EP3145996A1 - Polymers with modified surface properties and method of making the same - Google Patents

Abstract

Thermoplastic fibers with an additive that yields modified and/or reactive groups on the surface of the fiber are provided. Also provided are methods for production and articles of manufacture containing these thermoplastic fibers. In addition, methods and products with enhanced soil resistance are provided.

Description

POLYMERS WITH MODIFIED SURFACE PROPERTIES AND METHOD OF

MAKING THE SAME

RELATED APPLICATION

[0001] This application claim priority to U.S. Provisional Application No. 62/001853 filed May 22, 2014.

FIELD OF INVENTION

[0002] 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. In one embodiment, the substrate is a fiber or molded part and the additive is a polyol. When added during the polymer melt state, 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.

BACKGROUND

[0003] 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.

[0004] Various fibers with enhanced dyeing properties have been described. For example, 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. U.S. 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. However 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.

[0005] 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.

[0006] U.S. Published Patent Application No. 2009/0149590 Al, to Eroshov, discloses the use of polyhyd ic alcohols, which are chemically bonded to at least part of a polyamide, to improve wettability and give "a very good surface appearance and excellent mechanical properties". U.S. Published Patent Application No. 2013/0228728 Al, to Mathur, 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. Both of these patent applications focus on molded nylon, not fibers, and neither discusses the addition of molecules on the surface of the article after incorporation of the polyhydric compounds.

[0007] In the industrial production of textiles, such as carpet and apparel, it is common to treat such substrates with a composition to impart added desirable properties such as resistance to the build-up of oily and dry soil. Various fluorochemical compositions and methods for their application have been described for commercial use to impart soil resistance to polymer fiber caipets. For example, U.S. Patent 5,882,762 discloses carpet yarn comprising a plurality of filaments of thermoplastic polymers with a fluorochemical hydrophilicity imparting compound dispersed within the filaments. U.S. Patent 8,247,519 discloses articles fabricated from polyamides and comprising fiuoroether functionalized aromatic moieties with soil and oil resistance. U.S. 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.

[0008] Therefore, there is a need to provide polymeric fibers that have improved or modified surface properties, including built-in soil resistance, reactive surfaces and improved dye uptake or fastness. SUMMARY OF THE INVENTION

[0009] In the present disclosure, 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.

[0010] Accordingly, 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. In one embodiment, the additive is a polyol that yields reactive hydroxyl groups on the surface of a substrate produced from the polymer.

[0011] Another aspect of the present invention relates to a thermoplastic fiber or molded part. The 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. In one embodiment, the additive is a polyol that yields reactive hydroxyl groups on the surface of the fiber or molded part.

[0012] Another aspect of the present invention relates to a 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.

[0013] 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. In one embodiment, the additive is a polyol that yields reactive hydroxyl groups on the surface of the polymer, fiber or molded part.

[0014] 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. In one embodiment, the additive is a polyol that yields reactive hydroxyl groups on the surface of a substrate produced from the polymer. [0015] 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. In one embodiment, the additive is a polyol that yields reactive hydroxyl groups on the surface of the fiber.

[0016] 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, 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.

[0017] Another aspect of the present invention relates to a thermoplastic fiber or molded part comprising a thermoplastic polymer and an additive incorporated with the thermoplastic polymer for enhanced soil resistance.

[0018] Another aspect of the present invention relates to a 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.

[0019] 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. In one embodiment of this method, the additive is a polyol that yields reactive hydroxyl groups on the surface of the fiber or molded part.

[0020] 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.

BRIEF DESCRIPTION OF THE FIGURES

[0021] 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).

[0022] Figure 2 displays images of cross-sections and modification ratios (MR) of fibers spun from nylon 6,6 and various polyols. [0023] 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.

[0024] 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.

[0025] Figure 4 is a plot of chromameter data for carpets with and without DPE dyed at room temperature using Procion® Red MX-5B dye

[0026] 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.

[0027] 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.

[0028] Figure 6 is a plot of chromameter data for carpets with and without DPE dyed at room temperature using Remazol® Brilliant Orange dye

[0029] 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.

[0030] Figure 8 is an image of the soiled and cleaned cut-pile carpets from which the data in Figure 7 was collected.

[0031] 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.

[0032] 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.

[0033] 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. [0034] 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.

[0035] 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.

DETAILED DESCRIPTION OF THE INVENTION

[0036] Provided by the present disclosure are 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.

[0037] Examples of thermoplastic polymers useful in the present invention include polyamides, polyethylenes, polypropylenes, and combinations thereof. In one embodiment, 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. By "combinations thereof with respect to these polymers, it is meant to include, but is not limited to, block copolymers, random copolymers, terpolymers, as well as melt blends. In one embodiment, the thermoplastic polymer is nylon 6,6.

[0038] 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. By "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. In nonlimiting embodiments, 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. As used herein, non-covalent bonding, attachment or association includes dipole-dipole, ion-dipole, or hydrogen bonding interaction. For example, in one nonlimiting embodiment where the substrate is a fiber or molded part, incorporation of a polyol additive during the polymer melt state yields reactive hydroxyl groups on the surface of the fiber or molded part. (0039] Examples of additives useful in the present invention include, but are not limited to, polyols including, but not limited to, pentaerythiitol (MPE), dipentaerythritol (DPE),

tripentaerythritol (TPE), and combinations thereof, as well as 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^!hydroxyethoxy) -hexane-1 ,2-diol, 6-(2'- hydroxypropoxy)hexane- 1 ,2-diol, 1 ,1 ,1 -tris-[(2'-hydroxyethoxy)-methyl] -ethane, 1 ,1 ,1 -tris- [(2'-hydroxypropoxy)-methyl] -propane, 1,1,1 -tris- (4 '-hy droxyphenyl)-ethane, 1,1,1 -tris- (hydroxyphenyl)-propane, 1 ,1 ,3 -tris -(dihydroxy-3 -methylphenyl) -propane, 1 ,1 ,4-tris- (dihydroxyphenyl) -butane, 1, 1 , 5-tris(hydroxyphenyl)-3-methylpentane, di-trimethylopropane, trimethylolpropane ethoxylates, or trimethylolpropane propoxylates;, and saccharides, such as cyclodextrin,D-mannose, glucose, galactose, sucrose, fructose, xylose, arabinose, D-mannitol, D- sorbitol, D-or L-arabitol, xylitol, iditol, talitol, allitol, altritol, guilitol, erythritol, threitol and D- gulonic-y-lactone.

[0040] 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.

[0041] In one nonlimiting embodiment, 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%.

[0042] In one nonlimiting embodiment, the additive included is in an amount greater than about

300 ppm. In another nonlimiting embodiment, the additive included is in an amount greater than about 350 ppm. [0043] In nonlimiting embodiments 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.

[0044] 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.

[0045] In an embodiment of the present disclosure comprising a thermoplastic fiber, 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,

antimicrobials, insect repellents, fragrances and odor eliminators. By incorporating surface hydroxyl groups, targeted covalent attachment or improved non-covalent association is achievable and alternative dyeing processes, through use of reactive dyes, can be achieved. An example of a reactive dye useful in the present invention is disclosed in EP 0 785 304 B 1 , the teachings of which are incorporated by reference herein.

[0046] In another nonlimiting embodiment, 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. In one nonlimiting embodiment, the additive is incorporated in the range of less than about 2% by weight.

[0047] Through experimentation, the applicants discovered that a thermoplastic fiber with built in stain and soil resistance could be formed from embodiments of the current invention. In a nonlimiting embodiment, the thermoplastic fiber has improved stain resistance and the additive modifies the surface of the fiber to impart enhanced soil resistance. In this embodiment, 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. In another embodiment, 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. [0048] Suitable built-in stain blocking additives include those that are known to disable acid dye sites. For examples, in polyamides, such as Nylon 6,6 or Nylon 6, 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. In one nonlimiting, embodiment, 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.

[0049] The 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. In one nonlimting embodiment, 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. 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. In another nonlimting embodiment, 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) and solution dyed fiber. In another nonlimting embodiment, 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) and solution dyed nylon (SDN) fiber.

[0050] The additives described herein may also be incorporated into molded thermoplastics. In this embodiment, 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. [0051] 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.

[0052] In one embodiment of the present invention, the thermoplastic polymer contains no further additional reinforcing materials.

[0053] In an alternative embodiment of the present invention, thermoplastic fibers further comprise an additional reinforcing material or materials. Examples of 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.

[0054] Examples of additional components which may be added to the thermoplastics polymers of this invention include, but are not limited to, TiC% pigments, dye enhancing additives, sulfonated oligomers, lubricants and process modifiers.

[0055] The present invention also provides methods for manufacturing a thermoplastic polymer with a modified and/or reactive surface. In these methods, an additive which yields a modified and/or reactive surface is incorporated with a polymer during the polymer melt state. In one embodiment, the additive is a polyol. In one embodiment, 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.

[0056] 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. In one embodiment, the additive is a polyol. In one embodiment, 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.

[0057] 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. In one embodiment, the additive is a polyol. In one embodiment, 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. In another embodiment, 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.

[0058] Also provided by the present invention are articles of manufacture, at least a portion of which comprises a thermoplastic polymer with a modified and/or reactive surface produced by incorporating an additive which yields a modified and/or reactive surface; a 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; and/or a 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. In one embodiment, the additive is a polyol. In one embodiment, the additive yields or imparts hydroxyl groups and/or hydroxy! functionality on at least a portion of the surface of the article. 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.

[0059] 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. In addition, 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.

[0060] The presence of hydroxyl groups on fibers prepared in accordance with the present invention was verified using Fourier Transform Infrared Spectroscopy (FTIR) analysis and color indicators, specifically reactive dyes. Samples created with the polyamide nylon 6,6 and the polyhydric alcohol DPE exhibited a hydroxylated surface. Further, as evidenced by Figure 1 , carpets with dipentaerythritol (DPE) exhibited greater dye uptake as compared to the control after dyeing with reactive dye, Procion® Red MX-5B. This difference remained after 5 hot water extractions (HWE). Such results were again demonstrated when a new reactive dye type, Remazol® Brilliant Orange, was used (Figure 2). This demonstrates the presence of the hydroxyl groups at the surface as well as the fiber's reactivity with the selected dye. Without being bound by any particular theory, from the SEM images depicted in Figure 6, it is believed that the DPE is migrating or blooming to the surface of the fiber and recrystalizing upon cooling. This behavor explains the rough surface oberserved in the SEM images.

[0061] Melt-extruded single filaments of the thennoplastic and additive of the present invention, produced on a bench-scale microcompounder, were also dyed and some differences were seen between the compounded polymer and drawn filaments as well as between high and low denier filaments. Compounded polymer with and without the additive picked up very little dye. Those materials that were spun into fibers had more dye pick up. The thicker (higher denier fibers) appeared to have only a slight tinting with the dye while finer denier fibers picked up more dye. Without being bound to any specific theory, it is believed that 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.

[0062] The effects of addition of pentaerythritol and tri-pentaerythritol on dye uptake of fibers were also examined. 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.

[0063] In addition, at concentrations as high as 5% additive, no problems or breaks were observed during spinning on a pilot-scale melt-spinning machine. Processing conditions for this material were identical to unmodified nylon and mimic the processing conditions typically used in a manufacturing setting. The 5% concentration was remade using a new masterbatch loaded with 40% DPE and again no processing problems were observed.

[0064] All patents, patent applications, test procedures, priority documents, articles,

publications, manuals, and other documents cited herein are fully incorporated by reference to the extent such disclosure is not inconsistent with this disclosure and for all jurisdictions in which such incorporation is pennitted.

[0065] The following section provides further illustration of thermoplastic polymer

compositions, articles of manufacture and processes of the present invention. Compositions, examined in these nonlimiting examples comprised nylon 6,6 and either MPE, DPE or TPE. Well known by those skilled in the art, however, are other 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. Thus, these working examples are illustrative only and are not intended to limit the scope of the invention in any way.

EXAMPLES

[0066] 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 Charmore™ PM 15. The DPE used is commercially available from

Perstop under the trade name Charmore™ DP 40 and DP 15. The TPE used is commercially available from Sigma Aldrich under the product number 107646.

Example 1: Fiber Production

[0067] 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.

Table 1

After spinning, tubes were analyzed for surface moieties by FITR. Results indicated that the 1037 cm^"1 peak increased with increasing DPE concentrations. In addition, fibers were treated with reactive dyes. MPE and TPE were processed using a bench-scale microcompounder. Both powdered additions of the pure additive and polymer masterbatches of DPE were used. The masterbatch only provided ease of handling, but no additional processing benefits (greater concentrations of actives were not achieved). With MPE and TPE, only powder forms were used. To improve mixing, ½ of the pellets were first fed into the instrument followed by the desired amount of powdered actives, and finally, the remainder of the pellets was 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. Using this approach 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.

Example 2: Spinning of polyol varieties

[0068] 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

tripentaerythrital (TPE), were placed in an aluminum pay and dried in an oven at 50°C for a minimum of 24 hours to remove any excess moisture. 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.

Table 2

Sample 14 DPE 40 1.00%

Samp!e 15 DPE 40 1.50%

*denotes rough estimate. Actual size was not measured but size can be correlated to table salt.

Example 3: Reactive Dyeing of DPE incorporated fibers

[0069] Since reactive dyes are commonly used with cotton and known to react with hydroxyl groups on the article, they can indicate the presence of DPE on the fiber surface.

[0070] 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:

[0071] 166 g of DI H₂0 was placed in a beaker and warmed to (110°F). 18 grams of NaCl was added to the water and mixed until completely dissolved. 833 grams of DI water was then added. Inherently stain-resistant nylon 6,6 carpets were added to the salt water bath for 10 minutes. After 10 minutes the carpets were briefly removed and 0.75 g of Procion® Red MX-5B was added. The dye was dissolved before placing the swabs back into the bath. After 1 hour, 2 grams of sodium bicarbonate was added and stirred to dissolution. Samples were left to sit for 4 hours, then the carpets were removed and rinsed thoroughly with DI water 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, carpets were hot water extracted (HWE) using a Sandia Heated Spotter (3 Gallon, Model # 50-4000). To HWE, Flexiclean® detergent was added to the extractor at a ratio of 4 oz of product per gallon of water. HWE was completed by spraying the sample with detergent followed by a single pass of suction; three sprays and threes suctions were used to represent one HWE cycle. Therefore, 5 HWEs correlates to 15 individual passes of detergent and suction. After each HWE carpets were dried in the oven (60°C for 30 to 90 minutes). Carpets were photographed and LAB values were collected on dry carpets at each step. The a* values, which signifies the red/green colorspace are reported as the average of 3 measurements in Figure 3B. 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 4: Reactive Dyeing of DPE incorporated fibers at Room Temperature

[0072] To ensure that heat was not responsible for the dye uptake, 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

temperature using Procion® Red MX-5B dye.

Example 5: Reactive Dyeing of DPE incorporated fibers

[0073] 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. 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 5B. The a* values for the undyed carpets were 1.80±0.17 for the control and 1.58±0.07 for the 1.5% DPE carpet. Figure 5A shows dried carpets directly after dyeing and rinsing (control carpet, left; 1.5% DPE carpet, right). Figure 5B shows a* values (average of 3 measurements) for carpets with and without DPE using Remazol® Brilliant Orange dye. The a* values for the undyed carpets were 1.80±0.17 for the control and 1.58±0.07 for the 1.5% DPE carpet.

Example 6: Reactive Dyeing of DPE incorporated fibers at Room Temperature

To ensure that heat was not responsible for the dye uptake, 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. 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 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.

Example 7: Anti-soiling properties

[0074] 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. 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. 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.

[0075] Drum soiling data is recorded as Delta E (ΔΕ) and measured according to ASTM D6540, where a lower ΔΕ indicates a smaller difference in the color of the caipet before and after being soiled and vacuumed-clean. Within the reproducibility limitations of this test, 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. According to ASTM D6540, 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, ΔΕ*, and is based on L*, a*, and b* color differences in color space, known to those skilled in the field where

[0076] AE* = V((AL*)² * (Δα*)² * (Δδ^*)²)

[0077] The data, shown for the 2wt% DPE-PA66 carpets in Figures 7, 9, and 10 shows an improvement in soiling repellency, as exemplified by the decrease in ΔΕ of 4-5 units in test items when compared to the appropriate control having 0% DPE. There is also persistence of the effect even after the carpet undergoes hot water extraction (HWE) before being soiled. These carpets have no topical treatments of any kind. Since H WE did not change the performance of the two carpets, the plot in Figure 9 shows the same data but disregards the categorization of whether or not a pre-extraction of surface constituents was attempted before soiling. The 95% confidence intervals are still quite narrow at only 1 and 1.2 ΔΕ from the mean of the 0 and 2wt% DPE blends, respectively.

Example 8: Surface presence of hydroxyls and reduced adhesion of incompatible topical treatments

[0078] 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. 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. Lastly, 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). The presence of surface hydroxyl groups likely makes for pore adhesion of the highly electronegative fluorine dipoles present in the aforementioned anti-soiling treatment with the surface of the fiber, further supporting the claims of the present invention regarding the presence of surface hydroxyls that modify the surface properties of the fiber or molded part and the availability of those groups for targeted reactions. Example 9: Polyol melt-blended into Nylon 7

[0079] In order to show the additive could be spun in other polyamide fibers in accordance with the current invention, a nylon 7 fiber sample was spun. 2% by weight of DPE was melt blended into nylon 7 using a lab-scale twin-screw extruder and a single monofilament was spun and would onto a tube using standard processing conditions. The fiber was able to be spun and did not show any defects that would prevent effective industrial applicability.

Example 10: Anti-soil properties in stain resistant fibers

[0080] 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. The portion of the cross section occupied by the voids was 12% for all items in this example. The subsequent fibers were then processed and tufted into loop-pile carpets. These carpets were then tested using ASTM D6540 for soiling and compared with a control carpet samples and a carpet sample treated with a topical anti-soiling treatment that has a fluorochemical component as a minority ingredient (200 ppm F). Other end-use testing revealed no negative effects on the performance of the carpet as compared to standard nylon 6,6 controls. The results can be seen in Figures 12 and 13. Both Figures show that the carpets of the current invention have equal to or better soiling performance than the carpet treated with topical anti-soiling treatment.

Claims

What is claimed is:

1. A thermoplastic fiber comprising:

a thermoplastic polymer; and

an additive present in the thermoplastic fiber which yields modified and/or reactive groups on the surface of the fiber.

2. The thermoplastic fiber of claim 1 wherein the modified and/or reactive groups on the surface of the fiber comprise hydroxy! groups.

3. The thermoplastic fiber of claim 1 wherein the thermoplastic polymer is selected from a group consisting of polyamide, polyethylene, polypropylene and combinations thereof and/or their copolymers.

4. The thermoplastic fiber of claim 1 wherein the thermoplastic polymer is a polyamide.

5. The thermoplastic fiber of claim 1 wherein the polyamide is nylon 6,6.

6. The thermoplastic fiber of claim 1 wherein the additive is a polyol.

7. The thermoplastic fiber of claim 6 wherein the polyol is selected from the group consisting of pentaerythritol (MPE), dipentaerythritol (DPE), tripentaerythritol (TPE), and combinations thereof.

8. The thermoplastic fiber of claim 1 wherein the additive is incorporated in the range from about 0.03% to about 10% by weight.

9. The thermoplastic fiber of claim 1 further comprising a topical treatment and/or dye chemically or physically associated with the reactive group.

10. The thermoplastic fiber of claim 1 wherein the additive modifies the surface of the fiber to impart enhanced soil resistance.

11. The thermoplastic fiber of claim 1 further comprising a stain blocking additive capable of disabling acid dye sites in the thermoplastic polymer.

12. The thermoplastic fiber of claim 11 wherein the stain blocking additive is present in a range from about 1 to 10 percent by weight.

13. The thermoplastic fiber of claim 11 wherein the stain blocking additive is an aromatic sulfonate or an alkali metal salt thereof.

14. The thennoplastic fiber of claim 11 wherein the fiber has improved stain resistance and the additive modifies the surface of the fiber to impart enhanced soil resistance.

15. The thermoplastic fiber of claim 14 wherein the additive is incorporated in the range of less than about 2% by weight.

16. An article of manufacture, at least a portion of which comprises the thermoplastic fiber of any of claims 1 through 15.

17. The article of manufacture of claim 16 wherein the article is a carpet, rug, or fabric,

18. A method for manufacturing a thermoplastic fiber with a modified and/or reactive surface, said method comprising incoiporating an additive which yields a modified and/or reactive surface with a thermoplastic polymer during the polymer melt state.

19. A method 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.

20. 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.