USOO684933OB1 (12) United States Patent (10) Patent No.: US 6,849,330 B1 Morin et al. (45) Date of Patent: Feb. 1, 2005

(54) FIBERS EXHIBITING 5,811,045 A 9/1998 Pike ...... 264/168 DURABLE HIGH COLOR STRENGTH 5,912.292 A 6/1999 Sun ...... 524/301 CHARACTERISTICS 5,945,215 A 8/1999 Bersted et al...... 428/364 (List continued on next page.) (75) Inventors: Brian Morin, Moore, SC (US); Martin Cowan, Greer, SC (US) FOREIGN PATENT DOCUMENTS (73) Assignee: MillikenOT TO & Company, Spartanburg, SC EP O 806.611 237271 5/19972/1994 (US) JP 11061554. A 3/1999 JP 11140719 5/1999 (*) Notice: Subject to any disclaimer, the term of this JP P2002-302825 R patent is extended or adjusted under 35 WO O2/46502 6/2002 U.S.C. 154(b) by 0 days. OTHER PUBLICATIONS (21) Appl. No.: 10/651,777 Patent abstracts of Japan; publication No. 11-061554; date 1-1. of publication of application Mar. 5, 1999; Highly heat-re (22) Filed: Aug. 30, 2003 Sistant fiber; English translation. (51) Int. Cl...... D01F6/00; CO8J 0/00; (List continued on next page.) CO8L O/OO Primary Examiner N. Edwards (74) Attorney, Agent, or Firm Terry T. Moyer; John E. (52) U.S. Cl...... 428/364; 428/372; 428/394; Vick, Jr. 524/242; 524/387 (58) Field of Search ...... 524/242,387; (57) ABSTRACT 552/259; 428/364, 395,372, 394 Improvements in permitting brighter colorations within (56) References Cited polypropylene fibers and/or yarns while Simultaneously pro Viding more efficient production methods of manufacturing U.S. PATENT DOCUMENTS of such colored fibers as well are provided. Generally, such fibers and/or yarns have been colored with pigments, which 4,016,118 A 4/1977 Hamada et al...... 524/108 4,116,626 A 9/1978 Varner ...... 4/149 exhibit dulled results, or dyes, which exhibit high degrees of 4,132,817 A 1/1979 Tillotson . ... 427/244 extraction and low levels of lightfastness. Such dull 4,171,395 A 10/1979 Tollotson ...... 428/95 appearances, high extraction levels, and less than Stellar 4,463,113 A 7/1984 NaKahara et al. ... 524/117 lightfastness properties negatively impact the provision of 4,512.831. A 4/1985 Tillotson ...... 156/78 Such desirable colored polypropylene fibers and/or yarns 4,522,857 A 6/1985 Higgins ...... 428/95 which, in turn, prevents the widespread utilization of Such 4,560,734 A 12/1985 Fujishita et al...... 526/142 fibers and yarns in various end-use applications. Thus, it has 5,049,605 A 9/1991 Rekers ...... 524/108 Surprisingly been determined that brighter colorations, 5,136.520 A 8/1992 Cox ...... 364/470 excellent extraction, and more-than-acceptable lightfastneSS 5,208,592 A 5/1993 Johnson, Jr...... 341/63 5,231,126 A 7/1993 Shi et al...... 524/296 characteristics can be provided, preferably, through manu 5,342,868 A 8/1994 Kimura et al...... 524/108 facture with certain polymeric colorants that include poly 5,512.357 A 4/1996 Shimura et al...... 428/283 (oxyalkylene) groups thereon. Fabric articles comprising 5,540,968 A 7/1996 Higgins ...... 428/95 Such novel fibers and/or yarns are also encompassed within 5,545,276 A 8/1996 Higgins ...... 156/79 this invention. 5,753,736 A 5/1998 Bhat ...... 524/287 5,798,167 A 8/1998 Connor et al...... 428/171 51 Claims, 5 Drawing Sheets

10K US 6,849,330 B1 Page 2

U.S. PATENT DOCUMENTS OTHER PUBLICATIONS 5.948,500 A 9/1999 Higgins ...... 428/95 Patent abstracts of Japan; publication No. 11-181619; date 6,102.999 A 8/2000 Cobb, III et al. ... 106/243 of publication of application Jul. 6, 1999; Highly heat-re 6110.588 A 8/2OOO P 428/359 p pp ghly 6,127.440 A 838 S. al...... /74 Sistant polypropylene fiber and fiber-reinforced cement 6127.470 A 10/2000 Cobb, III et al. ... 524/367 molded product using the same; English translation. 6,135.987. A 10/2000 Tsai et al...... 604/365 Patent abstracts of Japan; publication No. 2001-081628; 6,162,887. A 12/2000 Yamada et al. . ... 526/351 date of publication Mar. 27, 2001; Flat yarn for base cloth of 6,203,881 B1 3/2001 Higgins ...... 428/95 needle-pouched carpel; English translation. E. R 3. Nine t al. - - - 33. Patent abstracts of Japan; publication No. 2002-302825; 621so11 B1 2: Rhia. O. 3. date of publication Oct. 18, 2002; Hihgly-resistant polypro 6,231976 B1 5/2001 Dean et al...... 257, pylene fiers, English translation. 6,238,615 B1 5/2001 Kobayashi et al...... 264/537 Article; Journal of applied Science, Vol. 62, 6,261,677 B1 7/2001 Tsai et al...... 428/221 1965–1975 (1996) John Wiley & Sons, Inc.; Spruiell et al. 6,270,608 B1 8/2001 Vair, Jr. et al...... 156/176 Article; The effects of pigments on the development of R 18.28; E. et al ------32. Structure and properties of polypropylene filaments: Antec 2- Y-Y-2 f ayama et al...... f 91; Lin et al. 6,358,450 B1 3/2002 Sun ...... 264/178 - 6,420,024 B1 7/2002 Perez et al. ... 428/359 Article; The role of crystallization kinetics in the develop 6,468,623 B1 10/2002 Higgins ...... 428/95 ment of the Structure and properties of polypropylene fila 6,528,564 B1 3/2003 Xia ...... 524/242 ments; (C) 1993 John Wiley & Sons, Inc.; CCC 0021-8995/ 6,534,574 B1 3/2003 Zhao et al...... 524/284 93/040623-9. 5. R 2. yer et al - - - 5. Article; Study on the formation of b-crystalline form iso 6550216 B1 3. 7N, N. ------522. tactic polypropylene fiber; fiber and films, Intern, Polymer 6,593,483 B2 * 7/2003 Xia ...... 552/259 Processing VI, 1991; Chen et al 6,656.404 B2 12/2003 Morin et al..... 264/210.5 Article: Heterogeneous Nucleation of Polypropylene and

2001/0040320 A1 11/2001 Kobayashi et al...... 264/537 Polpropylene Fibers; Marcincin et al., 1994. 2001/0048179 A1 12/2001 Stewart et al...... 264/211 2002/0002241 A1 1/2002 Raetzsch et al...... 123/556 * cited by examiner U.S. Patent Feb. 1, 2005 Sheet 1 of 5 US 6,849,330 B1

09 U.S. Patent Feb. 1, 2005 Sheet 2 of 5 US 6,849,330 B1 U.S. Patent Feb. 1, 2005 Sheet 3 of 5 US 6,849,330 B1 U.S. Patent Feb. 1, 2005 Sheet 4 of 5 US 6,849,330 B1

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U.S. Patent Feb. 1, 2005 Sheet 5 of 5 US 6,849,330 B1

US 6,849,330 B1 1 2 THERMOPLASTIC FIBERS EXHIBITING instance, there has been a continued desire to utilize low DURABLE HIGH COLOR STRENGTH denier polypropylene fibers in various different products, CHARACTERISTICS Such as apparel (due to highly effective Soft hand properties), and the like. Polyolefin fibers exhibit excellent strength characteristics, highly desirable hand and feel, and do not FIELD OF THE INVENTION easily degrade or erode when exposed to certain “destruc This invention relates to improvements in permitting tive” chemicals. However, even with such impressive and brighter colorations within thermoplastic fibers and/or yarns beneficial properties and an abundance of polyolefin (Such while Simultaneously providing more efficient production as polypropylene, , and the like), which is methods of manufacturing of Such colored fibers as well. relatively inexpensive to manufacture and readily available Generally, such fibers and/or yarns have been colored with as a petroleum refinery byproduct, Such fibers are not widely pigments, which exhibit dulled results, or dyes, which utilized in products that require fiber and/or yarn colorations exhibit high degrees of extraction and low levels of light therein. Specifically, although (such as polyeth fastness. Such dull appearances, high extraction levels, and ylene terephthalate, or PET) and (Such as less than Stellar lightfastness properties negatively impact 15 nylons) are generally more expensive to manufacture, Such the provision of Such desirable colored thermoplastic (Such fibers do not exhibit the same unacceptable color disadvan as, without limitation, polypropylene) fibers and/or yarns tages inherent within polyolefins. This is due in large part to which, in turn, prevents the widespread utilization of Such the difficulties inherent in providing sufficiently bright col fibers and yarns in various end-use applications. Thus, it has orations within Such target polyolefin fibers and/or yarns in Surprisingly been determined that brighter colorations, general. Thus, it is imperative to provide remedies to Such excellent extraction, and more-than-acceptable lightfastneSS issues to permit utilization of Such lower cost polymer characteristics can be provided through manufacture with materials in greater varieties of end-uses. certain polymeric colorants that include poly(oxyalklene) Pigments, the most prevalent of polyolefin fiber colorants groups thereon. Fabric articles comprising Such novel ther utilized throughout the fabric industry, as noted above, are, moplastic fibers and/or yarns are also encompassed within 25 as is well-known, Solid particles that require a relatively high this invention. amount to provide Sufficiently deep colorations within Such target materials. Because Such pigments exhibit colorations DISCUSSION OF THE PRIOR ART within the discrete areas in which they are actually present, All U.S. patents cited below are herein entirely incorpo complete pigment presence is required to fully color Such rated by reference. target fibers and/or yarns. If certain discrete areas of Such Thermoplastic fibers have been utilized many years for target materials do not include any or insufficient amounts of myriad different fabric and textile applications. In particular, pigments, streaks, uneven colorations, and other aestheti polyolefin, , and fibers have been promi cally displeasing results will most likely result. Hence, nent as replacements for naturally occurring fibers (such as proper color provision via pigment presence within poly cotton and wool, for instance) due to lower costs, more 35 olefin fibers and/or yarns requires large amounts of Such reliability in Supply, physical properties, and other like Solid particles to accord the needed level of colorations benefits. Colorations have been available for Such therein. However, with Such a large amount of pigment thermoplastic, Synthetic fibers in order to provide aesthetic, present within Such target fibers and/or yarns comes an identification, and other properties. Such colorations have inevitable dull appearance as well. Without intending to be been mostly provided through pigments that thoroughly 40 limited to any Specific Scientific theory, it has now been color the target fibers and exhibit sufficiently high lightfast hypothesized by the inventors that Such a dull appearance is neSS and crocking characteristics that use thereof has not attributable to the lack of transparency through the target been curtailed. Dyeing within baths is available for already fiber and/or yarn within which Such pigments are added. The formed fabrics (such as knit, woven, and/or non-woven Solid nature of Such pigment particles basically appears to textiles), if a Solid color is desired, and also for yarns with 45 fill the entire fiber and/or yarn to the extent that light cannot Selected properties through package dyeing procedures. pass through easily. Thus, the visible color provided by the However, accent yarns or other fibers that require individual fiber and/or yarn is limited to that portion of the scattered colorations requires coloring during production. In addition, light that is reflected back to the viewer alone. AS Such, the Some Such as polypropylene, polyethylene, etc., color appears dull to the eye thereby compromising the have not been heretofore able to accept dyes of any kind, and 50 resultant brightness effect of the fiber, and the ultimate fabric have thus been colored with pigment. Thus, although Such within which such a fiber is incorporated. Thus, there exists pigment colorants are prevalent and generally effective at the need to provide a distinct improvement on dullness providing color within Such thermoplastic fibers, there are (brightness) in this type of situation in order to permit certain drawbacks for which improvements have been utilization of more brightly colored polyolefin fibers and/or unavailable. For example, pigments are notoriously capable 55 yarns in order to permit, in turn, more aesthetically pleasing of Staining fiber manufacturing/extrusion machinery Such fabric articles from a coloration perspective. Furthermore, that control of discolorations within Subsequently produced and just as important, Such pigments are extremely difficult fibers is rather difficult, and the time required to change to purge from within manufacturing machinery, particularly colorS is high. Also, pigments impart a dulling appearance, within fiber extrusion units, Such that once a new color is a lack of brightness, and a low luster, all believed to be due 60 desired for target fiber materials, extensive purging is to the Solid nature of Such coloring agents. In addition, required for proper cleaning. Such cleaning is generally pigment Size and dispersion limits the processability of quite extensive and complicated Since a Small amount of small fibers, which are desirable for their improved touch residual pigment anywhere within the machinery can dis and feel. Thus, improvements in Such areas are desirable for color any amount of extruded fiber therein. Thus, utilization coloring agents to be introduced within thermoplastic fibers. 65 of either potentially harmful Solvents, in-depth and invasive In particular, it has been found that improvements in cleaning procedures throughout the entire unit, and/or coloring individual polyolefin fibers are needed. For wasteful flushing processes that also potentially result in US 6,849,330 B1 3 4 pigment effluent production within wastewater, and the example) fibers and/or yarns that exhibit extremely bright norm rather than the exception for pigment-colored polypro and aesthetically pleasing colorations as compared to pig pylene methods. mented products. A further object of the invention is to Dyes have also been utilized to color not only polyolefin provide Such colorations that are of very low, if nonexistent, extraction. A further object of the invention is to provide a fibers and/or yarns, but also materials. Such as nylon, specific method for the production of brightly colored ther polyesters, cotton, and other fiber types. AS noted above, in moplastic fibers that permits quick and efficient changeover general, polyolefins are an economically Superior fiber as from one colorant to another. Additionally, another object of compared with other Synthetic types (polyesters, nylons, for this invention is to provide a brightly colored thermoplastic example); however, its widespread use has been limited due fiber and/or yarn that exhibits outstanding lightfastness to Such issueS as this coloration problem. Thus, although properties, either alone or in the presence of minimal dyes have provided bright colorations in these other types of amounts of UV absorber additives. Another object of the fibers, extraction and lightfastneSS issues have, again, invention is to provide a process for manufacturing fibers Severely limited utilization of Such coloring agents within using liquid colors in which the shade can be adjusted to polyolefins. In essence, Such Soluble coloring agents do not match Some Standard. react readily within polyolefin without exhibiting migration 15 Accordingly, this invention encompasses a colored ther and extraction over time. Polyesters and nylons, as moplastic fiber compromising a liquid colorant present examples, include reactive groups that permit reaction therein in a rod-like configuration. Furthermore, this inven therein with dyes (Sulfonated types, for example) and which tion encompasses a colored thermoplastic fiber including at in turn do not exhibit appreciable extraction as a result. least one liquid colorant therein, wherein Said at least one Within polyolefins, to the contrary, extraction levels are liquid colorant therein exhibits a very low extraction and quite high for Such dyes and thus unevenneSS in color, crocking level there from. Additionally, this invention Streaking, if not complete loSS in color, are typical results. encompasses a method of producing a colored thermoplastic This problem is further amplified when fabrics made there fiber including the steps of a) providing a molten thermo from Such dyed polyolefins are Subjected to laundering formulation, optionally including colored thermo treatments. Lightfastness (the ability of the target fibers 25 plastic concentrates therein, wherein Said concentrates com and/or yarns to retain their desired color levels, if not colors prise at least one liquid polymeric colorant; and b) extruding at all) are generally unacceptable as well when dyes are said thermoplastic formulation of step “a” within a fiber utilized without having excessive amounts of protecting extrusion line to form a colored thermoplastic fiber, wherein, agents (UV absorbers, for example) added in addition. optionally at least one liquid polymeric colorant is Simulta Furthermore, the same machinery staining issues and poten neously injected within Said fiber extrusion line during tial wastewater problems are present with dyes as well, extrusion of Said thermoplastic formulation of Step “a”, and. albeit to a lesser degree because of the liquid nature of Such Optionally, this process has the additional steps of providing coloring agents. In any event, a certain degree of difficulty multiple liquid color constituents in step “a” or “b”, match Still exists within liquid dye processing within polyolefin ing the resulting fibers to a Standard, and adjusting the ratio fiber and/or yarn manufacturing (extruding, for example) 35 of the multiple liquid color constituents So provided to adjust due to Such staining characteristics. Thus, as for pigments the color of the resulting fiber to match the standard. This above, efficiency is compromised during fiber manufacture invention also encompasses the formation of a colored film Such that any cost benefits of utilizing polyolefin as com including Such liquid polymeric colorants, and the formation pared with other Synthetic fiber and/or yarn types are of colored tape fibers therefrom. reduced to a level that is unacceptable for displacement 40 As used herein, the term “thermoplastic' is intended to within the fabric industry. mean a polymeric material that will melt upon exposure to In addition, with pigment coloring of fibers, the pigments sufficient heat but will retain its solidified state, but not prior are normally matched to a Standard shade in a high concen shape without use of a mold or like article, upon Sufficient tration that is then diluted with uncolored cooling. Specifically, as well, Such a term is intended Solely polymer during the fiber manufacture. AS Such, if there is a 45 to encompass polymers meeting Such a broad definition that problem or mismatch between the color masterbatch, there also exhibit either crystalline or Semi-crystalline morphol is only limited adjustment available at the fiber manufac ogy upon cooling after melt-formation through the use of the turing Stage. This often necessitates re-manufacture of the aforementioned mold or like article. For this invention, masterbatch, adding expense and delaying the manufactur however, the thermoplastic is to be utilized to from fibers ing process. 50 and/or yarns through any number of techniques, including, without limitation, extrusion (for multifilament and All in all, it is evident that polyolefin has suffered from monofilament types), Spinning, water- and/or air-quenching, coloring limitations in the past Such that displacement of spun-bonded and/or melt-blown non-woven products, Staple more expensive fiber types has not been forthcoming and fibers, bicomponent/splittalbe fibers, tape and/or ribbon that the Standard coloring agents utilized today have neither 55 fibers (through slit film procedures, as one example), and the imparted the necessary brightness, extraction levels, light like. Particular types of polymers contemplated within Such fastneSS properties, and low Staining characteristics that a definition include, without limitation, polyolefins (such as appear to be the main obstacles to more widespread use of polyethylene, polypropylene, , and any combi colored polypropylene fibers within the fabric industry. To nation thereof), polyamides (such as nylon), , date, there Simply has not been any coloring agent that has 60 polyesters (Such as polyethylene terephthalate), polylactic accorded necessary bright colorations, excellent low (if not acids, and any copolymers of these broad types, either nonexistent) extraction levels, and Superior lightfastness within the same classification or not. Polypropylene fibers results within the polypropylene fiber and/or yarn industry. are most preferred, although polyesters are preferred as well. DESCRIPTION OF THE INVENTION The particular polypropylene fiber and/or yarn of this inven 65 tion may be of any denier, including microdeniers (below It is thus an object of the invention to provide thermo about 1.5 denier per fiber) or higher deniers 1.5 denier per plastic (Such as polypropylene, as one non-limiting fiber or higher), as merely examples. US 6,849,330 B1 S 6 The target fibers and/or yarns may also be textured in any The preferred colorants in this general class are repre manner commonly followed for polypropylene materials. sented by the following formula (1): One example of this is false-twist texturing, in which a twist is imparted to the fiber through the use of Spindles, and while R{A(B), (I) the fiber is in the twisted State it is heated and then cooled wherein to impart into the individual filaments a memory of the R is an organic chromophore; twisted state. The yarn is then untwisted, but retains bulk due A is a linking moiety in Said chromophore Selected to the imparted memory. In another texturing embodiment, from the group consisting of N, O, S, SON, and known as bulked continuous filament (BCF), the yarn is CO; pushed with air jets into a stuffer box where it is crowded in B is an alkyleneoxy constituent contains from 2 to 4 a non-uniform state with other fibers and heated to retain the carbon atoms, memory of this non-uniform State. The yarn is then cooled, n is an integer of from 2 to about 500; but again retains bulk due to the imparted memory. Of m is 1 when A is O, S, or CO, and m is 2 when A is course, other texturing methods, Such as air texturing, gear N or SON; and texturing, and the like, may be used. 15 X is an integer of from 1 to about 5. The term “polypropylene' is intended to encompass any The molecular weight of such colorants are at least 2000 polymeric composition comprising propylene , and, due to the high oxyalkylenation present, are highly either alone or in mixture or copolymer with other randomly water Soluble and liquid at room temperature. The organic Selected and oriented polyolefins, dienes, or other monomers chromophore is, more Specifically, one or more of the (Such as ethylene, butylene, and the like). Such a term also following types of compounds: azo, diazo, disazo, trisazo, encompasses any different configuration and arrangement of diphenylmethane, triphenylmethane, Xanthene, nitro, the constituent monomers (such as Syndiotactic, isotactic, nitroso, acridine, methine, Styryl, indamine, thiazole, and the like). Thus, the term as applied to fibers is intended oxazine, Stilbene, or anthraquinone. In an alternative to encompass actual long Strands, tapes, threads, and the embodiment, the chromophore may be optically inactive, at like, of drawn polymer. The polypropylene may be of any 25 least within the visible spectrum, but absorb uv radiation, as standard melt flow (by testing); however, standard fiber one example, thereby imparting ultraViolet protection to the grade polypropylene resins possess ranges of Melt Flow target fiberS. Preferably, R is one or more of azo, diazo, Indices between about 1 and 1000. triphenylmethane, methine, anthraquinone, or thiazole based Contrary to Standard manufacturing procedures and tech compounds. Such a group may produce coloring effects that niques for plaques, containers, sheets, and the like (Such as are evident to the eye; however, optical brightening chro taught within U.S. Pat. No. 4,016,118 to Hamada et al., for mophores are also contemplated in this respect. Group A is example), fibers clearly differ in structure since they must present on group R and is utilized to attach the polyoxy exhibit a length that far exceeds its cross-sectional area alkylene constituent to the organic chromophore. Nitrogen is (Such, for example, its diameter for round fibers). Fibers are the preferred linking moiety. The polyoxyalkylene group is extruded and drawn; articles are blow-molded or injection generally a combination of ethylene oxide and propylene molded, to name two alternative production methods. Also, 35 oxide monomers. Preferably propylene oxide is present in the crystalline morphology of polypropylene within fibers is the major amount, and most preferably the entire polyoxy different than that of Standard articles, plaques, sheets, and alkylene constituent is propylene oxide. the like. For instance, the dpf of Such polypropylene fibers The preferred number of moles (n) of polyoxyalkylene is at most about 5000; whereas the dpf of these other articles constituent per polyoxyalkylene chain is from 2 to 50, more is much greater. Polypropylene articles generally exhibit 40 preferably from 10 to 30. Also, preferably two such poly Spherulitic crystals while fibers exhibit elongated, extended meric chains are present on each polymeric colorant com crystal Structures. Thus, there is a great difference in Struc pound (X, above, is preferably 2). In actuality, the number of ture between fibers and polypropylene articles Such that any moles (n) per polymeric chain is an average of the total predictions made for spherulitic particles (crystals) of col number present since it is very difficult to control the ored polypropylene articles do not provide any basis for 45 addition of Specific numbers of moles of alkyleneoxy determining the effectiveness of coloring agents as additives groups. The Table below lists the particularly preferred within polypropylene fibers. For instance, plaques made with pigments can exhibit bright, deep Shades, and Still colorants (with the range of alkoxylation present on the appear transparent in fiber form, dullness (low brightness) colorant listed due to the inexactness of production of and opacity are prominent when deep shades of pigmented Specific chain lengths) for utilization in relation to Structure fibers are produced. Thus, the Significant differences in form 50 (I), above: and structure between sheet-like articles and fibers (and/or yarns) of the same thermoplastic, make it difficult to predict how effective a specific coloring agent may perform within COLORANT TABLE one through knowledge of the other. Preferred Poly(oxyalkylenated) Colorants The coloring agents particularly useful within this inven 55 tion are those that are liquid in nature, preferably, though not Col. # R A B(with moles) m x Color necessarily, polymeric in nature i.e., poly(oxyalkylenated) 1. Methine N 6-8 EO; 12-15 PO 2 1 Yellow to the extent that, upon introduction within Such target 2 Benzothiazole N 6-8 EO; 10-12 PO 2 1 Red polypropylene fibers, extraction therefrom is Severely diazo limited, if not nonexistent. The term “liquid” is intended to 60 3 Triphenylmethane N 2-4 EO; 12-15 PO 2 2 Cyan mean that Such colorants are liquid at room temperature and 4 Aminothiophene N 0-12 EO; 12-15 PO 2 1 Violet Standard pressure (25 C. at 1 atmosphere). Example colo Diazo rants that meet these limitations (and thus are defined by the 5 Phenyl Diazo N 8-10 EO; 10-12 PO 2 2 Orange term “liquid polymeric colorants' herein) are those that are available from Milliken & Company under the tradename 65 Such colorants provide the aforementioned, highly CLEARTINT(R). Alternatively, liquid dyestuffs may also be desirable, low extraction properties, as well as the significant utilized, although less preferred than polymeric types. bright colorations as compared with pigmented fibers. US 6,849,330 B1 7 8 Without intending on being limited to any Specific Scien greater efficiency in fiber and/or yarn manufacturing. tific theory, it appears that Such colorants are capable of Generally, these compounds include any structure that complete introduction within the target polypropylene fibers nucleateS polymer crystals within the target polypropylene to the extent that transparent thin rod-like configurations of after exposure to Sufficient heat to melt the initial pelletized the liquid colorants are present within the fibers after eXtru 5 polymer and upon allowing Such a melt to cool. The Sion. Such configurations thus permit an even distribution of compounds must nucleate polymer crystals at a higher color throughout the target fiber, and, apparently, with a temperature than the target polypropylene without the nucle ating agent during cooling. In Such a manner, the nucleator Strong cohesive nature while present therein Said fibers, Such compounds provide nucleation sites for polypropylene crys thin rod-like configurations are not amenable to easy migra tal growth which, in turn, appear to provide thick lamellae tion from therein either. In other words, although small within the fibers themselves which, apparently (without openings may exist within and/or at the Surface of Such intending on being bound to any specific Scientific theory) extruded polypropylene fibers, the rod-like configurations of increase the processability of the target fibers to Such a the colorants therein do not break, but appear to keep there degree that the tensions associated with high-speed spinning rod-like appearance and the liquid colorant thus does not can easily be withstood. The preferred nucleating com migrate or escape through Such Surface openings, even if 15 pounds include dibenzylidene Sorbitol based compounds, as Such fibers come into contact with adhesive Surfaces them well as leSS preferred compounds, Such as Sodium benzoate, Selves. Such a physical appearance is shown within the certain Sodium and lithium phosphate Salts (such as Sodium drawings discussed below. In essence, empirically the liquid 2,2'-methylene-bis-(4,6-di-tert-butylphenyl)phosphate, oth colorants (polymerics, preferably, although possible liquid erwise known as NA-11 or NA-21), Zinc glycerolate, and dyestuffs may function similarly) will appear as long Strands others. Sodium benzoate, in general, is not preferred because of color within extruded fibers if the methods of producing it is known to outgas corrosive benzoic acid, among other disclosed herein are employed when Viewed at proper mag deficiencies. Also, the amount of nucleating agent present nifications (such as from 300 to 1000x; proper viewing may within the inventive fiber is at least 10 ppm; preferably this be seen most readily between 500 and 600x). Cross amount is at least 100 ppm, and most preferably is at least Sectionally, Such long Strands will appear as Small dots 25 1250 ppm. Any amount of Such a nucleating agent should within the target fibers. These dots will be the tops of these Suffice to provide the desired shrinkage rates after heat rod-like structures which can then be noticed from side Setting of the fiber itself; however, excessive amounts (e.g., ViewS as the aforementioned Strands. Thus, Since these above about 10,000 ppm and even as low as about 6,000 Strands are basically pools of liquid color Stretched during ppm) should be avoided, primarily due to costs, but also due the fiber extrusion process, these structures will exhibit to potential processing problems with greater amounts of aspect ratios (length to diameter) of from 10:1 to 500,000:1, additives present within the target fibers. preferably from 50:1 to 100,000:1, more preferably from Another potentially preferred class of nucleators Suitable 50:1 to 10,000:1, and most preferably from 100:1 to 1,000:1. for incorporation within the inventive colored fibers include Thus, the term rod-like is intended to encompass these high Saturated metal or organic Salts of bicyclic dicarboxylates, aspect ratio Strands of liquid color within target thermoplas 35 preferably Saturated metal or organic Salts of bicyclic tic fibers. Since the thermoplastic will be colorless, or at dicarboxylates, preferably, bicyclo2.2.1]heptane least sufficiently different in color from the added liquid dicarboxylates, or, generally, compounds conforming to coloring agent, it is relatively easy to view Such rod-like Structures through Side ViewS coupled with cross-sectional Formula (I) ViewS. Again, the continuous Strands of color or easily 40 viewed from the side; the “dots” of tops of different strands (I) are easily viewed in cross-section. This rod-like configuration also provides effective and even colorations throughout Such target fibers because of the ability of light to pass through Such fibers and transparent 45 film-like Structures Simultaneously. Thus, light is transmitted through such fibers as well as absorbed by the colorants therein due to the transparent appearance of the resultant fiber. The resultant appearance is, unexpectedly, very bright in nature, much more So, for example, than the empirical 50 wherein R, R2, R, R, Rs, R, R-7, Rs, Ro, and Rio are appearance of the above discussed pigmented fibers that individually Selected from the group consisting of hydrogen, require a large amount of Solid particles therein to provide C-C alkyl, hydroxy, C-Co alkoxy, C-C alkyleneoxy, even colorations throughout, but which, as a result, also amine, and C-C alkylamine, halogen, phenyl, alkylphenyl, exhibit very dull appearances as well. The colored transpar and geminal or vicinal carbocyclic having up to nine carbon ent nature available with these inventive liquid colorants 55 atoms, R' and R" are the same or different and are individu produces the bright colorations, much like a colored filter ally Selected from the group consisting of hydrogen, C-Co placed over a light imparts a bright, colored effect when the alkyl, hydroxy, amine, polyamine, polyoxyamine, C-Co light Shines therethrough. The fibers themselves are gener alkylamine, phenyl, halogen, C-Co alkoxy, C-Co ally Solid in nature, and, cross-sectionally, appear as round, polyoxyalkyl, C(O)-NRC(O)O-R", and C(O)O-R", triangular, Square, and/or rectangular in shape, but may have 60 wherein R is selected from the group consisting of C-Co any croSS Sectional shape, Such as octalobal which is popular alkyl, hydrogen, C-Co alkoxy, and C-C polyoxyalkyl, in carpet fibers. and wherein R" is Selected from the group consisting of Such fibers (or yarns comprising Such fibers) may also hydrogen, a metal ion (Such as, without limitation, Na', K", include the presence of certain compounds that quickly and Li, Ag" and any other monovalent ions), an organic cation effectively provide rigidity and/or tensile Strength to the 65 (Such as ammonium as one non-limiting example), polyoxy target polypropylene fiber to a level heretofore unavailable, C-Cls-alkylene, C-C so alkyl, C-Cso alkylene, C-Co particularly in terms of permitting high-Speed Spinning for alkyleneoxy, a steroid moiety (for example, cholesterol), US 6,849,330 B1 9 10 phenyl, polyphenyl, C-C alkylhalide, and C Co alky dibenzylidene sorbitol (DBS), monomethyldibenzylidene lamine; wherein at least one of R' and R" is either C(O)- sorbitol, such as 1,3:2,4-bis(p-methylbenzylidene) Sorbitol NRC(O)O-R" or C(O)O-R", wherein if both R" and R" (p-MDBS), dimethyl dibenzylidene Sorbitol, such as 1,3:2, are C(O)OR" then R" both R' and R" may be combined into 4-bis(3,4-dimethylbenzylidene) sorbitol (3,4-DMDBS); a single bivalent metalion (such as Ca", as one non-limiting other compounds of this type include, again, without example) or a single trivalent metal overbase (such as limitation, sodium benzoate, NA-11, NA-21, bicyclic dicar Al-OH, for one non-limiting example). Preferably, R' and boxylate Salts, and the like. The concentration of Such R" are the same and R" is either Na' or combined together nucleating agents (in total) within the target polypropylene for both R" and R" and Cat". Other possible compounds are fiber is at least 100 ppm, preferably at least 1250 ppm. Thus, discussed in the preferred embodiment Section below. from about 100 to about 5000 ppm, preferably from about Preferably, as noted above, Such a compound conforms to 500 ppm to about 4000 ppm, more preferably from about the structure of Formula (II) 1000 ppm to about 3500 ppm, still more preferably from about 1500 ppm to about 3000 ppm, even more preferably

(II) from about 2000 ppm to about 3000 ppm, and most pref 15 erably from about 2500 to about 3000 ppm. Also, without being limited by any Specific Scientific theory, it appears that the potential, but not required, nuclea tors which perform the best are those which exhibit rela tively high solubility within the propylene itself. Thus, compounds which are readily Soluble, Such as 1,3:2,4-bis (p-methylbenzylidene) Sorbitol provides the lowest shrink age rate for the desired polypropylene fibers. The DBS derivative compounds are considered the best Shrink wherein M and M are the same or different and are reducing nucleators within this invention due to the low independently Selected from the group consisting of metal or 25 crystalline sizes produced by Such compounds. Other organic cations or the two metal ions are unified into a single nucleators, Such as NA-11, also impart acceptable charac metal ion (bivalent, for instance, Such as calcium, for teristics to the target polypropylene fiber in terms of, for example), and R, R2, R3, R1, RS, R, R-7, Rs, Ro, and Rio example, withstanding high Speed spinning tensions, are individually Selected from the group consisting of however, apparently due to poor dispersion of NA-11 in hydrogen, C-C alkyl, hydroxy, C-C alkoxy, C-Co polypropylene and the large and varied crystal sizes of alkyleneoxy, amine, and C-Co alkylamine, halogen, NA-11 within the fiber itself, the performance is less con phenyl, alkylphenyl, and geminal or vicinal carbocyclic sistent than for the highly soluble, low crystal-size polypro having up to 9 carbon atoms. Preferably, the metal cations pylene produced by well-dispersed 3,4-DMDBS or, are Selected from the group consisting of calcium, Strontium, preferably, P-MDBS. barium, magnesium, aluminum, Silver, Sodium, lithium, 35 It has been determined that the nucleator compounds that rubidium, potassium, and the like. Within that Scope, group exhibit good Solubility in the target molten polypropylene I and group II metal ions are generally preferred. Among the resins (and thus are liquid in nature during that Stage in the group I and II cations, Sodium, potassium, calcium and fiber-production process) provide more effective fiber prop Strontium are preferred, wherein Sodium and calcium are erties for withstanding high Speed Spinning tension levels. most preferred. Furthermore, the M and M groups may 40 Thus, Substituted DBS compounds (including DBS, 3,4- also be combined to form a single metal cation (Such as DMDBS, and, preferably P-MDBS) appear to provide fewer calcium, Strontium, barium, magnesium, aluminum, includ manufacturing issueS as well as lower shrink properties ing monobasic aluminum, and the like). Although this within the finished polypropylene fibers themselves. invention encompasses all Stereochemical configurations of Although 3,4-DMDBS is preferred for Such low denier Such compounds, the cis configuration is preferred wherein 45 fibers, any of the above-mentioned nucleators may be uti cis-endo is the most preferred embodiment. The preferred lized within this invention. Mixtures of such nucleators may embodiment polyolefin articles and additive compositions also be used during processing in order to provide Such for polyolefin formulations comprising at least one of Such Spinning efficiencies and low-shrink properties as well as compounds, broadly Stated as Saturated bicyclic carboxylate possible organoleptic improvements, facilitation of Salts, are also encompassed within this invention. 50 processing, or cost. AS they apply to this invention, then, the terms In addition to those compounds noted above, Sodium “nucleators”, “nucleator compound(s)”, “nucleating agent', benzoate and NA-11 are well known as nucleating agents for and “nucleating agents' are intended to generally Standard polypropylene compositions (Such as the afore encompass, Singularly or in combination, any additive to mentioned plaques, containers, films, sheets, and the like) polypropylene that produces nucleation sites for polypropy 55 and exhibit excellent recrystallization temperatures and very lene crystals from transition from its molten State to a Solid, quick injection molding cycle times for those purposes. The cooled Structure. Hence, Since the polypropylene composi dibenzylidene Sorbitol types exhibit the same types of prop tion (including nucleator compounds in certain cases) must erties as well as excellent clarity within Such Standard be molten to eventually extrude the fiber itself, the nucleator polypropylene forms (plaques, sheets, etc.). For the purposes compound will provide Such nucleation sites upon cooling 60 of this invention, it has been found that the dibenzylidene of the polypropylene from its molten State. The only way in Sorbitol types are preferred as nucleator compounds within which Such compounds provide the necessary nucleation the target polypropylene fibers. Sites is if Such Sites form prior to polypropylene recrystal Furthermore, Such fibers may include other coloring lization itself. Thus, any compound that exhibits Such a agents, Such as pigments, titanium dioxide, and the like, as beneficial effect and property is included within this defini 65 well as fixing agents for lightfastneSS purposes. To that end, tion. Such nucleator compounds more Specifically include certain ultraViolet absorbers provide excellent protection dibenzylidene Sorbitol types, including, without limitation, from ultraViolet radiation and thus aids in reducing, if not US 6,849,330 B1 11 12 preventing, color degradation due to Such exposure. Any tially preferred embodiment of producing the inventive type of ultraviolet absorber compound or formulation that is low-shrink polypropylene fibers and together with the dispersible within may be utilized within this description Serve to explain the principles of the invention invention. However, Some non-limiting examples of Such wherein: components include phenolic antioxidants, Such as HOS FIG. 1 is a schematic of the potentially preferred method TANOXCR 245, O10, O14, O16, O3, and blends with HOS of producing colored polypropylene fibers through typical TANOXOR M, all available from Clariant; processing Spinning machinery. stabilizers, such as HOSTANOXOR PAR 24, SAN DOSTABOR PEPQ (from Clariant), and blends with SAN FIG. 2 is a schematic of the potentially preferred method DOSTABOR OB; Sulfur-containing co-stabilizers, such as of producing colored polypropylene tape fibers. HOSTANOXCE) SE 4 or SE 10; metal deactivators, such as FIG. 3 is a schematic of the potentially preferred method HOSTANOX(R) OSP 1; light stabilizers, such as of producing colored polypropylene fibers through typical NYLOSTAB(RS-EED (from Clariant, as well); and straight high-speed spinning machinery. forward ultraviolet absorbers, such as CHIMASSORB(R) FIG. 4 is a side-view color microphotograph of a green 2020, 944, 119, and/or 119FL, TINUVINGR 783, 353, 234, colored inventive polypropylene fiber magnified at 565x 1577, and/or 622 (all available from Ciba Specialty 15 colored with a liquid polymeric colorant. Chemicals). Preferred is TINUVINGR 783 for such a pur pose. FIG. 5 is a side-view color microphotograph of a com In terms of providing effective colorations for brightness, parative green-colored polypropylene yarn magnified at it is further desirable to avoid pigments as nucleating agents, 565x having pigments present throughout. however, if desired, slight amounts of Such pigments may be FIG. 6 is a cross-sectional view of a plurality of green added for nucleation or coloration purposes if Such are colored inventive polypropylene fibers magnified at 565x desired end results. Other additives may also be present, colored with a liquid polymeric colorant. including antistatic agents, brightening compounds, clarify DETAILED DESCRIPTION OF THE DRAWING ing agents, antioxidants, antimicrobials (preferably Silver AND OF THE PREFERRED EMBODIMENT based ion-exchange compounds, such as ALPHASANGR) 25 antimicrobials available from Milliken & Company), fillers, FIG. 1 depicts the non-limiting preferred procedure fol and the like. Furthermore, any fabrics made from Such lowed in producing the inventive low denier polypropylene inventive fiberS may be, without limitation, woven, knit, fibers. The entire fiber production assembly 10 comprises an non-woven, in-laid Scrim, any combination thereof, and the extruder 11 including a metering pump (not illustrated) for like. Additionally, such fabrics may include fibers other than introduction of Specific amounts of polymer into the the inventive polypropylene fibers, including, without extruder 11 (to control the denier of the ultimate target limitation, natural fibers, Such as cotton, wool, abaca, hemp, manufactured fiber and/or yarn) which also comprises four ramie, and the like, Synthetic fibers, Such as polyesters, five different Zones 12, 14, 16, 18, 20 through which the polyamides, polyaramids, other polyolefins (including non polymer (not illustrated) passes at different, increasing tem low-shrink polypropylene), polylactic acids, and the like; 35 peratures. The molten polymer is mixed with the liquid inorganic fiberS Such as glass, boron-containing fibers, and polymeric colorant (here, Example 1 from the Colorant the like; and any blends thereof. Table, above, preferably) within a mixer Zone 22. Basically, In addition, this invention can be practiced with any melt the polymer (not illustrated) is introduced within the fiber extrudable thermoplastic polymer, Such as polyester, nylon, production assembly 10, in particular within the extruder 11. poly lactic acid, and the like, with Similar results. 40 The temperatures, as noted above, of the individual extruder Such inventive fibers can be included in a fabric Such as Zones 12, 14, 16, 18, 20 and the mixing Zone 22 are as a carpet, upholstery fabric, woven fabric, knit fabric, follows: first extruder Zone 12 at 210 C., second extruder nonwoven, pile fabric, netting, and the like. In addition, Zone 14 at 220 C., third extruder Zone 16 at 230 C., fourth these fibers can be combined in Such fabric Structures as extruder Zone 18 at 235° C., fifth extruder Zone 20 at 240° accent yarns, especially if the additional non-inventive fibers 45 C., and mixing Zone 22 at 240° C. The molten polymer (not are dye accepting. In Such a case, the inventive yarns provide illustrated) then moves into a spinneret area 24 Set at a accent yarns with bright appearance. In addition, individual temperature of 240 C. for strand extrusion. All such tem yarns may be incorporated within non-fabric Structures, Such peratures may be modified as needed, and these levels are as, as one non-limiting example, fishing lures, and other non-limiting and Simply potentially preferred. The fibrous end-uses in which brightly colored Strong fibers are desir 50 Strands 28 then pass through an air-blown treatment Shroud able. area 26 set at a temperature of 175 C. and then through a Inventive yarns and fibers can be used in any Standard treatment area 29 whereupon a lubricant, Such as water or an textile process, including, without limitation, Such methods oil, is applied thereto the strands 28. The strands 28 are then as yarn texturing processes Such as Stuffer box, bulk con collected into a bundle 30 via a take-up roll 32 to form a tinuous filament (BCF), air jet texturing, twisting, false twist 55 multifilament yarn 33 which then passes to a series of testing, and the like. They can also be combined with other tensioning rolls 34, 36 prior to drawing. The yarn 33 then yarns or used in other processes to make "elegant’ or passes through a series of two different sets of draw rolls 38, "fancy yarns, Such as chenille, slub yarns, stria yarns, etc., 40, 42, 44 which increase the speed of the collected finished with all of the incumbent advantages of combining the strands 33 as compared with the speed of the initially technologies. In addition, the transparent nature of the color 60 extruded strands 28. The finished strands 33 extend in length can be used in light weight fabrics to make colored trans due to a greater pulling Speed in excess of Such an initial parent fabrics Such as may be desirable to show a pattern on extrusion speed within the extruder 11. The strands 33 are a substrate covered by the inventive fabric. then passed through a series of relax rolls 46, 48 and ultimately to a winder 50 for ultimate collection on a spool BRIEF DESCRIPTION OF THE DRAWINGS 65 (not illustrated). The speed of the winder 50 ultimately The accompanying drawings, which are incorporated in dictates the Speed and efficiency of the entire apparatus in and constitute a part of this specification, illustrate a poten terms of permitting high Speed manufacturing and Spinning US 6,849,330 B1 13 14 (drawing) with minimal, if any, breakage of the target fibers extruder Zones 212, 214, 216, 218, 220 and the mixing Zone during Such a procedure. The draw rolls are heated to a very 22 are as follows: first extruder Zone 212 at 205 C., second low level as follows: first draw rolls 38, 40 60–70° C. and extruder Zone 214 at 215 C., third extruder Zone 216 at 225 the second set of draw rolls 42, 44 80-90° C., as compared C., fourth extruder Zone 218 at 235 C., fifth extruder Zone with the remaining areas of high temperature exposure as 220 at 240° C., and mixing Zone 222 at 245° C. The molten well as comparative fiber drawing processes. The draw rolls polymer (not illustrated) then moves into a spinneret area 38, 40, 42, 44 individually and, potentially independently 224 set at a temperature of 250 C. for strand extrusion. All rotate at a speed of from about 1000 meters per minute to as Such temperatures may be modified as needed, and these high as about 5000 meters per minute. The second draw rolls levels are non-limiting and Simply potentially preferred. The 42, 44 generally rotate at a higher speed than the first in fibrous strands 228 then pass through an air-blown treatment excess of about 800 meters per minute up to 1000 meters per area 226 and then through a treatment area 229 whereupon minute over those of the first set. a lubricant, Such as water or an oil, is applied thereto the FIG. 2 depicts the non-limiting preferred procedure fol strands 228. The strands 228 are then collected into abundle lowed in producing the inventive low-shrink polypropylene 230 via a take-up roll 232 to form a multifilament yarn 233 tape fibers. The entire fiber production assembly 110 com 15 which then passes to a series of tensioning rolls 234, 236 prises a mixing manifold 111 for the incorporation of molten prior to drawing. The yarn 233 then passes through a Series polymer and additives (Such as the aforementioned nucleator of two different sets of draw rolls 238,240, 242, 244 which compound) which then move into an extruder 112. The increase the speed of the collected finished strands 233 as extruded polymer is then passed through a metering pump compared with the Speed of the initially extruded Strands 114 to a die assembly 116, whereupon the film 117 is 228. The finished strands 233 extend in length due to a produced. The film 117 then immediately moves to a greater pulling Speed in excess of Such an initial extrusion quenching bath 118 comprising a liquid, Such as water, and speed within the extruder 211. The strands 233 are then the like, set at a temperature from 5 to 95 C. (here, passed through a series of relax rolls 246,248 and ultimately preferably, about room temperature). The drawing speed of to a winder 250 for ultimate collection on a spool (not the film at this point is dictated by draw rolls and tensionsing 25 illustrated). The speed of the winder 250 ultimately dictates rolls 120, 122, 124, 126, 128 set at a speed of about 100 the Speed and efficiency of the entire apparatus in terms of feet/minute, preferably, although the Speed could be any permitting high Speed manufacturing and Spinning where from about 20 feet/minute to about 200 feet/minute, (drawing) with minimal, if any, breakage of the target fibers as long as the initial drawing speed is at most about vs" that during Such a procedure. The draw rolls are heated to a very of the heat-draw speed later in the procedure. The quenched low level as follows: first draw rolls 238,240 68 C. and the film 119 should not exhibit any appreciable crystal orienta second set of draw rolls 242, 24488 C., as compared with tion of the polymer therein for further processing. Sanding the remaining areas of high temperature exposure as Well as rolls 130, 131,132,133,134, 135, may be optionally utilized comparative fiber drawing processes. The draw rolls 238, for delustering of the film, if desired. The quenched film 119 240, 242, 244 individually and, potentially independently then moves into a cutting area 36 with a plurality of fixed 35 rotate at a speed of from about 1000 meters per minute to as knives 138 spaced at any distance apart desired. Preferably, high as about 5000 meters per minute. The second draw rolls such knives 138 are spaced a distance determined by the 242, 244 generally rotate at a higher Speed than the first in equation of the Square root of the draw speed multiplied by excess of about 800 meters per minute up to 1000 meters per the final width of the target fibers (thus, with a draw ratio of minute over those of the first set. 5:1 and a final width of about 3 mm, the blade gap mea 40 In FIG. 4, the presence of rod-like structures of color is surements should be about 6.7 mm). Upon slitting the evident throughout the fiber. Such rod-like structures are quenched film 119 into fibers 140, such fibers are moved basically the liquid polymeric colorants stretched in the uniformly through a Series of nip and tensioning rolls 142, Same manner as the resin fiber is stretched during extrusion. 143, 144, 145 prior to being drawn into a high temperature The shear of extrusion forms long high aspect ratio rod-like oven 146 set at a temperature level of between about 280 and 45 configurations of liquid colorant within the target fiber. Such 350 C., in this instance about 310 C., at a rate as noted a rod-like Structure thus imparts colorations to the target above, at least 5 times that of the initial drawing Speed. Such fiber while Simultaneously allowing transmission of light an increased drawing Speed is effectuated by a Series of therethrough. AS Such, the fiber remains transparent to light, heated drawing rolls 141, 150 (at temperatures of about thereby exhibiting an increased brightness and luster. 360-400 F. each) over which the now crystal-oriented 50 Furthermore, these rod-like Structures, although they remain fibers 154 are passed. A last tensioning roll 152 leads to a liquid in nature, are not in individual pools of color, but are spool (not illustrated) for winding of the finished tape fibers Stretched in Such a rod-like manner, Such that the liquid 154. component cannot be easily extracted from within the target FIG. 3 depicts the non-limiting preferred procedure fol fiber without damaging the fiber itself. lowed in producing the inventive low denier polypropylene 55 In FIG. 5, the presence of pigment particles is evident fibers. The entire fiber production assembly 210 comprises throughout the fiber. Such pigment particles are Solid in an extruder 211 including a metering pump (not illustrated) nature. The color imparted to the target fiber is thus Sub for introduction of Specific amounts of polymer into the Stantially reliant upon absorption of light by Such Solid extruder 211 (to control the denier of the ultimate target particles. There is little chance of light transmission through manufactured fiber and/or yarn) which also comprises five 60 the fiber Such that the fiber lackS transparency. As a result, different Zones 212, 214, 216, 218, 220 through which the brightness and luster are compromised Such that the fiber polymer (not illustrated) passes at different, increasing tem exhibits a dulling effect, particularly in comparison with the peratures. The molten polymer is mixed with the nucleator fiber of FIG. 4. compound (also molten) within a mixer Zone 222. Basically, In FIG. 6, the presence of “dots” of color can be seen the polymer (not illustrated) is introduced within the fiber 65 within the cross-sectional views of the target fibers (as in production assembly 210, in particular within the extruder FIG. 4). Such “dots” are the portions of the rod-like high 211. The temperatures, as noted above, of the individual aspect ratio Structures of the liquid colorants that were US 6,849,330 B1 15 16 stretched during extrusion. The plurality of “dots” thus shows the inclusion of numerous different rod-like Structures TABLE #2-continued throughout individuals fibers. Coupled with the side view (as in FIG. 4), it can be seen how a liquid coloring agent Procedural Conditions (polymeric type, preferably, though not necessarily) is Fiber Extrusion Conditions Stretched from a starting pool of liquid into this high aspect Color Draw Heat Set ratio Strand (rod-like structure). Sample ID Polymer Color Level Ratio ( C.) Inventive Fiber and Yarn Production 5 Amoco 7550 10% Colorant #3 0.5 3.44 25 6 Amoco 7550 10% Colorant #3 0.5 3.53 25 EXAMPLE 1. 1O 7 Amoco 7550 10% Colorant #5 0.5 3.49 25 8 Amoco 7550 10% Colorant #5 0.5 3.44 25 9 Amoco 7550 10% Colorant #5 0.5 4.56 25 Polymeric Colorant Fibers 1O Amoco 7550 10% Colorant #2 0.5 3.44 25 11 Amoco 7550 10% Colorant #2 1.0 3.44 25 Yarns were made using a commercially available polypro 12 Amoco 7550 10% Colorant #2 1.0 3.44 25 pylene fiber grade resin Amoco 7550 (melt flow of 18), 15 13 Amoco 7550 10% Colorant #2 1.0 3.55 25 using a Standard fiber Spinning apparatus as described pre 14 Amoco 7550 10% Colorant #4 0.5 3.49 25 15 Amoco 7550 10% Colorant #4 0.5 3.94 25 viously. The five colorants from the COLORANT TABLE, 16 Amoco 7550 10% Colorant #4 0.5 4.56 25 above, were formed into 10% concentrates premixed with 17 Amoco 7550 10% Colorant #1 0.5 4.56 25 fiber grade polypropylene resin and fed into the hopper of 18 Amoco 7550 10% Colorant #1 0.5 3.44 25 the extruder during fiber extrusion. In one preferred 19 Amoco 7550 10% Colorant #1 0.5 3.53 25 embodiment, fiber grade resin polypropylene was fed into 2O Amoco 7550 Blue Pigment 0.5 3.44 25 the extruder on an Alex James & ASSociates multifilament 21 Amoco 7550 Red Pigment 0.5 3.44 25 fiber extrusion line as noted above in FIG. 1 along with a 22 Amoco 7550 Yellow Pigment 0.5 3.44 25 10% color concentrate including the required liquid poly meric colorants. Yarn was produced with the extrusion line conditions shown in Table 1 using a 68 hole Spinneret, 25 TABLE if1 giving a yarn of nominally 150 denier. The godet roll Experimental temperatures were 67° C. (for 38, 40 in FIG. 1), 85°C. (for Fiber Properties 42, 44), and 125 C. (for 46, 48), respectively, with a nominal winder speed of about 1300 m/min. Pigmented 3% 130C Denier Elongation Tenacity Modulus Shrinkage fibers were also made for comparative purposes. Sample ID (g/9000 m) (%) (g/den) (gden) (%) The extruder and cooling conditions were as follows: 1. 53.8 53.0 4.6 41.6 6.6 2 85.7 32.1 6.5 67.9 9.9 TABLE if1 3 59.7 67.9 4.7 44.4 11.1 35 4 72.7 61.5 5.0 44.0 14.8 Procedural Conditions 5 47.4 74.4 4.6 42.4 8.5 6 50.7 66.1 4.2 38.9 9.6 Extruder Temperature Zone #1 210° C. 7 49.5 41.1 4.4 41.2 7.2 Extruder Temperature Zone #2 220° C. 8 55.1 54.7 4.1 38.7 8.0 Extruder Temperature Zone #3 230° C. 9 69.2 46.6 5.6 51.O 10.4 Extruder Temperature Zone #4 235° C. 40 1O 56.2 51.1 5.0 43.9 13.6 Mixer Temperature 240° C. 11 81.0 SO.O 4.6 42.8 9.O Spinneret Temperature #1 240° C. 12 53.8 46.6 4.9 45.3 9.5 Spinneret Temperature #2 240° C. 13 53.6 35.5 4.8 45.4 13.6 Shroud Temperature 1759 C. 14 54.1 47.7 4.3 39.5 11.2 15 51.4 48.0 4.4 4.1.8 7.0 16 68.8 27.0 5.3 51.4 15.3 45 Winder take-up speeds of 1290 m/min with draw ratios of 17 77.3 44.8 5.2 46.7 11.5 approximately 3.5 were utilized and deniers between 150 18 49.9 58.1 4.6 43.4 11.7 19 50.7 48.4 4.6 43.O 14.8 and 200 were produced. A minimum of 3 samples were 2O 53.7 84.7 3.8 35.8 N/A produced with concentrations of /2 and or 1% color in the 21 50.7 66.8 3.3 35.8 N/A Amoco 7550 for each of the colors. Extrusion conditions and 22 51.6 40.6 4.3 40.8 N/A physical properties of these Samples are detailed in the 50 following tables. Additionally, comparative pigmented The above Samples have similar physical properties to Samples were produced with three pigments provided by those of fibers spun with pigments (Solution dyed) in the Standridge Color Concentrate 86600 blue 25% GSP, fade Same polypropylene resin, however the luster of the colors red HUV and yellow HG 25% which are identified in the is significantly different. It is also important to note that the table below as blue, red and yellow pigment, respectively. 55 polymeric colorants are generally non-nucleating and will, under the same processing conditions have similar physical TABLE i2 properties while the pigments (specifically the blue pigment-Sample 20) generally are nucleating which often Procedural Conditions requires the fiber Spinning equipment to be operated under Fiber Extrusion Conditions 60 different conditions to obtain Similar physical properties Color Draw Heat Set note the higher elongation of Sample 20 in comparison to Sample ID Polymer Color Level Ratio ( C.) Samples 21 and 22. 1. Amoco 7550 None O 3.49 125 EXAMPLE 2 2 Amoco 7550 None O 4.56 125 3 Amoco 7550 None O 3.44 125 65 Polymeric Colorant Fibers with TiO, and Pigments 4 Amoco 7550 10% Colorant #3 0.5 4.56 125 A Series of polypropylene Samples was produced under the Standard fiber Spinning conditions described in Example US 6,849,330 B1 17 1 to test the ability to combine both solid pigments and liquid polymeric colorants in the same fibers. The drawing TABLE i2 conditions for these example yarns are detailed in the following table. Fiber Additives 5 Polymer TABLE if3 Colorant Pigment TiO2 Sample Level Level Level Procedural Conditions ID Color (%) (%) (%) Spinning Conditions P1 Green 1.8 O O Roll Speed Roll Temperature 1O P2 Green 1.5 1.5 O (m/min) o C. P3 Green O 1.5 O P4 Red O 1.5 9 Feed Roll 8OO Not heated P5 Red 2 1.5 9 Draw Roll 1 805 55 P6 Black O 1.5 O Draw Roll 2 1450 75 P7 Black 2 O O Draw Roll 3 (A + B) 2OOO 12O 15 P8 Black 2 1.5 O Relax Roll 198O Not heated

Using the Standard fiber Spinning conditions as described EXAMPLE 3 above, a Series of 10 experiments were performed to produce samples with liquid polymeric colorants labeled by Milliken 2O Polymeric Colorant Fibers with Nucleators & Company Product numbers, and TiO, which is commonly A Series of experiments were conducted using commer used in the production of thermoplastic fibers to produce cially available nucleators in combination with the liquid dull (9%. TiO) and semi-dull (3%. TiO) appearance. The polymeric colorants (from the COLORANT TABLE, above) fibers were Successfully produced at all of the conditions to produce continuous filament fibers. Using the same con tested and the list of colorants, TiO levels and fiber prop 25 ditions as described in Example 1 above, 13 Samples were erties are detailed in the Table below using polymeric liquid produced using a commercially available polypropylene colorant mixtures available from Milliken & Company nucleator, Millad 3940 (MDBS). Fiber compositions for the under the tradename CLEARTINTE). 13 experimental samples are found in Fiber Additives Table

TABLE i2 Fiber Properties Polymeric Polymeric Color 5% Color Concentrate TiO, Secant Sample (Colorf Level Level Denier Elongation Tenacity Modulus ID Number) (%) (%) (g/9000 m) (%) (gden) (g/den) T1 Blue 9805 2O N/A 166 50.60 4.626 32.49 T2 Blue 9805 2O 9 152 57.20 5.345 37.40 T3 Blue 5603 1O N/A 153 53.44 5.872 42.94 T4 Blue 5603 5 3 157.92 47.75 5.053 39.01 T5 Smoke 9809 1O N/A 161 31.56 4.323 37.81 T6 Smoke 9809 1O 3 158 39.79 4.824 37.56 T7 Amber 98.08 2O N/A 164 51.38 4.898 36.89 T8 Amber 98.08 2O 3 161 57.77 4.83 34.70 T9 Green 5062 1O N/A 158 51.81 5.225 40.38 T10 Green 5062 5 3 153 54.55 S.42 40.50

#3 below and the physical properties of the final fibers are In addition to experiments with TiO2 a Series of experi 50 found in Fiber Properties Table #4. ments were conducted to determine the viability of Spinning polypropylene fibers with the liquid polymeric colorants and TABLE if3 Standard fiber pigments. A Series of 8 experiments, listed in Fiber Additives the table below, were produced under the Standard Spinning 55 Nucleated Fiber Conditions conditions described above. The pigments, obtained from Addi Standridge Color Concentrate, Social Circle, Ga., are com tive Color Heat mercially available and are typical of the pigments used Sample Addi- Level Level Set Draw within the polypropylene fiber industry. Specifically, the ID Polymer tive (ppm) Color % (C) Ratio green pigment is identified as SCC 3654, the red pigment is 60 A Amoco M3940 2750 10% O.S. 125 4.O 7550 Colorant #3 SCC 4591 and the black pigment is SCC 23005. The B Amoco M3940 2750 10% 0.5 125 5.1 polymeric colorants in these example experiments are iden 7550 Colorant #3 C Amoco M3940 2750 10% 0.5 125 3.4 tified as PP Green 5720, PP Red 5718, and PP Smoke 5719 7550 Colorant #3 for the green, red and black liquid polymeric colorant 65 D Amoco M3940 2750 10% 0.5 125 3.4 respectively (all available under the tradename CLEART 7550 Colorant #5 INTR) from Milliken & Company). US 6,849,330 B1 19 20

TABLE if3-continued TABLE if4

Fiber Additives Fiber Additives Nucleated Fiber Conditions Colorant UV UV Stabilizer Addi Sample Concentration Stabilizer Concentration tive Color Heat ID (%) (name) (ppm) Sample Addi- Level Level Set Draw ID Polymer tive (ppm) Color % (C) Ratio Y1 2 Tnuvin 783 1OOO Y2 1. N/A N/A E Amoco M3940 2750 O% 0.5 25 4.0 1O Y3 1. Tnuvin 783 1OOO 7550 Colorant #2 Y4 1. Tnuvin 783 2OOO F Amoco M3940 2750 O% 0.5 25 3.4 Y5 1. Tnuvin 783 500 7550 Colorant #2 Y6 1. Tnuvin 783 1OOOO G Amoco M3940 2750 O% 0.5 25 5.1 Y7 1. Tnuvin 783 15OOO 7550 Colorant #2 Y8 1. Tnuvin 622 1OOOO H Amoco M3940 2750 O% 0.5 25 5.1 15 Y9 1. Chimassorb 844 1OOOO 7550 Colorant #4 Y1O 2 Tnuvin 783 1OOOO I Amoco M3940 2750 O% 0.5 25 4.0 7550 Colorant #4 J Amoco M3940 2750 O% 0.5 25 3.4 7550 Colorant #4 EXAMPLE 5 K Amoco M3940 2750 O% 0.5 25 5.1 7550 Colorant #1 L Amoco M3940 2750 O% 0.5 25 4.0 Textured Polymeric Colorant Fibers 7550 Colorant #1 M Amoco M3940 2750 O% 0.5 25 3.4 Yarns containing 1% of the polymeric colorants PP 7550 Colorant #1 Orange 9802 and PPViolet 9804 were air jet textured. The starting yarns were 150 denier, 72 filament yarns with 25 Standard physical properties produced in the same manner as those fibers described in Example #1 above. Two orange TABLE if4 yarns were air jet textured with one violet yarn to produce Fiber Properties a collaged air jet textured yarn. Colored and Nucleated Fibers EXAMPLE 6 130C Sample Denier Elongation Tenacity 3% Modulus Shrinkage Polymeric Colorant Fibers from Liquid Colorant ID (g/9000 m) (%) (g/den) (g/den) (%) Injection A. 129 65.996 4.805 46.823 8.524 B 152.5 41.467 5.555 56.61 9.64 35 For two colors, a Second Set of yarns was produced by C 154.5 93.919 3.939 36.697 6.595 directly injecting the liquid colorant into the feed throat of D 151.1 73.769 3.825 39.584 6.973 the extruder of the fiber spinning equipment. Basell PDC E 131 30.29 4.474 46.237 8.678 F 155.4 40.265 3.446 36.636 5.995 1302, a 35 MFI HPP, was fed into the extruder at an G 160.4 28.747 5.044 52.14 8.136 extrusion temperature of 200 C. The polymeric colors were H 153.8 23.227 5.208 52.764 8.893 40 then injected directly into the hopper of the extrusion line I 134 23.895 3.94 39.574 8.79 using a peristaltic pump (Maguire, Model PA-6-18). In each J 151.3 50.934 3.06 32.392 7.019 case the pump was Set to the lowest possible Setting, due to K 1634 20.941 5.218 54.94 9.255 L 1321 37.146 4.768 50.275 8.849 Size of the extrusion line and the throughput of the melt M 159.7 72.707 3.309 34.248 6.976 pump. The two colorants used were 10% concentrates of the violet and red colorants from the COLORANT TABLE, 45 above. All yarns were produced under the Spinning condi Additionally using other commercially available nucleator tions described in Table 5 below. compounds a Series of yarns were produced using a Basell 35MFI fiber grade resin, Grade PDC-1302, using the green TABLE is liquid colorant (PP Green 5720). In each case 1.2% of the 50 green liquid colorant were combined with 2500 ppm of Procedural Conditions Millad 3940 (MDBS), Millad 3988 (DMDBS), HPN-68 and Roll Speed Roll Temperature NA-21. (m/min) o C. Feed Roll % 500 Not Heated EXAMPLE 4 55 Draw Roll 1 505 55 Draw Roll 2 1OOO 75 Draw Roll 3 (A + B) 1250 12O Polymeric Colorant Fibers with UV Absorbers Relax Roll 1240 Not Heated To test the spinnability of polypropylene fibers with both the liquid polymeric colorants and a range of UV stablizers, 60 At these conditions, yarns of different deniers were produced 10 samples using a 10% concentrate of Yellow 485 poly by adjusting the melt pump Speed. meric colorant and various UV Stabilizers were generated. The 10 Samples were spun under Standard Sampling condi EXAMPLE 7 tions as described in Example 2 above. The table below details the combinations and amounts of UV stabilizers with 65 Polymeric Colorant Monofilament two different concentrations of the yellow colorant from the Polymeric colorant concentrates were let down into two COLORANT TABLE, above. PPresins: the first with an MFI of 12–18 g/10 min (Exxon US 6,849,330 B1 21 22 1154) and the second with an MFI of 4 g/10 min (Exxon There are, of course, many alternative embodiments and 2252) at a level of 10% to give 1% colorant in the final modifications of the present invention which are intended to polymer fiber. This mixture, consisting of PPresin and the be included within the spirit and scope of the following polymeric colorant additive, was extruded using a single claims. Screw extruder through monofilament Spinnerets with 60 What we claim is: holes. The PP melt throughput was adjusted to give a final 1. A polypropylene fiber comprising at least one liquid monofilament denier of approximately 520 g/9000 m. The polymeric colorant and at least one nucleator compound, molten Strands of filament were quenched in room tempera therein, wherein Said at least one liquid polymeric colorant ture water (about 25 C.), and then transferred by rollers to defines a plurality of elongate colored rods within Said fiber. a battery of airs knives, which dried the filaments. The 2. The fiber in claim 1 wherein said fiber is present as a filaments, having been dried, were run acroSS the first of four Structure Selected from the group consisting of a monofila Sets of large rolls, all rotating at a Speed of between 49 and ment fiber, a tape fiber, a Staple fiber, a melt spun non-woven 126 ft/min (dependent on draw ratio), before entering an fiber, a bicomponent/splittable fiber, and a slit film fiber. oven approximately 14 ft long set to a temperature of 360 3. The fiber in claim 2 wherein said fiber is present as a F. After leaving the first oven, the filaments were transferred 15 Structure Selected from the group consisting of a multifila to the Second Set of large rollers running at a speed of 524 ment fiber, a monofilament fiber, a tape fiber, a Staple fiber, ft/min (dependent on draw ratio) and then into Second oven, a melt spun non-woven fiber, a bicomponent/splittable fiber, set at a temperature of 360 F. The final two sets of rolls were and a slit film fiber. both set at 630 ft/min and the oven between them was set at 4. The fiber in claim 1 wherein said fiber is textured. a temperature of 300 F. The individual monofilament fibers 5. The fiber in claim 2 wherein said fiber is textured. were then traversed to winders where they were individually 6. The fiber in claim 3 wherein said fiber is textured. wound. These final fibers are thus referred to as the PP 7. A multifilament yarn comprising at least one fiber as monofilaments. Several monofilament fibers were made in defined in claim 1. this manner with the following PP Red 9803, PP Violet 8. A multifilament yarn comprising at least one fiber as 9804, PP Blue 9805, and PP Green 9807. 25 defined in claim 2. 9. A multifilament yarn comprising at least one fiber as EXAMPLE 8 defined in claim 3. 10. A multifilament yarn comprising at least one fiber as Melt Blown Non-Woven with Polymeric Colorants defined in claim 4. A colored melt blown non-woven fabric was produced 11. A multifilament yarn comprising at least one fiber as using a Nordson Fiber systems pilot melt blown system. The defined in claim 5. equipment consisted of a % Single Screw extruder (24:1.) L.D 12. A multifilament yarn comprising at least one fiber as ratio manufactured by J/M Laboratories-Model DTMB. defined in claim 6. The airflow was set to 30 Scfm with a max temperature of 13. The fiber in claim 7 wherein said fiber is a bulk 625F. The orange colorant from the COLORANT TABLE, 35 continuous filament. above, in a 10% concentrate, was let down into Basell 35 14. The fiber in claim 8 wherein said fiber is a bulk MFI fiber grade resin to give a final color loading of 1% in continuous filament. the melt blown fabric. 15. The fiber in claim 9 wherein said fiber is a bulk continuous filament. EXAMPLE 9 40 16. The fiber in claim 10 wherein said fiber is a bulk continuous filament. Polyester Polymeric Colorant Fibers from Liquid 17. The fiber in claim 11 wherein said fiber is a bulk Color Injection continuous filament. 18. The fiber in claim 12 wherein said fiber is a bulk A Set of experiments similar to Example #6 was con 45 continuous filament. ducted using a low IV (0.62) PET resin. Two liquid poly 19. The fiber in claim 1 wherein said fiber comprises at meric colorants, PET Yellow 236 and PET Orange 226, least one pigment. available from Milliken & Company, were used to produce 20. The fiber in claim 2 wherein said fiber comprises at yarn samples. Free fall fiber was collected from the least one pigment. Spinneret, which had the Similar vibrant color as Seen with 50 21. The fiber in claim 1 wherein said fiber comprises at the polypropylene fibers of Example 6. least one ultraviolet absorber. EXAMPLE 10 22. The fiber in claim 2 wherein said fiber comprises at least one ultraviolet absorber. BCF Fibers Including Liquid Polymeric Colorants 23. A fabric comprising at least one fiber as defined in 55 claim 1. Cyan 9806 (from Milliken & Company) polymeric colo 24. A fabric comprising at least one fiber as defined in rant was used to produce a colored bulk continuous filament claim 2. (BCF) textured PP yarn. A three ply BCF 300 denier 72 25. A fabric comprising at least one fiber as defined in filament yarn was produced using Standard BCF equipment. claim 3. Additionally using the liquid polymeric PP Orange 98.02 60 26. A fabric comprising at least one fiber as defined in colorant a single ply BCF 250 denier 72 filament textured claim 4. yarn was also produced using Standard BCF equipment. The 27. A fabric comprising at least one fiber as defined in colorant was added to the extrusion line using a 10% claim 5. concentrate to give a final color level of 1% in the yarns. 28. A fabric comprising at least one fiber as defined in Knitted Structures (Socks) of the above Examples (except 65 claim 6. for Example #8 which was already made into a non-woven 29. A fabric comprising at least one fiber as defined in fabric) were then produced. claim 21. US 6,849,330 B1 23 24 30. A fabric comprising at least one multifilament yarn as 40. A multifilament yarn comprising at least one fiber as defined in claim 7. defined in claim 36. 31. A fabric comprising at least one multifilament yarn as 41. A multifilament yarn comprising at least one fiber as defined in claim 8. defined in claim 37. 32. A fabric comprising at least one multifilament yarn as 42. A multifilament yarn comprising at least one fiber as defined in claim 9. defined in claim 38. 33. A fabric comprising at least one multifilament yarn as 43. A multifilament yarn comprising at least one fiber as defined in claim 10. defined in claim 39. 34. A fabric comprising at least one multifilament yarn as 44. A fabric comprising at least one fiber as defined in defined in claim 11. claim 36. 35. A fabric comprising at least one multifilament yarn as 45. A fabric comprising at least one fiber as defined in defined in claim 12. claim 37. 36. A colored transparent polypropylene fiber comprising 46. A fabric comprising at least one fiber as defined in at least one nucleator compound and at least one liquid claim 38. polymeric colorant defining a plurality of elongate colored 15 47. A fabric comprising at least one fiber as defined in rods within said fiber. claim 37. 37. The fiber in claim 36 wherein said fiber is present as 48. A fabric comprising at least one multifilament yarn as a structure Selected from the group consisting of a monofila defined in claim 40. ment fiber, a tape fiber, a Staple fiber, a melt spun nonwoven 49. A fabric comprising at least one multifilament yarn as fiber, a bicomponent/splittable fiber, and a slit film fiber. defined in claim 41. 38. The fiber in claim 37 wherein said fiber is present as 50. A fabric comprising at least one multifilament yarn as a structure Selected from the group consisting of a multifila defined in claim 42. ment fiber, a monofilament fiber, a tape fiber, a Staple fiber, 51. A fabric comprising at least one multifilament yarn as a melt spun nonwoven fiber, a bicomponent/splittable fiber, defined in claim 43. and a slit film fiber. 25 39. The fiber in claim 38 wherein Said fiber is textured. UNITED STATES PATENT AND TRADEMARK OFFICE CERTIFICATE OF CORRECTION

PATENT NO. : 6,849,330 B1 Page 1 of 1 DATED : February 1, 2005 INVENTOR(S) : Brian Morin and Martin Cowan

It is certified that error appears in the above-identified patent and that said Letters Patent is hereby corrected as shown below:

Column 24 Line 16, after the word "claim" delete the number -- 37 -- and insert the number -- 39 --.

Signed and Sealed this Twenty-third Day of August, 2005 WDJ

JON W. DUDAS Director of the United States Patent and Trademark Office