EP1446518B1 - Polyolefinbasierende synthesefasern und verfahren zu deren herstellung - Google Patents

Polyolefinbasierende synthesefasern und verfahren zu deren herstellung Download PDF

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EP1446518B1
EP1446518B1 EP01975559A EP01975559A EP1446518B1 EP 1446518 B1 EP1446518 B1 EP 1446518B1 EP 01975559 A EP01975559 A EP 01975559A EP 01975559 A EP01975559 A EP 01975559A EP 1446518 B1 EP1446518 B1 EP 1446518B1
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Prior art keywords
polyolefin
yarn
yam
polymer
fibril forming
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French (fr)
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EP1446518B9 (de
EP1446518A1 (de
EP1446518A4 (de
Inventor
Luca Bertamini
Luigi Marco Pontarin
Mauro Caldara
William C. Mallonee
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Aquafil SpA
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Aquafil SpA
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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/46—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyolefins
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/253—Formation of filaments, threads, or the like with a non-circular cross section; Spinnerette packs therefor

Definitions

  • the invention relates to a polyolefin-based synthetic yam characterized by improved mechanical properties, improved dyeability and a method for making the yarn for use as carpet face yarn, textiles and upholstery.
  • Polyolefin-based yarns are characterized by a low cost and by a chemical resistance towards many liquids and are therefore of interest in for making carpet and textiles including upholstery yarn where staining is a problem. Polyolefin-based yarns are also suitable for technical applications, such as in filters.
  • Tg glass transition temperature
  • room temperature i.e., between - 5 and -15°C. Due to the low Tg of polyolefin-based yarns, the shape retention of the yam under an external force at room temperature is limited.
  • Polyolefin-based yarns tend to adapt to a new shape through molecular motion in the polymer.
  • the resilience of carpets made with a polyolefin-based yam is undesirably low for use as a carpet fiber.
  • the resilience and other mechanical properties of the yarn are even lower.
  • Heat-setting the polyolefin-based yam enables relaxation of the internal stresses in the yarn fibers and helps retain the shape for the yarn after twisting, but heat-setting can not lead to a permanent yarn shape if a sufficient external force is applied.
  • nylon has been the main choice for carpets, where high quality and resilience is required.
  • nylon is not without drawbacks.
  • carpeting made with nylon yarn is susceptible to developing static electrical charges and thus must be chemically or physically treated to reduce the building up of static charges.
  • Another disadvantages of nylon carpeting is that it will readily stain. Accordingly, nylon carpeting usually contains treatments which reduce its staining tendencies. These treatments do not, however, prevent all staining, nor will the treatments be effective for the life of the carpet.
  • carpets made from polyolefin materials are very resistant to staining and are naturally antistatic.
  • polypropylene is a less resistant fiber and will not maintain its appearance or shape under prolonged or heavy use or after repeated deformations.
  • polyolefin-based yarns Similar considerations with respect to polyolefin-based yarns can be addressed for the textile sector, including upholstery yarns, where stain removal is extremely difficult.
  • the use of the polyolefin-based yarns could be even more beneficial due to the low costs of the polymer and to its excellent hydro-repellency, dry fastness and resistance to staining.
  • use of polyolefin-based yarns is limited by its low mechanical properties and limited shape retention due to the low resilience of such yarns and to the fact that mechanical properties of such yarns at temperatures above room temperature tend to decrease rapidly.
  • polyolefin-based yarns As is the case for the polyester or for nylon fibers. Accordingly, polyolefin polymers or copolymers, such as ethylene/acrylic copolymers, have been used in conjunction with the polyolefin-based yarns. Other additives with similar properties were developed to introduce amino groups in the polyolefin polymer during the polymerization phase. To obtain dyeability of polyolefin-based yarns with disperse dyes, polyester-based additives and polar copolymers were used. Dyeing of polyolefin-based yarns with ligand-forming dyes was made possible through the addition of nickel compounding.
  • Dyeing with hydrocarbon soluble dyes with long alkyl-chains was also proposed for standard polyolefin polymers.
  • a dyeable polypropylene polymer was provided by the use of special dendrimers and hyperbranched polymers. Plasma treatments have been proposed on a laboratory scale to introduce reactive groups into the yam surface.
  • the invention provides a method for making fibers and yarns having a weight in grams of 9000 m of filament (denier per filament (dpf) size) ranging from about 1 to about 30 dpf and improved mechanical properties.
  • the method includes blending from about 55 to about 95 wt.% polyolefin polymer and from about 5 to about 45 wt.% fibril forming polymer to provide a mixture of polyolefin and fibril forming polymers the fibril forming polymer being immiscible with the polyolefin polymer.
  • a hot melt extruder to which the mixture is fed is used to provide a substantially homogenous molten mixture of polyolefin and fibril forming polymers.
  • the molten mixture is then forced through a spinneret having an length to diameter (L/D) ratio ranging from about 3 to about 30 at a shear rate ranging from about 1000 to about 5000 reciprocal seconds to provide a fiber having a polyolefin matrix and elongate, substantially discontinuous fibrils of the fibril forming polymer dispersed in the polyolefin matrix, whereby an exterior surface of the fibers is substantially devoid of fibrils.
  • L/D length to diameter
  • the method of the present invention can further comprise drying the polyolefin polymer, fibril forming polymer and compatibilizer to provide a mixture containing less than about 500 ppm moisture.
  • the method of the present invention can further comprise drying the polyolefin polymer and fibril forming polymer to provide a mixture containing less than about 500 ppm moisture.
  • the method of the present invention can further comprise dyeing the fibers with a dispersed dye, a reactive dye or a mixture of both to provide dyed fibers, the dyeing being preferably conducted at a pressure ranging from about 1 to about 4 bar and at a pressure ranging from about 1.5 to about 2 bar.
  • the present invention further provides the use of the yarn of the present invention comprising a BCF yarn as a carpet face yam, use of the yarn of the present invention comprising a POY, FDY or LDY yarn as a textile yarn, use of the yarn of the present invention as an upholstery yarn and use of the yarn of the present invention as a staple yarn.
  • the invention provides a yam having improved mechanical properties and enhanced dyeability.
  • the yam includes from about 55 to about 95 wt.% polyolefin continuous phase and from about 5 to about 45 wt.% discontinuous phase of fibrils dispersed in the polyolefin continuous phase, the fibrils being derived from a fibril forming polymer selected from the group consisting of polyamide polymers and polyester polymers.
  • the polyolefin continuous phase is substantially devoid of fibrils on an exposed surface thereof, the yam is dyeable, particularly with reactive dyes such as acid or cationic dyes, and the yarn exhibits an irreversible deformation at about 25°C of less than about 3 %.
  • the present invention is an improvement on the invention described in related U.S. Patent Nos. 5,587,118 ; 5,597,650 ; 5,620,797 ; and 5,811,040 to Mallonee, which provides a method for blending immiscible polymers to provide an improved carpet face yam. It has been found that filaments made according to the invention have a substantially continuous polyolefin phase and a substantially discontinuous fibril phase interspersed in the polyolefin phase.
  • the discontinuous fibril phase provides to a polyolefin-based carpet yarn, polyamide- and/or polyester-type properties in terms of resiliency and color fastness, but without the apparent characteristic drawbacks of the material forming the fibrils.
  • the yarn exhibits the excellent anti-staining properties of polyolefin and their favorable flame retardancy and anti-static properties, but does not exhibit the weak points of the conventional polyolefin fibers.
  • the yam is also less costly to produce than many polyamide and polyester filaments, since polypropylene is currently up to about 60% cheaper per pound than polyamide and up to about 40% cheaper than polyester.
  • USP 5 811 040 discloses method for making fiber for a carpet face yarn
  • the method comprises conducting a mixture comprising from about 5 to about 40% by weight of a fibril-forming polymer selected from the group consisting of polyamide and polyester with from about 60 to about 95% by weight polyolefin through a hot melt extruder to produce a substantially homogeneous molten mixture which is forced at a shear rate within the range of from about 1000 to about 5000 reciprocal seconds through a spinnerette containing a plurality of capillary openings to produce individual filaments, drawing and hot air texturizing the filaments at a temperature ranging from about 120°C to about 130 °C. to provide drawn and texturized filaments having a denier ranging from about 12 to about 25 and combining the drawn and texturized filaments to provide a synthetic carpet face yarn.
  • a fibril-forming polymer selected from the group consisting of polyamide and polyester with from about 60 to about 95% by weight polyolefin
  • the yarn of the invention comprising polyolefin matrix and polyester fibrils has a matt finish thus reducing the need for the addition of fillers such as titanium dioxide to decrease the luster of the yam as is required with conventional polyamide carpet yarns.
  • the synthetic fibers and yarns made according to the invention using a blend of immiscible polymers have a weight in grams of 9000 m of filament (denier per filament (dpf) size) ranging from about 1 to about 30. Because the polyolefin and fibril-forming polymer immiscible with the polyolefin are melt blended and forced through capillary openings of a spinneret as a molten blend, each of the resulting filaments contains essentially the same amount of polyolefin and fibril-forming polymer as the molten blend.
  • the resulting fibers are characterized by a polyolefin continuous phase matrix having interspersed therein substantially co-linear, discontinuous, elongate fibrils throughout the matrix.
  • An important feature of the synthetic, polyolefin-based yarn of the invention is that it has a resiliency similar to polyamide yarns such as nylon 6 and nylon 66, yet has the stain resistance of polyolefin yarns such as polypropylene.
  • the synthetic yam of the invention has a much higher dyeability, flame retardance and mechanical resistance at temperatures higher than room temperature than pure or virgin polyolefin polymer.
  • the synthetic yam of the invention is resistant to the formation of a static electric charge common to polyamide-based carpet yarns.
  • a mixture containing from about 55 % to about 95% by weight polyolefin is blended with from about 5 to about 45% by weight fibril forming polymer.
  • the blend of polyolefin and fibril-forming polymer used to make the fibers and yarns of the invention contain from about 60 to about 95 wt. %, more preferably from about 70 to about 85 wt. %, and most preferably 75 wt.% polyolefin.
  • the fibril forming polymer is preferably present in the blend in an amount ranging from about 5 to about 40 wt. %, more preferably from about 15 to about 30 wt. %, and most preferably 25 wt% fibril- forming polymer.
  • the polyolefins which may be used to produce the yarn and fibers of the invention include, but are not limited to, polyethylene, polypropylene, both homopolymer and copolymers, poly(1-butene), poly(3-methyl-1-butene), poly(4-methyl-1-pentene) and the like as well as combinations or mixtures of two or more of the foregoing.
  • polypropylene homopolymer is particularly preferred.
  • Bulk polypropylene suitable for making the yarn of the invention is available from, but not limited to, Shell Chemical Company of Houston, Texas, under the trade name designations NRDS-126-3, 5E40 and 5E70, Basell Polyolefins Company N.V.
  • the fibril-forming polymer blended with the polyolefin to make the filaments may be selected from the group consisting of polyamide and / or polyester.
  • Polyamide polymers which may be used include the condensation product of a dibasic acid and a diamine such as adipic acid and hexamethylene diamine (nylon 66), and the addition reaction products of monomers containing both an acid and an amine group in the molecule, such as the polymerization product of e-caprolactam to form polycaproamide (nylon 6). Higher analogs or blends of nylon 6 and 66 may also be used.
  • nylon 6 is the most preferred polyamide for use in forming the carpet face yam of the invention.
  • Suitable sources of polyamide polymers include, but are not limited to, the nylon 6 polymers available from AQUAFIL S.P.A. of Arco, Italy, under the trade name AQ2700 and from BASF Corporation of Asheville, N.C. under the trade name designation Type 403. Other sources of polyamide polymer may be suitable as well.
  • Polyester polymers which may be used to make the yam of the invention include, but are not limited to, the polycondensation products of dicarboxylic acids or anhydrides with dihydric alcohols and mixtures of the polycondensation products.
  • Dicarboxylic acids and anhydrides which may be reacted with the dihydric alcohols include the saturated or unsaturated fatty acids and anhydrides such as maleic, fumaric, phthalic and adipic acids and anhydrides.
  • a particularly preferred dicarboxylic acid or anhydride is phthalic acid or anhydride.
  • the dihydric alcohols which are reacted with the dicarboxylic acids or anhydrides to provide the polyester polymers include, but are not limited to, the alkylene glycols having from about 2 to about 10 carbon atoms.
  • Preferred dihydric alcohols include ethylene glycol, propylene glycols, diethylene glycol and dipropylene glycol.
  • Particularly preferred polycondensation products of dicarboxylic acids or anhydrides and dihydric alcohols include polyethylene terephthalate, polybutylene terephthalate and polytrimethylene terephthalate.
  • polyester polymer A suitable source of polyester polymer is the polyethylene terephthalate polymer available from Wellman Corporation, of Johnsonville. S.C. under the trade name designation PERMACLEAR PET.
  • Other sources of polyester polymer which may be used include polybutylene terephthalate polymer available from Montefibre of Milano, Italy under the trade name TQ9/04/N and from BASF Corporation of Portsmouth, Virginia under the trade name ULTRADUR B 4500.
  • Another source is polytrimethylene terephthalate available from Du Pont Company of Wilmington, Delaware under the trade name 3GT or SONORA and that of Shell Chemical Company under the trade name CORTERRA as well as other suitable sources.
  • the blend may contain from about 0 wt. % to 20 wt. % interphase modifier.
  • Interphase modifiers that may be used, can be selected for several polyolefin polymers reacted with acids or anhydrides including fumaric acid, acrylic acid or methacrylic acid as well as maleated polyolefins.
  • maleated polyolefins examples include maleated polypropylene maleated ethylene-propylene, maleated styrene-butadiene-styrene, maleated styrene-ethylene-butadiene-styrene, maleated ethylene-propylene rubber (EPR), maleated ethylene-propylene-diene monomer (EPDM) and mixtures thereof.
  • Sources of maleated polyolefins include, but are not limited to, POLYBOND 3200 available from Uniroyal. Chemicals of Middleburg, Connecticut and EPOLENE E-43 available from Eastman Chemical Company of Kingsport, Tennessee.
  • the synthetic yarn of the invention may also contain any one or more additives selected from flame retardants, dyes, pigments, antioxidants, fillers, antistatic agents, melt processing aids, UV and thermal stabilizers, plasticizers and the like.
  • a particular advantage of the invention is the synergistic flame retardance of the yarn and fibers. Even though the filaments of the yam may contain a non-halogenated fibril-forming polymer and no flame retardants, the yarns according to the invention may exhibit about 45 to about 75% increase in flame retardance relative to the flame retardance of pure polyolefin yam. In order to further improve the flame retardance to the synthetic yarn of the invention, the fibril forming polymer may be halogenated.
  • one or both of the dicarboxylic acid or anhydride and dihydric alcohols used to make the polyester polymer may be halogenated.
  • Halogens which may be used include chlorine, bromine, and fluorine.
  • Halogenated polyester compounds prepared from the halogenated acids or alcohols may also be mixed with other well known halogenated and non-halogenated flame retardants if desired to further increase the flame retadancy of the fibers and yarns of the invention.
  • the polyolefin/fibril forming polymer mixture of the invention may also contain other flame retardants.
  • Flame retardants suitable for use with one or both the components of the mixture include, but are not limited to, brominated polystyrene, hexabromocyclododecane, decabromodiphenyl oxide, ethylene-bis(tetrabromophthalimide), ethylene-bis(dibromonorborane dicarboximide), pentabromodiphenyl oxide, octabromodiphenyl oxide, decabromo-diphenoxyethane, poly-dibromophenylene oxide, halogenated phosphate ester, tetrabromophthalic anhydride, bis(tribromophthalic anhydride), tetrabromobisphenol-A bis(2-hydroxyethyl-ether), tetrabromobisphenol-A bis(2,3-dibromopropyl ether), di
  • a preferred flame retardant system will generally contain a halogenated organic compound and a flame retardant synergist such as antimony oxide.
  • the total amount of flame retardant in the yam may range from about 5 to about 15 wt. % of the total weight of fibers. At about 10 wt. % flame retardant, there is often about a 50% increase in flame retardance as determined by the radiant panel flame retardance test.
  • Thermal stabilizers useful with the components used to produce the fibers of the invention include, but are not limited to, calcium powders, calcium stearate, phenols and hindered phenols, zinc oxide, aryl esters, hydroxybenzophenone, hydroxybenzotriazole and the like.
  • Antioxidant additives may be selected from alkylated phenols and bisphenols, alkylidene-bisphenols, alkylidene-trisphenols, alkylidene polyphenols, thiophenols, dithio-bisphenols, dithio-trisphenols, thio-polyalkylated phenols, phenol condensation products, amines, dilauryl thiodipropionate, distearyl thiodipropionate, dimyristyl thiodipropionate, ditridecyl thiodipropionate, pentaerythritol tetrakis(b-lauryl thiopropionate), p-benzoquinone, 2,5-ditert-butylhydroquinone and the like.
  • Antibacterial and anti dust-mites additives may also be used.
  • the inorganic, glassy phase or zeolite-based additives may be selected.
  • Other types of antibacterial, anti dust-mites additives may also be used.
  • polyolefin, fibril-forming polymer and optional additives may be combined in a variety of ways, however it is preferred to dry blend the components prior to feeding the blend to an extruder.
  • each of the polyolefin, fibril-forming polymer components and optional ingredients may be fed directly to the extruder in any order provided there is sufficient residence time in the extruder to assure substantially homogeneous mixing of the components. It will be recognized that a preblended essentially homogeneous mixture of polyolefin and fibril-forming polymer may also be fed to an extruder.
  • the mixture of polyolefin and polyester is melt-blended and extruded under pressure to provide an essentially homogenous mixture of the two components.
  • Pressures ranging from about 700 to about 2000 psia (about 4.8 MPa to about 13.8 MPa) are preferably used to obtain a homogeneous mixture of the components prior to extrusion.
  • the molten mixture is forced from the extruder spinneret at a temperature within the range of 240° to about 300°C through the spinneret openings.
  • the extruder temperature used is a function of the viscosity of the fibril-forming polymer in the blend.
  • the extrusion temperature is preferably in the range of from about 250° to about 290°C.
  • the extrusion temperature is preferably in the range of from about 260° to about 300°C.
  • FIG. 1 illustrates a capillary opening (10) for a spinneret for use in producing filaments for making fibers and yarns according to the invention.
  • the capillary opening is preferably a trilobal capillary configuration.
  • the capillary opening (10) has legs (12) of substantially equal length so that the melted mixture flows through the capillary opening (10) in legs (12) thereby increasing the shear rate on the molten mixture and causing the filament to set in a generally trilobal cross-sectional configuration (14) as illustrated in FIG. 2 or a delta cross-sectional configuration (16) as illustrated in FIG. 3.
  • the polyolefin (18) provides the bulk of the filament with elongate, longitudinally oriented fibrils (20) made of the fibril forming polymer dispersed within the filament generally concentrated toward the center of the filament.
  • shear rate of the molten mixture during extrusion is another important factor in practicing the present invention for optimal results.
  • Shear rates in the range of from about 1000 to about 5000 reciprocal seconds are preferred. Particularly preferred is a shear rate within the range of from about 2000 to about 4000 reciprocal seconds, with a shear rate of from about 2500 to about 3800 reciprocal seconds being especially preferred.
  • a particularly important parameter to be taken into consideration is the ratio of depth or length (L) of the capillary hole to the average hydraulic diameter (D) of the capillary 10 through which the molten mixture is forced.
  • a preferred L/D ratio is in the range of from about 3 to about 30, depending on the melt viscosity of the polyolefin and of the fibril forming polymer and on the shear rate in the capillary opening 10.
  • a ratio in the range of from about 6 to about 10 is preferably used to minimize or substantially eliminate fibrils on an exterior surface of the filaments.
  • Reactive dyeability of the fibers using acid or cationic dyes may be enhanced by use of an L/D ratio ranging from about 1 to about 3. Accordingly, an appropriately selected L/D ratio enhances the concentration of the fiber forming polymer inside the polyolefin matrix and reduces the average diameter of the fibrils.
  • the properties of the fibers and yarns of the invention are due, at least in part, to the in-situ formation of elongated, substantially discontinuous fibrils in a continuous polyolefin phase.
  • the in-situ fibril formation is believed to be promoted by the immiscibility of the components of the mixture with one another, and the shear forces exerted on the molten mixture as it is forced through the capillary openings 10 of the spinneret.
  • the presence of a compatibilizer aids to increase the spinnability and the mechanical strength of the interface between the polyolefin matrix and the immiscible polymer.
  • the forming polymer fibrils concentrate in generally longitudinally aligned orientation toward the center of the capillary openings 10 of the spinneret where the shear forces are the least.
  • the elongate fibrils are interspersed in a continuous polyolefin phase which is concentrated near the walls of the capillary openings of the spinneret where the shear forces are the greatest.
  • Polyamide and/or polyester fibrils and/or other polymers fibrils immiscible with polyolefin which are produced by the shear forces associated with passage of the material through the capillary openings 10 have a diameter in the range of a fraction of a micron to a few microns and a length of several tens of microns, whereas the overall cross-sectional length of each side of the trilobal or delta filaments containing the fibrils may range from about 1 to about 3 millimeters.
  • the fibrils will have an average diameter of from about 0.1 to about 5 microns and an average length ranging from about 100 to about 1000 microns, depending on viscosity ratio and spinning parameters.
  • the polyolefin forms into a continuous phase providing a matrix encapsulating the polymeric fibrils.
  • the polymeric fibrils provide reinforcing to the polyolefin matrix similar to reinforcing provided by fiberglass in a thermoplastic or thermoset resin. Accordingly, the polymeric fibrils which are more resilient than the polyolefin improve the resiliency of the yarn and fibers over conventional polyolefin fibers and yarns making an excellent material for carpet face yarn, textiles and upholstery.
  • polypropylene has a melt viscosity of about 240 poises at 280°C, at the capillary wall.
  • the melt viscosity for the same temperature and shear rate for polyester having an intrinsic viscosity of 0.64 is 2600 poises and is 7800 poises for polyester having an intrinsic viscosity of 0.81 at 280°C. Accordingly, the ratio of polyester polymer melt viscosity to polyolefin melt viscosity is preferably within the range of from about 10:1 to about 40:1 for producing the filaments of the invention containing polyester fibrils in a polyolefin matrix.
  • polypropylene has a melt viscosity of 330 poises at 260°C, at the capillary wall.
  • the melt viscosity for the same temperature and shear rate for nylon 6 having a relative viscosity of 2.4 is 700 poises and is 1160 poises for nylon 6 having a relative viscosity of 2.7.
  • the ratio of polyamide polymer melt viscosity to polyolefin melt viscosity is preferably within the range of from about 2:1 to about 3:1 for producing filaments containing polyamide fibrils in a polyolefin matrix.
  • the filaments are drawn one or more times, preferably three times, and then texturized with either a hot air jet or a steam jet.
  • Spinning, drawing and texturizing can be done both with the one-step or with the two step process, depending on the type of final product desired, like BCF yarn, CF yarn, POY yarn, FDY yarn, staple fibers and with parameters set as a function of the specific facilities employed.
  • the filaments of the invention may be spun, drawn and texturized essentially continuously without the need for an intermediate curing or a waiting period. In the alternative, an intermediate waiting period may be used between the spinning, drawing and/or texturizing steps.
  • the components which are combined to make the yarns of the invention may each contain pigments or chemical dyes, or the finished yarn or fibers may be dyed.
  • Useful inorganic pigments include, but are not limited to, cadmium mercury, cadmium mercury orange, cadmium sulfide yellow, cadmium sulfoselenide, titanium dioxide, titanium yellow, titanium green, titanium blue, cobalt aluminate, manganese blue, manganese violet, ultramarine red, ultramarine blue, ultra- marine violet, and the like.
  • Organic pigments include, but are not limited to, permanent red 2B, perylene red, quinacridone red, diazo orange, otiazo yellow, isoindolinone, hansa yellow, phthalocyanine green, phthalocyanine blue, quinacridone violet, dopamine violet and the like.
  • Chemical dyes include, but are not limited to, the mono- and disulfonated acid dyes, as well as triphenylmethane, pyrazolone, azine, nitro and quinoline dyes.
  • the pigment dyes may be predispersed in the polyolefin master batch before the polyolefin and fibril-forming polymer are extruded, or may be introduced after the extrusion process using a side extruder system.
  • pigment dyes are typically used during yam manufacturing to give the polyolefin its color in a process known as "solution dyeing". Solution dyeing results in a permanent color that is highly resistant to staining or fading due to UV light.
  • the fibers and yarns of the invention may be dyed with disperse dyes, in addition to the use of pigment dyes during manufacturing, and once dyed, the fibers and yarns of the invention have been found to exhibit stain resistant properties similar to pure polyolefin fibers and yarns.
  • the fibril-forming polymer used with the polyolefin to make the filaments is a polyamide
  • acid or cationic dyes it is preferred to use a mixture of an acid dye and a disperse dye to dye the filaments.
  • the mixture of dyes may contain from 0 to about 50 percent disperse dye and from about 50 to about 100 percent acid dye.
  • a particularly preferred dye is a mixture of about 50 percent by weight acid dye and about 50 percent by weight disperse dye.
  • a disperse dye is preferably used.
  • Disperse dyes are generally used with a carrier fluid which is compatible with the particular dye. Suitable carrier fluids are known to those of ordinary skill in the art.
  • the amount of dye in the carrier fluid used to color the filaments may range from about 0.15 to about 0.7 percent by weight of the dye and carrier fluid, preferably from about 0.2 to about 0.5 percent by weight of the dye and carrier fluid.
  • the filaments are preferably first washed with hot water usually containing about 0.5 % by weight of a base such as NAOH, KOH or NH 3 OH.
  • a base such as NAOH, KOH or NH 3 OH.
  • the temperature of the hot water wash ranges from about 60° to about 80°C, and should be hot enough to remove any residual finish oils which may be on the filaments.
  • the filaments are preferably dyed in a dye bath at about 90° to about 100°C, for at least 15 minutes or longer.
  • a fiber or yam made of a polyolefin/polyester mixture may be dyed using from about 0.2 to about 0.6 percent by weight disperse dye at the same temperature and pressure or at a temperature ranging from about 115°C to about 120°C, while maintaining the dye under a slight pressure.
  • the polyolefin based synthetic yam of the invention may be dyed with acid or cationic reactive dyes, with or without disperse dyes, using high pressure systems with pressures ranging from about 1 to about 5 bars. In this case a very high stable color fastness towards washing, shampoo, UV light, ozone may be obtained for fibers and yarns exposed to temperatures up to about 100°C.
  • Two types of polypropylene polymer were evaluated in a dry blend mixture containing 15 wt.% nylon 6 pellets having a relative viscosity of 2.7 (type BS-700 from BASF Corporation) and 85 wt.% polypropylene pellets having a melt index of 20 (5-1466 from Union Carbide Corporation) and polypropylene pellets having a melt index of 9 (5E40 from Union Carbide Corporation).
  • the 5E40 pellets had a crystallinity ratio of 50 to 55%.
  • the dry blend mixture was fed from a feed hopper directly into a 3.81 cm (1 1 ⁇ 2 inch) hot melt extruder wherein a homogeneous molten mixture was obtained.
  • the 85 wt.% polypropylene portion consisted of 4 wt.% beige color concentrate (SCC-13524 from Standridge Color Corporation) and 2 wt.% grafted maleic anhydride (POLYBOND 3200 from Uniroyal Chemical Company).
  • the molten mixture was then pumped through a pack of screens to remove any particles greater than 20 microns.
  • the screened mixture was pumped to a spinneret having 67 trilobal capillary openings in order to form filaments.
  • Each trilobal capillary had leg lengths of 0.05207 cm (0.0205 inch) and leg widths of 0.02032 cm (0.008 inch).
  • the extrusion rate was 0.11325 kg/h (0.25 pounds per hour) per capillary opening at 260°C thereby producing a shear rate of 3245 reciprocal seconds.
  • Carpet yam was spun from the filaments thus formed in a one-step process. The spin-draw was done using nylon 6 extrusion conditions at 1200 m/min. The trilobal-shaped filaments were spun at a weight in grams of 9000 m of filament (denier) of 3900 per 67 filaments at a temperature of 256°C. The yarns were drawn three times at 125°C and hot air jet texturized at 150°C. Drawing yielded a textured yarn having a weight in grams of 9000 m of filament (denier) of 1150 per 67 filaments.
  • the relaxation ratio was 0.71:1 and the drawn weight in grams of 9000 m of filament (denier) was targeted for 1150 with 67 filaments.
  • the physical properties of yarns made according to this process and comparative yarns are given in the following Table 1. Table 1 Run No. Description Weight in grams of 9000 m of filament. Tenacity Elongation at break (%) Bulk (%) (125°C) g/den.
  • mixtures of polypropylene and nylon exhibited substantially lower elongation than the pure polymers of either polypropylene or nylon while the other properties of the fibers were substantially the same.
  • the fiber made with nylon 6 and polypropylene having a melt index of 9 exhibited the highest tenacity and elongation at break of the mixed polymers.
  • Carpet face yarns were made from the fibers formed in Example 1.
  • the 1150 g/9000 m of filament (denier) polyolefin/nylon (PP/PA) filaments were twisted and heat set. Twisting of the filaments was at 4.25 X 4.25 tpi and the yam was heat set on a SUPERBA stuffer box at a tunnel temperature of 132°C for the polypropylene control sample and 121°C for the nylon control sample.
  • carpet formed from the PP/PA fibers exhibited a Carpet Research Institute (GRI) floor rating 29-62% better than pure polypropylene yarn and Run 4 exhibited a floor rating of 18 % better than pure nylon yarn.
  • GPI Carpet Research Institute
  • a spinneret with 64 holes, having an L/D ratio of 3 was used, with a shear rate at the capillary of about 2900 reciprocal seconds.
  • Blends of the polymers are given in Table 3.
  • both the nylon 6 (PA6) and the PP-AM were dried.
  • the moisture content in the PA6 was 300 ppm.
  • Blended yarns were made using polypropylene (PP) (UC 5E40 from Union Carbide) and nylon 6 (PA) (AQ 27000 from Aquafil) using variable amounts of PA and PP and different yarn counts. The results are shown in the following Table 4. Table 4 Run No.
  • yam made according to the invention exhibited a wear behavior which is better than that of the pure PP yarn and comparable to that of the pure nylon 6 carpet.
  • Spinning of a blend containing 20 wt.% nylon 6 and 3 wt.% of compatibilizer was performed using different spinnerets characterized by L/D ratios ranging from 2 to 15. The spinnerets were manufactured with different sizes, in order to maintain a constant shear rate of about 2900 reciprocal seconds. Spinning characteristics of the 1330 dtex / 64 filament BCF yam was similar to that of Example 3.
  • a metallographic analysis was performed to evaluate the distribution of the nylon 6 in the filaments.
  • the surface of the filaments was analyzed using a Jeol Scanning Electron Microscope (SEM) at the laboratories of the University of Trento in Italy before and after their immersion in acetic acid in order to remove nylon 6 on the external surface of the yam.
  • SEM Jeol Scanning Electron Microscope
  • the photomicrographs labeled Figs. 5-8 show the amount of nylon 6 present on the external surface of the filaments available for staining or soiling as dark space or holes where the nylon 6 was dissolved by the acid from the surface of the filaments for each of the L/D ratios used.
  • Blend spinning was performed according to Example 3, but the yam had a delta cross-section rather than a trilobal cross-section.
  • a polypropylene-based master batch was used to produce a solution dyed yam. Both beige and black color concentrates were used.
  • the blend mixture had following composition: 72 wt.% polypropylene (PP), 20 wt.% nylon 6 (PA6), 6 wt.% maleic anhydride grafted polypropylene (PP-AM), 2 wt% color concentrate.
  • the BCF yarn was extruded through a spinneret with delta cross-section holes. The shear rate inside the spinneret was 2900 reciprocal seconds and the L/D ratio of the spinneret was 3.
  • the spin-drawn speed was 2500 m/min. Hot air texturizing was performed at 130°C. The drawing ratio was 4.5. After spinning, the resulting yam had a yam count of 650 dtex with 30 filaments. The yarn had a tenacity of 3.35 g/dtex (3.7 g/den), with an elongation at break of 45% and an increase in tenacity of 15% with respect of the 100 wt. % PP.
  • the yam was dyed using an Ahiba machine using a disperse dye at 95°C for 30 minutes. The color fastness after washing was then determined. Washing was performed for 30 minutes using a water solution with a commercial shampoo at a pH of 7. The temperature at which color started to change was recorded. Results indicated that only slight color changes occurred when washing at temperatures up to 85°C.
  • Blend spinning was performed following the specification of Example 7 to produce a solution dyed yam. Both beige and black color concentrates were used.
  • the blend mixture had following composition: 72 wt% PP, 20 wt.% PA6, 6 wt.% PP-AM, 2wt% color concentrate.
  • the BCF yam was extruded through a spinneret with delta cross-section holes. The shear rate inside the spinneret was 2900 reciprocal seconds and the L/D ratio of the spinneret was 3. The spin-drawn speed was 2500 m/min. Hot air texturizing was performed at 130°C. The drawing ratio was 4.5. After spinning the resulting yam had a yam count of 650 dtex with 30 filaments.
  • the yam had a tenacity of 3.05 g/dtex (3.4 g/den), with an elongation at break of 45% and an increase in tenacity of 15% with respect of the 100 wt. % PP.
  • the yam was woven for use as upholstery, floor coverings, seating, trims, panels. Several cloth densities were manufactured as a function of the final application.
  • a wear resistance characterization was performed on the cloth with density of 11.6 yarns/cm, with a total density of 454 g/m 2 ; the warp content was 46.6%, with a remaining weft density of 53.3%.
  • the abrasion resistance of the cloth was tested using a nylon brush, with a force of 0.8 kg/cm 2 and compared to the resistance of a standard polyester based cloth manufactured using the same density after the same type of test. Testing of the polyester cloth was stopped after 2,500 cycles, and after 10,000 cycles for the claimed yam. Results are presented in Figs.9a (polyester cloth after 2,500 brush cycles) and Fig.9b (cloth made with fiber according to Example 8 after 10,000 brush cycles).
  • the claimed synthetic yarn was manufactured on a POY spinning plant.
  • An 83 wt. % PP, 15 wt. % PA6, 2 wt. %PP-AM mixture was pre-blended and fed into the extruder after drying below 300 ppm of moisture.
  • Spinning was performed at three speeds (2000, 2500 and 3000 m/min).
  • a 100/24 POY yarn was produced.
  • the resulting mechanical properties of the POY are presented in the following Table. After spinning an FDY was manufactured. A drawing ratio of 1.374 was applied, using a godet temperature of 60°C. Results are presented in Table 6.
  • the performance of the claimed synthetic yam in terms of resilience and mechanical properties as a function of temperature was characterized at high temperatures and compared with the performances of the same yarn manufactured using 100 wt.% PP.
  • the effect of the heat treatment was also tested.
  • the resilience of the yarn was evaluated using laboratory tests by imposing a deformation to the yarn and evaluating its capability to recover it after deloading. Tests were performed at room temperature and at higher temperatures. In the tests performed using the dynamic apparatus at the University of Trento, Department of Materials, a maximum deformation of 16 mm was imposed to the yam with a frequency of 5 Hz. To test the yarn a static load of 0.05 N/dtex was applied onto a single filament.
  • Fig. 10 demonstrated that the yam made according to the invention (Curve A) provided a much higher shape retention at room temperature, when compared to 100 wt.% PP yam (Curve C), which started to have a irreversible deformation above -20°C, i.e. above its glass transition temperature. At 25°C the deformation of the claimed yam was below 3 %, indicating an excellent resilience, while the 100 wt.% PP yam had already reached 30% of permanent deformation.
  • Examples of use of yarn made according to the invention include but are not limited to: underwear, outwear, sportswear, leisure, socks, apparel, strings, filters for the chemical industry.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Artificial Filaments (AREA)
  • Chemical Treatment Of Fibers During Manufacturing Processes (AREA)
  • Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)

Claims (20)

  1. Verfahren zur Herstellung von Fasern und Garnen mit einem im Bereich von etwa 1 bis etwa 30 liegenden Gewicht in Gramm von 9000 m des Filaments (Denier pro Filament (dpf)) und verbesserten mechanischen Eigenschaften, umfassend:
    Vermengen von etwa 55 bis etwa 95 Gew.% Polyolefin-Polymer und von etwa 5 bis etwa 45 Gew.% Fibrillen bildendem Polymer, um eine Mischung aus Polyolefin- und Fibrillen bildenden Polymeren bereitzustellen, wobei das Fibrillen bildende Polymer mit dem Polyolefin-Polymer unmischbar ist;
    Zuführen der Mischung zu einem Schmelzextruder, um eine im wesentlichen homogene geschmolzene Mischung aus Polyolefin- und Fibrillen bildenden Polymeren bereitzustellen;
    Pressen der geschmolzenen Mischung durch eine Spinndüse mit einem Längen zu Durchmesserverhältnis (L/D) im Bereich von etwa 3 bis etwa 30, bei einer Schergeschwindigkeit im Bereich von etwa 1000 bis etwa 5000 reziproken Sekunden, um eine Faser mit einer Polyolefin-Matrix und langgestreckten, im wesentlichen diskontinuierlichen Fibrillen des in der Polyolefin-Matrix dispergierten Fibrillen bildenden Polymers bereitzustellen, wodurch eine äußere Oberfläche der Fasern im wesentlichen frei von Fibrillen ist.
  2. Verfahren nach Anspruch 1, worin das Fibrillen bildende Polymer aus der Gruppe gewählt ist, die aus Polyamid-Polymeren und Polyester-Polymeren besteht.
  3. Verfahren nach Anspruch 1, worin das Polyolefin-Polymer Polypropylen enthält.
  4. Verfahren nach Anspruch 1, worin die Mischung von etwa 15 bis etwa 30 Gew.% an Fibrillen bildendem Polymer enthält.
  5. Verfahren nach Anspruch 1, worin das L/D-Verhältnis der Spinndüse im Bereich von etwa 6 bis etwa 10 liegt.
  6. Verfahren nach Anspruch 1, worin die Mischung aus Polyolefin und Fibrillen bildendem Polymer etwa 0 bis etwa 20 Gew.% Polyolefin-Kompatibilisierungsmittel enthält, ausgewählt aus der Gruppe bestehend aus Polypropylen-Maleat, Ethylen/Propylen-Maleat-Copolymer, Styrol/Butadien/Styrol-Maleat-Copolymer, Styrol/Ethylen/Butadien/Styrol-Maleat-Copolymer, monomeres Ethylen/Propylen/Dien-Maleat-Copolymer und Ethlen/Propylen-Maleat-Kautschuk.
  7. Verfahren nach Anspruch 6, weiterhin umfassend Trocknen des Polyolefin-Polymers, Fibrillen bildenden Polymers und Kompatibilisierungsmittels, um eine Mischung bereitzustellen, die weniger als etwa 500 ppm Feuchtigkeit enthält.
  8. Verfahren nach Anspruch 1, weiterhin umfassend Trocknen des Polyolefin-Polymers und Fibrillen bildenden Polymers, um eine Mischung bereitzustellen, die weniger als etwa 500 ppm Feuchtigkeit enthält.
  9. Verfahren nach Anspruch 1, weiterhin umfassend Färben der Fasern mit einem Dispersionsfarbstoff, einem Reaktivfarbstoff oder einer Mischung aus beiden, um gefärbte Fasern bereitzustellen.
  10. Verfahren nach Anspruch 9, worin das Färben bei einem sich von etwa 1 bis etwa 4 bar erstreckenden Druck vorgenommen wird.
  11. Verfahren nach Anspruch 9, worin das Färben bei einem sich von etwa 1,5 bis etwa 2 bar erstreckenden Druck vorgenommen wird.
  12. Garn mit verbesserten mechanischen Eigenschaften, umfassend von etwa 55 bis 95 Gew.% kontinuierliche Polyolefinphase und von etwa 5 bis etwa 45 diskontinuierliche Phase von Fibrillen, die in der kontinuierlichen Polyolefinphase dispergiert sind, wobei die Fibrillen abgeleitet sind aus einem Fibrillen bildenden Polymer, ausgewählt aus der aus Polyamid-Polymeren und Polyester-Polymeren bestehenden Gruppe, worin die kontinuierliche Polyolefinphase auf einer exponierten Oberfläche davon im wesentlichen frei von Fibrillen ist und worin das Garn färbbar ist und eine irreversible Deformation bei etwa 25 °C von weniger als etwa 3 % hat.
  13. Garn nach Anspruch 12, worin die kontinuierliche Polyolefinphase Polypropylen enthält.
  14. Garn nach Anspruch 13, worin die Fibrillen Polyester enthalten.
  15. Garn nach Anspruch 13, worin die Fibrillen Polyamid enthalten.
  16. Garn nach Anspruch 12, worin die Fibrillen kationisches färbbares Polyamid umfassen.
  17. Verwendung des Garns nach Anspruch 12, umfassend ein BCF-Garn als Teppichgarn.
  18. Verwendung des Garns nach Anspruch 12, umfassend ein POY-, FDY- oder LDY-Garn als Textilgarn.
  19. Verwendung des Garns nach Anspruch 12 als Polstergarn.
  20. Verwendung des Garns nach Anspruch 13 als Stapelgarn.
EP01975559A 2001-09-28 2001-09-28 Polyolefinbasierende synthesefasern und verfahren zu deren herstellung Expired - Lifetime EP1446518B9 (de)

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EP1446518A4 EP1446518A4 (de) 2005-09-07
EP1446518B1 true EP1446518B1 (de) 2007-10-10
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DE102006020661A1 (de) * 2006-05-04 2007-11-22 TAG Textilausrüstungs-Gesellschaft Schroers GmbH & Co KG Verfahren und Färbung moderner Sauberfasern
ITMI20072383A1 (it) * 2007-12-19 2009-06-20 Eugenio Magni Processo per la preparazione di polipropilene tingibile.
US20120231207A1 (en) * 2011-03-07 2012-09-13 Moshe Rock Textile fabric with high insulation to weight ratio
CN104204313B (zh) * 2012-03-23 2018-04-20 东丽株式会社 聚甲基戊烯复合纤维或聚甲基戊烯多孔质纤维以及包含它们的纤维结构体
DE102013100613A1 (de) * 2013-01-22 2014-07-24 Boockmann Gmbh Textiler Materialstrang sowie Verfahren zu seiner Herstellung
CN104862824A (zh) * 2014-02-20 2015-08-26 南通永盛纤维新材料有限公司 大有光涤锦复合纤维及其生产方法
EP3562980B1 (de) * 2016-12-27 2024-01-10 SABIC Global Technologies B.V. Fasern mit fibrilliertem verstärkungsmaterial

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US5811040A (en) * 1994-11-14 1998-09-22 Mallonee; William C. Process of making fiber for carpet face yarn

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CA2461945C (en) 2010-04-20
DK1446518T3 (da) 2007-11-05
WO2003029536A1 (en) 2003-04-10
CA2461945A1 (en) 2003-04-10
EP1446518A1 (de) 2004-08-18
EP1446518A4 (de) 2005-09-07
ATE375412T1 (de) 2007-10-15
DE60130931T2 (de) 2008-07-17
AU2001294875B2 (en) 2007-07-05
DE60130931D1 (de) 2007-11-22
ES2295212T3 (es) 2008-04-16

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