication et des articles de fabrication contenant ces fibres thermoplastiques. L'invention concerne également des procédés et des produits présentant une plus grande résistance à la salissure.
PCT/US2015/031935 2009-10-30 2015-05-21 Polymères ayant des propriétés de surface modifiées et procédés de fabrication de ceux-ci WO2015179616A1 (fr)

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JP2016568927A JP6839983B2 (ja) 2014-05-22 2015-05-21 改質された表面特性を有するポリマー及びそれらの作製方法
AU2015264103A AU2015264103B2 (en) 2014-05-22 2015-05-21 Polymers with modified surface properties and method of making the same
CA2949532A CA2949532A1 (fr) 2014-05-22 2015-05-21 Polymeres ayant des proprietes de surface modifiees et procedes de fabrication de ceux-ci
CN201580039911.8A CN107001792A (zh) 2014-05-22 2015-05-21 具有改性表面特性的聚合物和其制造方法
EP15795331.6A EP3145996A4 (fr) 2014-05-22 2015-05-21 Polymères ayant des propriétés de surface modifiées et procédés de fabrication de ceux-ci
US15/312,322 US20170081783A1 (en) 2009-10-30 2015-05-21 Polymers with modified surface properties and method of making the same

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US201462001853P 2014-05-22 2014-05-22
US62/001,853 2014-05-22

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CN110387597B (zh) * 2019-06-19 2021-10-26 东华大学 一种基于一步法牵伸工艺的高强尼龙6长丝及其制备方法

Citations (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3236685A (en) 1962-06-20 1966-02-22 Eastman Kodak Co Process for treating textile fibers and other shaped products with coatings
US4863664A (en) 1985-04-22 1989-09-05 Basf Corporation High speed process of making polyamide filaments
US4904408A (en) * 1987-04-03 1990-02-27 Alexander Kud Use of graft polymers based on polyalkylene oxides as grayness inhibitors in the wash and aftertreatment of textile material containing synthetic fibers
US5135697A (en) 1990-08-28 1992-08-04 Hoescht Celanese Corporation Polyester copolymer fiber having enhanced strength and dyeability properties
US5155178A (en) 1990-08-08 1992-10-13 E. I. Du Pont De Nemours And Company Antistain block copolymer compositions of modified nylon copolymers and high carbon nylons
WO1993020269A1 (fr) * 1992-04-03 1993-10-14 United States Of America, As Represented By The Se Fibres thermo adaptables modifiees par glyoxal et leur procede de preparation
US5272246A (en) 1990-08-28 1993-12-21 Hoechst Celanese Corporation Polyester copolymer fiber having enhanced strength and dyeability properties
DE4309436A1 (de) 1993-03-24 1994-09-29 Sandoz Ag Sauer modifizierte synthetishe Polyamide
US5487856A (en) 1993-08-16 1996-01-30 Basf Corporation Process for the manufacture of a post-heat set dyed fabric of polyamide fibers having improved dye washfastness and heat stability
WO1997033019A1 (fr) * 1996-03-07 1997-09-12 Minnesota Mining And Manufacturing Company Fil pour moquette ayant une grande resistance aux salissures
EP0785304B1 (fr) 1991-10-21 2000-12-27 Tencel Limited Traitement de fibres filées à partir d'une solution afin de réduire leur tendance à fibriller
US6284864B1 (en) 2000-05-31 2001-09-04 Arteva North America S.A.R.L. Permanent deep-dye polyester
US20030138625A1 (en) * 1995-08-31 2003-07-24 Studholme Matthew Benjamin Stain-resistant polyamide composition and fibers
US6610107B1 (en) * 1999-06-28 2003-08-26 Industrial Technology Research Institute Method for modifying fiber surfaces
US6623853B2 (en) 1998-08-28 2003-09-23 Wellman, Inc. Polyethylene glycol modified polyester fibers and method for making the same
US6635346B2 (en) 1997-10-22 2003-10-21 Prisma Fibers, Inc. Stain-resistant polyamide composition and fibers and method of production thereof
US20090149590A1 (en) 2005-09-29 2009-06-11 Nilit Ltd. Modified Polyamides, Uses Thereof and Process for Their Preparation
US8247519B1 (en) 2011-06-22 2012-08-21 E I Du Pont De Nemours And Company Shaped articles fabricated from polyamides comprising fluoroether functionalized aromatic moieties
US8304513B2 (en) 2009-09-02 2012-11-06 E I Du Pont De Nemours And Company Polyesters comprising fluorovinylether functionalized aromatic moieties
US20130228728A1 (en) 2011-08-31 2013-09-05 Invista North America S.A.R.L. Compositions of polyhydric alcohols and polyamides
US8697831B2 (en) 2011-06-22 2014-04-15 E I Du Pont De Nemours And Company Process for preparing polyamides comprising fluoroether functionalized aromatic moieties
CN103757731A (zh) 2013-12-11 2014-04-30 巢湖亚塑网具制造有限公司 一种耐酸碱渔网

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5879052A (ja) * 1981-11-05 1983-05-12 Unitika Ltd 耐久性の優れたポリアミド樹脂及び成形品
DE3673008D1 (de) * 1983-12-16 1990-08-30 Monsanto Co Fleckenabweisende nylonteppiche.
EP0639664A1 (fr) * 1993-08-16 1995-02-22 Basf Corporation Fibres de nylon avec solidité au lavage et stabilité thermique améliorées
US6433107B1 (en) * 1995-08-31 2002-08-13 Prisma Fibers, Inc. Fiber-forming polyamide with concentrate of polyamide and sulfonated aromatic acid
US10300415B2 (en) * 2013-03-09 2019-05-28 Donaldson Company, Inc. Fine fibers made from reactive additives
US20140288220A1 (en) * 2013-03-25 2014-09-25 E I Du Pont De Nemours And Company Heat resistant polyamide compositions

Patent Citations (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3236685A (en) 1962-06-20 1966-02-22 Eastman Kodak Co Process for treating textile fibers and other shaped products with coatings
US4863664A (en) 1985-04-22 1989-09-05 Basf Corporation High speed process of making polyamide filaments
US4904408A (en) * 1987-04-03 1990-02-27 Alexander Kud Use of graft polymers based on polyalkylene oxides as grayness inhibitors in the wash and aftertreatment of textile material containing synthetic fibers
US5155178A (en) 1990-08-08 1992-10-13 E. I. Du Pont De Nemours And Company Antistain block copolymer compositions of modified nylon copolymers and high carbon nylons
US5135697A (en) 1990-08-28 1992-08-04 Hoescht Celanese Corporation Polyester copolymer fiber having enhanced strength and dyeability properties
US5272246A (en) 1990-08-28 1993-12-21 Hoechst Celanese Corporation Polyester copolymer fiber having enhanced strength and dyeability properties
EP0785304B1 (fr) 1991-10-21 2000-12-27 Tencel Limited Traitement de fibres filées à partir d'une solution afin de réduire leur tendance à fibriller
WO1993020269A1 (fr) * 1992-04-03 1993-10-14 United States Of America, As Represented By The Se Fibres thermo adaptables modifiees par glyoxal et leur procede de preparation
DE4309436A1 (de) 1993-03-24 1994-09-29 Sandoz Ag Sauer modifizierte synthetishe Polyamide
US5487856A (en) 1993-08-16 1996-01-30 Basf Corporation Process for the manufacture of a post-heat set dyed fabric of polyamide fibers having improved dye washfastness and heat stability
US20030138625A1 (en) * 1995-08-31 2003-07-24 Studholme Matthew Benjamin Stain-resistant polyamide composition and fibers
US5882762A (en) 1996-03-07 1999-03-16 Minnesota Mining And Manufacturing Company Carpet yarn having high soil resistance
WO1997033019A1 (fr) * 1996-03-07 1997-09-12 Minnesota Mining And Manufacturing Company Fil pour moquette ayant une grande resistance aux salissures
US6635346B2 (en) 1997-10-22 2003-10-21 Prisma Fibers, Inc. Stain-resistant polyamide composition and fibers and method of production thereof
US6623853B2 (en) 1998-08-28 2003-09-23 Wellman, Inc. Polyethylene glycol modified polyester fibers and method for making the same
US6610107B1 (en) * 1999-06-28 2003-08-26 Industrial Technology Research Institute Method for modifying fiber surfaces
US6284864B1 (en) 2000-05-31 2001-09-04 Arteva North America S.A.R.L. Permanent deep-dye polyester
US20090149590A1 (en) 2005-09-29 2009-06-11 Nilit Ltd. Modified Polyamides, Uses Thereof and Process for Their Preparation
US8304513B2 (en) 2009-09-02 2012-11-06 E I Du Pont De Nemours And Company Polyesters comprising fluorovinylether functionalized aromatic moieties
US8247519B1 (en) 2011-06-22 2012-08-21 E I Du Pont De Nemours And Company Shaped articles fabricated from polyamides comprising fluoroether functionalized aromatic moieties
US8697831B2 (en) 2011-06-22 2014-04-15 E I Du Pont De Nemours And Company Process for preparing polyamides comprising fluoroether functionalized aromatic moieties
US20130228728A1 (en) 2011-08-31 2013-09-05 Invista North America S.A.R.L. Compositions of polyhydric alcohols and polyamides
CN103757731A (zh) 2013-12-11 2014-04-30 巢湖亚塑网具制造有限公司 一种耐酸碱渔网

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP3145996A4 *

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JP6839983B2 (ja) 2021-03-10
EP3145996A4 (fr) 2018-01-10
AU2015264103A1 (en) 2016-12-08
AU2015264103B2 (en) 2019-02-07
JP2017518445A (ja) 2017-07-06
CA2949532A1 (fr) 2015-11-26
EP3145996A1 (fr) 2017-03-29
CN107001792A (zh) 2017-08-01

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