WO2005024104A1 - Fibres thermoplastiques presentant des caracteristiques durables d'intensite de couleur elevee - Google Patents

Fibres thermoplastiques presentant des caracteristiques durables d'intensite de couleur elevee Download PDF

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Publication number
WO2005024104A1
WO2005024104A1 PCT/US2004/024154 US2004024154W WO2005024104A1 WO 2005024104 A1 WO2005024104 A1 WO 2005024104A1 US 2004024154 W US2004024154 W US 2004024154W WO 2005024104 A1 WO2005024104 A1 WO 2005024104A1
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WIPO (PCT)
Prior art keywords
fiber
fabric
textured
multifilament
thermoplastic
Prior art date
Application number
PCT/US2004/024154
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English (en)
Inventor
Martin E. Cowan
Joseph R. Royer
Sonya Dai
Brian G. Morin
Original Assignee
Milliken & Company
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Publication date
Priority claimed from US10/651,444 external-priority patent/US20050048281A1/en
Priority claimed from US10/651,776 external-priority patent/US20050046065A1/en
Priority claimed from US10/651,777 external-priority patent/US6849330B1/en
Application filed by Milliken & Company filed Critical Milliken & Company
Publication of WO2005024104A1 publication Critical patent/WO2005024104A1/fr

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Classifications

    • 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
    • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/04—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyolefins
    • D01F6/06—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyolefins from polypropylene
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/04—Pigments
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/06—Dyes
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D01F1/106—Radiation shielding agents, e.g. absorbing, reflecting agents
    • 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
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/06—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyolefin as constituent
    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
    • D02G3/22—Yarns or threads characterised by constructional features, e.g. blending, filament/fibre
    • D02G3/34—Yarns or threads having slubs, knops, spirals, loops, tufts, or other irregular or decorative effects, i.e. effect yarns
    • D02G3/346—Yarns or threads having slubs, knops, spirals, loops, tufts, or other irregular or decorative effects, i.e. effect yarns with coloured effects, i.e. by differential dyeing process
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/54—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by welding together the fibres, e.g. by partially melting or dissolving
    • D04H1/56—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by welding together the fibres, e.g. by partially melting or dissolving in association with fibre formation, e.g. immediately following extrusion of staple fibres
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
    • D04H3/08—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating
    • D04H3/16—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating with bonds between thermoplastic filaments produced in association with filament formation, e.g. immediately following extrusion

Definitions

  • This invention relates to improvements in permitting brighter colorations within thermoplastic fibers and/or yarns while simultaneously providing more efficient production methods of manufacturing of such colored fibers as well.
  • fibers and/or yams have been colored with pigments, which exhibit dulled results, or dyes, which exhibit high degrees of extraction and low levels of lightfastness.
  • Such dull appearances, high extraction levels, and less than stellar lightfastness properties negatively impact the provision of such desirable colored thermoplastic (such as, without limitation, polypropylene) fibers and/or yams which, in turn, prevents the widespread utilization of such fibers and yams in various end-use applications.
  • thermoplastic fibers have been utilized many years for myriad different fabric and textile applications.
  • polyolefin, polyester, and polyamide fibers have been prominent as replacements for naturally occurring fibers (such as cotton and wool, for instance) due to lower costs, more reliability in supply, physical properties, and other like benefits.
  • Colorations have been available for such thermoplastic, synthetic fibers in order to provide aesthetic, identification, and other properties. Such colorations have been mostly provided through pigments that thoroughly color the target fibers and exhibit sufficiently high lightfastness and crocking characteristics that use thereof has not been curtailed.
  • Dyeing within baths is available for already-formed fabrics (such as knit, woven, and/or non-woven textiles), if a solid color is desired, and also for yams with selected properties through package dyeing procedures.
  • accent yams or other fibers that require individual colorations requires coloring during production.
  • some polymers such as polypropylene, polyethylene, etc., have not been heretofore able to accept dyes of any kind, and have thus been colored with pigment.
  • pigment colorants are prevalent and generally effective at providing color within such thermoplastic fibers, there are certain drawbacks for which improvements have been unavailable.
  • pigments are notoriously capable of staining fiber manufacturing/extrusion machinery such that control of discolorations within subsequently produced fibers is rather difficult, and the time required to change colors is high.
  • pigments impart a dulling appearance, a lack of brightness, and a low luster, all believed to be due to the solid nature of such coloring agents.
  • pigment size and dispersion limits the processability of small fibers, which are desirable for their improved touch and feel.
  • improvements in such areas are desirable for coloring agents to be introduced within thermoplastic fibers.
  • improvements in coloring individual polyolefin fibers are needed.
  • polyesters such as polyethylene terephthalate, or PET
  • polyamides such as nylons
  • PET polyethylene terephthalate
  • nylons such fibers
  • Pigments the most prevalent of polyolefin fiber colorants utilized throughout the fabric industry, as noted above, are, as is well-known, solid particles that require a relatively high amount to provide sufficiently deep colorations within such target materials.
  • Dyes have also been utilized to color not only polyolefin fibers and/or yams, but also materials such as nylon, polyesters, cotton, and other fiber types.
  • polyolefms are an economically superior fiber as compared with other synthetic types (polyesters, nylons, for example); however, its widespread use has been limited due to such issues as this coloration problem.
  • pigments efficiency is compromised during fiber manufacture such that any cost benefits of utilizing polyolefin as compared with other synthetic fiber and/or yarn types are reduced to a level that is unacceptable for displacement within the fabric industry.
  • the pigments are normally matched to a standard shade in a high concentration masterbatch that is then diluted with uncolored polymer during the fiber manufacture.
  • there is a problem or mismatch between the color masterbatch there is only limited adjustment available at the fiber manufacturing stage. This often necessitates re-manufacture of the masterbatch, adding expense and delaying the manufacturing process.
  • thermoplastic such as polypropylene, as one non-limiting example
  • fibers and/or yams that exhibit extremely bright and aesthetically pleasing colorations as compared to pigmented products.
  • a further object of the invention is to provide such colorations that are of very low, if nonexistent, extraction.
  • a further object of the invention is to provide a specific method for the production of brightly colored thermoplastic fibers that permits quick and efficient changeover from one colorant to another.
  • another object of this invention is to provide a brightly colored thermoplastic fiber and/or yarn that exhibits outstanding lightfastness properties, either alone or in the presence of minimal amounts of UV absorber additives.
  • Another object of the invention is to provide a process for manufacturing fibers using liquid colors in which the shade can be adjusted to match some standard. Accordingly, this invention encompasses a colored thermoplastic fiber compromising a liquid colorant present therein in a rod-like configuration. Furthermore, this invention encompasses a colored thermoplastic fiber including at least one liquid colorant therein, wherein said at least one liquid colorant therein exhibits a very low extraction and crocking level therefrom.
  • this invention encompasses a method of producing a colored thermoplastic fiber including the steps of a) providing a molten thermoplastic formulation, optionally including colored thermoplastic concentrates therein, wherein said concentrates comprise at least one liquid polymeric colorant; and b) extruding said thermoplastic formulation of step "a" within a fiber extrusion line to form a colored thermoplastic fiber, wherein, optionally at least one liquid polymeric colorant is simultaneously injected within said fiber extrusion line during extrusion of said thermoplastic formulation of step "a"; and.
  • this process has the additional steps of providing multiple liquid color constituents in step "a” or "b", matching the resulting fibers to a standard, and adjusting the ratio of the multiple liquid color constituents so provided to adjust the color of the resulting fiber to match the standard.
  • This invention also encompasses the formation of a colored film including such liquid polymeric colorants, and the formation of colored tape fibers therefrom.
  • thermoplastic is intended to mean a polymeric material that will melt upon exposure to sufficient heat but will retain its solidified state, but not prior shape without use of a mold or like article, upon sufficient cooling.
  • thermoplastic is to be utilized to from fibers and/or yams through any number of techniques, including, without limitation, extrusion (for multifilament and mono filament types), spinning, water- and/or air-quenching, spun-bonded and/or melt-blown non-woven products, staple fibers, bicomponent/splittalbe fibers, tape and/or ribbon fibers (through slit film procedures, as one example), and the like.
  • polymers contemplated within such a definition include, without limitation, polyolefins (such as polyethylene, polypropylene, polybutylene, and any combination thereof), polyamides (such as nylon), polyurethanes, polyesters (such as polyethylene terephthalate), polylactic acids, and any copolymers of these broad types, either within the same classification or not.
  • Polypropylene fibers are most preferred, although polyesters are preferred as well.
  • the particular polypropylene fiber and/or yarn of this invention may be of any denier, including microdeniers (below about 1.5 denier per fiber) or higher deniers 1.5 denier per fiber or higher), as merely examples.
  • the target fibers and/or yarns may also be textured in any manner commonly followed for polypropylene materials.
  • BCF bulked continuous filament
  • polypropylene is intended to encompass any polymeric composition comprising propylene monomers, either alone or in mixture or copolymer with other randomly selected and oriented polyolefins, dienes, or other monomers (such as ethylene, butylene, and the like). Such a term also encompasses any different configuration and arrangement of the constituent monomers (such as syndiotactic, isotactic, and the like). Thus, the term as applied to fibers is intended to encompass actual long strands, tapes, threads, and the like, of drawn polymer.
  • the polypropylene may be of any standard melt flow (by testing); however, standard fiber grade polypropylene resins possess ranges of Melt Flow Indices between about 1 and 1000. Contrary to standard manufacturing procedures and techniques for plaques, containers, sheets, and the like (such as taught within U.S. Pat. No. 4,016,118 to Hamada et at, for example), fibers clearly differ in structure since they must exhibit a length that far exceeds its cross-sectional area (such, for example, its diameter for round fibers). Fibers are extruded and drawn; articles are blow-molded or injection molded, to name two alternative production methods. Also, the crystalline morphology of polypropylene within fibers is different than that of standard articles, plaques, sheets, and the like.
  • the dpf of such polypropylene fibers is at most about 5000; whereas the dpf of these other articles is much greater.
  • Polypropylene articles generally exhibit spheralitic crystals while fibers exhibit elongated, extended crystal structures.
  • any predictions made for spheralitic particles (crystals) of colored polypropylene articles do not provide any basis for determining the effectiveness of coloring agents as additives within polypropylene fibers.
  • plaques made with pigments can exhibit bright, deep shades, and still appear transparent, hi fiber form, dullness (low brightness) and opacity are prominent when deep shades of pigmented fibers are produced.
  • the coloring agents particularly useful within this invention are those that are liquid in nature, preferably, though not necessarily, polymeric in nature [i.e., poly(oxyalkylenated)] to the extent that, upon introduction within such target polypropylene fibers, extraction therefrom is severely limited, if not nonexistent.
  • the term "liquid” is intended to mean that such colorants are liquid at room temperature and standard pressure (25°C at 1 atmosphere).
  • Example colorants that meet these limitations are those that are available from Milliken & Company under the tradename CLEARTINT®. Alternatively, liquid dyestuffs may also be utilized, although less preferred than polymeric types.
  • the preferred colorants in this general class are represented by the following formula
  • R is an organic chromophore
  • A is a linking moiety in said chromophore selected from the group consisting of N, O, S, SO 2 N, and CO 2
  • B is an alkyleneoxy constituent contains from 2 to 4 carbon atoms
  • n is an integer of from 2 to about 500
  • m is 1 when A is O, S, or CO 2
  • m is 2 when A is N or SO 2 N
  • x is an integer of from 1 to about 5.
  • the molecular weight of such colorants are at least 2000 and, due to the high oxyalkylenation present, are highly water soluble and liquid at room temperature.
  • the organic chromophore is, more specifically, one or more of the following types of compounds: azo, diazo, disazo, trisaz ' o, diphenylmethane, triphenylmethane, xanthene, nitro, nitroso, acridine, methine, styryl, indamine, thiazole, oxazine, stilbene, or anthraquinone.
  • the chromophore may be optically inactive, at least within the visible spectrum, but absorb uv radiation, as one example, thereby imparting ultraviolet protection to the target fibers.
  • R is one or more of azo, diazo, triphenylmethane, methine, anthraquinone, or thiazole based compounds. Such a group may produce coloring effects that are evident to the eye; however, optical brightening chromophores are also contemplated in this respect.
  • Group A is present on group R and is utilized to attach the polyoxyalkylene constituent to the organic chromophore. Nitrogen is the preferred linking moiety.
  • the polyoxyalkylene group is generally a combination of ethylene oxide and propylene oxide monomers.
  • propylene oxide is present in the major amount, and most preferably the entire polyoxyalkylene constituent is propylene oxide.
  • the preferred number of moles (n) of polyoxyalkylene constituent per polyoxyalkylene chain is from 2 to 50, more preferably from 10 to 30. Also, preferably two such polymeric chains are present on each polymeric colorant compound (x, above, is preferably 2). In actuality, the number of moles (n) per polymeric chain is an average of the total number present since it is very difficult to control the addition of specific numbers of moles of alkyleneoxy groups.
  • the Table below lists the particularly preferred colorants (with the range of alkoxylation present on the colorant listed due to the inexactness of production of specific chain lengths) for utilization in relation to Structure (I), above:
  • Such colorants provide the aforementioned, highly desirable, low extraction properties, as well as the significant bright colorations as compared with pigmented fibers. Without intending on being limited to any specific scientific theory, it appears that such colorants are capable of complete introduction within the target polypropylene fibers to the extent that transparent thin rod-like configurations of the liquid colorants are present within the fibers after extrusion. Such configurations thus permit an even distribution of color throughout the target fiber, and, apparently, with a strong cohesive nature while present therein said fibers, such thin rod-like configurations are not amenable to easy migration from therein either.
  • such long strands will appear as small dots within the target fibers. These dots will be the tops of these rod-like structures which can then be noticed from side views as the aforementioned strands.
  • these strands are basically pools of liquid color stretched during the fiber extrusion process, these stractures will exhibit aspect ratios (length to diameter) of from 10:1 to 500,000:1, preferably from 50:1 to 100,000:1, more preferably from 50:1 to 10,000:1, and most preferably from 100:1 to 1,000:1.
  • the term rod-like is intended to encompass these high aspect ratio strands of liquid color within target thermoplastic fibers.
  • thermoplastic Since the thermoplastic will be colorless, or at least sufficiently different in color from the added liquid coloring agent, it is relatively easy to view such rod-like stractures through side views coupled with cross- sectional views. Again, the continuous strands of color or easily viewed from the side; the "dots" of tops of different strands 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 film-like stractures 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 appearance of the above-discussed pigmented fibers that require a large amount of solid particles therein to provide even colorations throughout, but which, as a result, also exhibit very dull appearances as well.
  • the colored transparent nature available with these inventive liquid colorants produces the bright colorations, much like a colored filter placed over a light imparts a bright, colored effect when the light shines therethrough.
  • the fibers themselves are generally solid in nature, and, cross-sectionally, appear as round, triangular, square, and/or rectangular in shape, but may have any cross sectional shape, such as octalobal which is popular in carpet fibers.
  • Such fibers may also include the presence of certain compounds that quickly and effectively provide rigidity and/or tensile strength to the target polypropylene fiber to a level heretofore unavailable, particularly in terms of permitting highspeed spinning for greater efficiency in fiber and/or yarn manufacturing.
  • these compounds include any structure that nucleates polymer crystals within the target polypropylene after exposure to sufficient heat to melt the initial pelletized polymer and upon allowing such a melt to cool. The compounds must nucleate polymer crystals at a higher temperature than the target polypropylene without the nucleating agent during cooling.
  • the nucleator compounds provide nucleation sites for polypropylene crystal growth which, in turn, appear to provide thick lamellae within the fibers themselves which, apparently (without intending on being bound to any specific scientific theory) increase the processability of the target fibers to such a degree that the tensions associated with high-speed spinning can easily be withstood.
  • the preferred nucleating compounds include dibenzylidene sorbitol based compounds, as well as less preferred compounds, such as sodium benzoate, certain sodium and lithium phosphate salts (such as sodium 2,2'-methylene-bis-(4,6-di-tert- butylphe ⁇ yl)phosphate, otherwise known as NA-11 or NA-21), zinc glycerolate, and others.
  • the amount of nucleating agent present within the inventive fiber is at least 10 ppm; preferably this amount is at least 100 ppm; and most preferably is at least 1250 ppm. Any amount of such a nucleating agent should suffice to provide the desired shrinkage rates after heat-setting of the fiber itself; however, excessive amounts (e.g., above about 10,000 ppm and even as low as about 6,000 ppm) should be avoided, primarily due to costs, but also due to potential processing problems with greater amounts of additives present within the target fibers.
  • nucleators suitable for incorporation within the inventive colored fibers include saturated metal or organic salts of bicyclic dicarboxylates, preferably saturated metal or organic salts of bicyclic dicarboxylates, preferably, bicyclo[2.2.1]heptane-dicarboxylates, or, generally, compounds conforming to Formula (I) (I)
  • R l5 R , R 3 , P ⁇ , R 5 , R 6 , R 7 , R 8 , R 9 , and R 10 are individually selected from the group consisting of hydrogen, C ⁇ .-C 9 alkyl, hydroxy, -C 9 alkoxy, C ⁇ -C 9 alkyleneoxy, amine, and C1 .
  • R' and R" are the same or different and are individually selected from the group consisting of hydrogen, Ci-C 3 o alkyl, hydroxy, amine, polyamine, polyoxyamine, Ci-C 3 o alkylamine, phenyl, halogen, -C 30 alkoxy, C ⁇ -C 30 polyoxyalkyl, C(O)-NR ⁇ C(O)O- R'", and C(O)O-R'", wherein ⁇ is selected from the group consisting of C1 .
  • R' is selected from the group consisting of hydrogen, a metal ion (such as, without limitation, Na + , K , Li + personallyAg + and any other monovalent ions), an organic cation (such as ammonium as one non-limiting example), polyoxy-C 2 -C 18 -alkylene, C ⁇ -C 30 alkyl, C 1 -C3 0 all lene, C1-C 30 al yleneoxy, a steroid moiety (for example, cholesterol), phenyl, polyphenyl, C1.-C 30 alkylhalide, and -C 30 allcylamine; wherein at least one of R' and R" is either C(O)-NR n C(O)O-R'" or C(O)O-R'", wherein if both R' and R" are C(O)O-R'" then R'"
  • R' and R" are the same and R'" is either Na or combined together for both R' and R" and Ca .
  • R' and R" are either Na or combined together for both R' and R" and Ca .
  • Other possible compounds are discussed in the preferred embodiment section below.
  • such a compound conforms to the structure of Formula (II) ( ⁇ )
  • M 1 and M are the same or different and are independently selected from the group consisting of metal or organic cations or the two metal ions are unified into a single metal ion (bivalent, for instance, such as calcium, for example), and R l5 R 2 , R 3 , R , R 5 , R 6 , R , R 8 , R 9 , and Rio are individually selected from the group consisting of hydrogen, C 1 -C 9 alkyl, hydroxy, -C 9 alkoxy, C ⁇ -C 9 alkyleneoxy, amine, and C ⁇ -C 9 alkylamine, halogen, phenyl, alkylphenyl, and geminal or vicinal carbocyclic having up to 9 carbon atoms.
  • the metal cations are selected from the group consisting of calcium, strontium, barium, magnesium, aluminum, silver, sodium, lithium, rubidium, potassium, and the like.
  • group I and group II metal ions are generally preferred.
  • group I and TJ cations sodium, potassium, calcium and strontium are preferred, wherein sodium and calcium are most preferred.
  • the Mi and M 2 groups may also be combined to form a single metal cation (such as calcium, strontium, barium, magnesium, aluminum, including monobasic aluminum, and the like).
  • this invention encompasses all stereochemical configurations of such compounds, the cis configuration is preferred wherein cis-endo is the most preferred embodiment.
  • polyolefin articles and additive compositions for polyolefin formulations comprising at least one of such compounds, broadly stated as saturated bicyclic carboxylate salts, are also encompassed within this invention.
  • the terms "nucleators”, “nucleator compound(s)”, “nucleating agent”, and “nucleating agents” are intended to generally encompass, singularly or in combination, any additive to polypropylene that produces nucleation sites for polypropylene crystals from transition from its molten state to a solid, cooled structure.
  • the nucleator compound will provide such nucleation sites upon cooling of the polypropylene from its molten state.
  • the only way in which such compounds provide the necessary nucleation sites is if such sites form prior to polypropylene recrystallization itself.
  • any compound that exhibits such a beneficial effect and property is included within this definition.
  • Such nucleator compounds more specifically include dibenzylidene sorbitol types, including, without limitation, dibenzylidene sorbitol (DBS), monomethyldibenzylidene sorbitol, such as l,3:2,4-bis(p-methylbenzylidene) sorbitol (p-MDBS), dimethyl dibenzylidene sorbitol, such as l,3:2,4-bis(3,4-dimethylbenzylidene) sorbitol (3,4-DMDBS); other compounds of this type include, again, without limitation, sodium benzoate, NA-11, NA-21, bicyclic dicarboxylate salts, and the like.
  • DBS dibenzylidene sorbitol
  • p-MDBS monomethyldibenzylidene sorbitol
  • p-MDBS dimethyl dibenzylidene sorbitol
  • 3,4-DMDBS dimethyl dibenzylidene sorbito
  • the concentration of such nucleating agents (in total) within the target polypropylene fiber is at least 100 ppm, preferably at least 1250 ppm.
  • concentration of such nucleating agents (in total) within the target polypropylene fiber is at least 100 ppm, preferably at least 1250 ppm.
  • nucleators which perform the best are those which exhibit relatively high solubility within the propylene itself.
  • DBS derivative compounds are considered the best snrink-reducing nucleators within this invention due to the low crystalline sizes produced by such compounds.
  • nucleators such as NA-11
  • NA-11 also impart acceptable characteristics to the target polypropylene fiber in terms of, for example, withstanding high speed spinning tensions; however, apparently due to poor dispersion of NA-11 in polypropylene and the large and varied crystal sizes of NA-11 within the fiber itself, the performance is less consistent than for the highly soluble, low crystal-size polypropylene produced by well-dispersed 3,4- DMDBS or, preferably, p-MDBS. It has been determined that the nucleator compounds that exhibit good solubility in the target molten polypropylene resins (and thus are liquid in nature during that stage in the fiber- production process) provide more effective fiber properties for withstanding high speed spinning tension levels.
  • substituted DBS compounds include DBS, 3,4-DMDBS, and, preferably p-MDBS
  • DBS 3,4-DMDBS
  • p-MDBS p-MDBS
  • any of the above-mentioned nucleators may be utilized within this invention. Mixtures of such nucleators may also be used during processing in order to provide such spinning efficiencies and low-shrink properties as well as possible organoleptic improvements, facilitation of processing, or cost.
  • sodium benzoate and NA-11 are well known as nucleating agents for standard polypropylene compositions (such as the aforementioned plaques, containers, films, sheets, and the like) and exhibit excellent recrystallization temperatures and very quick injection molding cycle times for those purposes.
  • the dibenzylidene sorbitol types exhibit the same types of properties as well as excellent clarity within such standard polypropylene forms (plaques, sheets, etc.).
  • the dibenzylidene sorbitol types are preferred as nucleator compounds within the target polypropylene fibers.
  • such fibers may include other coloring agents, such as pigments, titanium dioxide, and the like, as well as fixing agents for lightfastness purposes.
  • thermoplastics any type of ultraviolet absorber compound or formulation that is dispersible within thermoplastics maybe utilized within this invention.
  • phenolic antioxidants such as HOSTANOX® 245, O10, O14, O16, O3, and blends with HOSTANOX® M, all available from Clariant; processing stabilizers, such as HOSTANOX® PAR 24, SANDOSTAB® PEPQ (from Clariant), and blends with SANDOSTAB® QB; sulfur-containing co-stabilizers, such as HOSTANOX® SE 4 or SE 10; metal deactivators, such as HOSTANOX® OSP 1; light stabilizers, such as NYLOSTAB® S- EED (from Clariant, as well); and straightforward ultraviolet absorbers, such as
  • Preferred is TESIUVIN® 783 for such a purpose.
  • additives may also be present, including antistatic agents, brightening compounds, clarifying agents, antioxidants, antimicrobials (preferably silver-based ion-exchange compounds, such as ALPHASAN® antimicrobials available from Milliken & Company), fillers, and the like.
  • antistatic agents preferably silver-based ion-exchange compounds, such as ALPHASAN® antimicrobials available from Milliken & Company
  • antimicrobials preferably silver-based ion-exchange compounds, such as ALPHASAN® antimicrobials available from Milliken & Company
  • fillers preferably silver-based ion-exchange compounds, such as ALPHASAN® antimicrobials available from Milliken & Company
  • any fabrics made from such inventive fibers may be, without limitation, woven, knit, non- woven, in-laid scrim, any combination thereof, and the like.
  • such fabrics may include fibers other than the inventive polypropylene fibers, including, without limitation, natural fibers, such as cotton, wool, abaca, hemp, ramie, and the like; synthetic fibers, such as polyesters, polyamides, polyaramids, other polyolefins (including non-low- shrink polypropylene), polylactic acids, and the like; inorganic fibers such as glass, boron- containing fibers, and the like; and any blends thereof.
  • this invention can be practiced with any melt extradable thermoplastic polymer, such as polyester, nylon, poly lactic acid, and the like, with similar results.
  • inventive fibers can be included in a fabric such as a carpet, upholstery fabric, woven fabric, knit fabric, nonwoven, pile fabric, netting, and the like.
  • these fibers can be combined in such fabric stractures as accent yarns, especially if the additional non-inventive fibers are dye accepting.
  • the inventive yams provide accent yarns with bright appearance.
  • individual yams maybe incorporated within non- fabric stractures, such as, as one non-limiting example, fishing lures, and other end-uses in which brightly colored strong fibers are desirable.
  • Inventive yams and fibers can be used in any standard textile process, including, without limitation, such methods as yarn texturing processes such as stuffer box, bulk continuous filament (BCF), air jet texturing, twisting, false twist testing, and the like. They can also be combined with other yams or used in other processes to make "elegant" or “fancy” yarns, such as chenille, slub yams, stria yams, etc., with all of the incumbent advantages of combining the technologies.
  • the transparent nature of the color can be used in light weight fabrics to make colored transparent fabrics such as may be desirable to show a pattern on a substrate covered by the inventive fabric.
  • FIG. 1 is a schematic of the potentially preferred method of producing colored polypropylene fibers through typical spinning machinery.
  • FIG. 2 is a schematic of the potentially preferred method of producing colored polypropylene tape fibers.
  • FIG. 3 is a schematic of the potentially preferred method of producing colored polypropylene fibers through typical high-speed spinning machinery.
  • FIG. 4 is a side-view color microphotograph of a green-colored inventive polypropylene fiber magnified at 565X colored with a liquid polymeric colorant.
  • FIG. 1 is a schematic of the potentially preferred method of producing colored polypropylene fibers through typical spinning machinery.
  • FIG. 2 is a schematic of the potentially preferred method of producing colored polypropylene tape fibers.
  • FIG. 3 is a schematic of the potentially preferred method of producing colored polypropylene fibers through typical high-speed spinning machinery.
  • FIG. 4 is a side-view color microphotograph of a green-colored inventive polypropylene fiber magnified at 565X colored with a liquid polymeric colorant.
  • FIG. 5 is a side-view color microphotograph of a comparative green-colored polypropylene yarn magnified at 565X having pigments present throughout.
  • FIG. 6 is a cross-sectional view of a plurality of green-colored inventive polypropylene fibers magnified at 565X colored with a liquid polymeric colorant.
  • FIG. 1 depicts the non-limiting preferred procedure followed in producing the inventive low denier polypropylene fibers.
  • the entire fiber production assembly 10 comprises an extruder 11 including a metering pump (not illustrated) for introduction of specific amounts of polymer into the extruder 11 (to control the denier of the ultimate target manufactured fiber and/or yarn) which also comprises four [five] different zones 12, 14, 16, 18, 20 through which the polymer (not illustrated) passes at different, increasing temperatures.
  • the molten polymer is mixed with the liquid polymeric colorant (here, Example 1 from the Colorant Table, above, preferably) within a mixer zone 22.
  • the polymer (not illustrated) is introduced within the fiber production assembly 10, in particular within the extrader 11.
  • the temperatures, as noted above, of the individual extruder zones 12, 14, 16, 18, 20 and the mixing zone 22 are as follows: first extrader zone 12 at 210°C, second extrader zone 14 at 220°C, third extruder zone 16 at 230°C, fourth extruder zone 18 at 235°C, [fifth extruder zone 20 at 240°C,] and mixing zone 22 at 240°C.
  • the molten polymer (not illustrated) then moves into a spinneret area 24 set at a temperature of 240° C for strand extrasion. All such temperatures may be modified as needed, and these levels are non- limiting and simply potentially preferred.
  • the fibrous strands 28 then pass through an air- blown treatment shroud [area] 26 set at a temperature of 175°C and then through a treatment area 29 whereupon a lubricant, such as water or an oil, is applied thereto the strands 28.
  • the strands 28 are then collected into a bundle 30 via a take-up roll 32 to form a multifilament yarn 33 which then passes to a series of tensioning rolls 34, 36 prior to drawing.
  • the yam 33 then passes through a series of two different sets of draw rolls 38, 40, 42, 44 which increase the speed of the collected finished strands 33 as compared with the speed of the initially extruded strands 28.
  • the finished strands 33 extend in length due to a greater pulling speed in excess of such an initial extrasion speed within the extruder 11.
  • the strands 33 are then passed through a series of relax rolls 46, 48 and ultimately to a winder 50 for ultimate collection on a spool (not illustrated).
  • the speed of the winder 50 ultimately dictates the speed and efficiency of the entire apparatus in terms of permitting high speed manufacturing and spinning (drawing) with minimal, if any, breakage of the target fibers during such a procedure.
  • the draw rolls are heated to a very low level as follows: first draw rolls 38, 40 60-70°C and the second set of draw rolls 42, 44 80-90°C, as compared with the remaining areas of high temperature exposure as well as comparative fiber drawing processes.
  • FIG. 2 depicts the non-limiting preferred procedure followed in producing the inventive low-shrink polypropylene tape fibers.
  • the entire fiber production assembly 110 comprises a mixing manifold 111 for the incorporation of molten polymer and additives (such as the aforementioned nucleator compound) which then move into'an extrader 112.
  • the extruded polymer is then passed through a metering pump 114 to a die assembly 116, whereupon the film 117 is produced.
  • the film 117 then immediately moves to a quenching bath 118 comprising a liquid, such as water, and the like, set at a temperature from 5 to 95°C (here, preferably, about room temperature).
  • the drawing speed of the film at this point is dictated by draw rolls and tensionsing rolls 120, 122, 124, 126, 128 set at a speed of about 100 feet/minute, preferably, although the speed could be anywhere from about 20 feet/minute to about 200 feet/minute, as long as the initial drawing speed is at most about l/5 th that of the heat-draw speed later in the procedure.
  • the quenched film 119 should not exhibit any appreciable crystal orientation of the polymer therein for further processing.
  • Sanding rolls 130, 131, 132, 133, 134, 135, may be optionally utilized for delustering of the film, if desired.
  • the quenched film 119 then moves into a cutting area 36 with a plurality of fixed knives 138 spaced at any distance apart desired.
  • such knives 138 are spaced a distance determined by the equation of the square root of the draw speed multiplied by the final width of the target fibers (thus, with a draw ratio of 5: 1 and a final width of about 3 mm, the blade gap measurements should be about 6.7 mm).
  • the entire fiber production assembly 210 comprises an extrader 211 including a metering pump (not illustrated) for introduction of specific amounts of polymer into the extrader 211 (to control the denier of the ultimate target manufactured fiber and/or yarn) which also comprises five different zones 212, 214, 216, 218, 220 through which the polymer (not illustrated) passes at different, increasing temperatures.
  • the molten polymer is mixed with the nucleator compound (also molten) within a mixer zone 222.
  • the polymer (not illustrated) is introduced within the fiber production assembly 210, in particular within the extruder 211.
  • the temperatures, as noted above, of the individual extrader zones 212, 214, 216, 218, 220 and the mixing zone 22 are as follows: first extrader zone 212 at 205°C, second extrader zone 214 at 215°C, third extrader zone 216 at 225°C, fourth extrader zone 218 at 235°C, fifth extruder zone 220 at 240°C, and mixing zone 222 at 245°C.
  • the molten polymer (not illustrated) then moves into a spinneret area 224 set at a temperature of 250°C for strand extrasion. All such temperatures may be modified as needed, and these levels are non-limiting and simply potentially preferred.
  • the fibrous strands 228 then pass through an air-blown treatment area 226 and then through a treatment area 229 whereupon a lubricant, such as water or an oil, is applied thereto the strands 228.
  • a lubricant such as water or an oil
  • the strands 228 are then collected into a bundle 230 via a take-up roll 232 to form a multifilament yarn 233 which then passes to a series of tensioning rolls 234, 236 prior to drawing.
  • the yarn 233 then passes through a series of two different sets of draw rolls 238, 240, 242, 244 which increase the speed of the collected finished strands 233 as compared with the speed of the initially extruded strands 228.
  • the finished strands 233 extend in length due to a greater pulling speed in excess of such an initial extrasion speed within the extruder 211.
  • the strands 233 are then passed through a series of relax rolls 246, 248 and ultimately to a winder 250 for ultimate collection on a spool (not illustrated).
  • the speed of the winder 250 ultimately dictates the speed and efficiency of the entire apparatus in terms of permitting high speed manufacturing and spinning (drawing) with minimal, if any, breakage of the target fibers during such a procedure.
  • the draw rolls are heated to a very low level as follows: first draw rolls 238, 240 68°C and the second set of draw rolls 242, 244 88°C, as compared with the remaining areas of high temperature exposure as well as comparative fiber drawing processes.
  • the draw rolls 238, 240, 242, 244 individually and, potentially independently rotate at a speed of from about 1000 meters per minute to as high as about 5000 meters per minute.
  • the second draw rolls 242, 244 generally rotate at a higher speed than the first in excess of about 800 meters per minute up to 1000 meters per minute over those of the first set.
  • FIG. 4 the presence of rod-like stractures of color is evident throughout the fiber.
  • Such rod-like structures are basically the liquid polymeric colorants stretched in the same manner as the resin fiber is stretched during extrasion.
  • the shear of extrusion forms long high aspect ratio rod-like configurations of liquid colorant within the target fiber.
  • Such a rodlike structure thus imparts colorations to the target fiber while simultaneously allowing transmission of light therethrough.
  • the fiber remains transparent to light, thereby exhibiting an increased brightness and luster.
  • these rod-like stractures although they remain liquid in nature, are not in individual pools of color, but are stretched in such a rod-like manner, such that the liquid component cannot be easily extracted from within the target fiber without damaging the fiber itself.
  • the presence of pigment particles is evident throughout the fiber.
  • Such pigment particles are solid in nature.
  • the color imparted to the target fiber is thus substantially reliant upon absorption of light by such solid particles. There is little chance of light transmission through the fiber such that the fiber lacks transparency. As a result, brightness and luster are compromised such that the fiber exhibits a dulling effect, particularly in comparison with the fiber of FIG. 4.
  • Inventive Fiber and Yam Production Example #1 - Polymeric Colorant Fibers Yarns were made using a commercially available polypropylene fiber grade resin Amoco 7550 (melt flow of 18), using a standard fiber spinning apparatus as described previously.
  • the five colorants from the COLORANT TABLE, above, were formed into 10% concentrates premixed with fiber grade polypropylene resin and fed into the hopper of the extrader during fiber extrasion.
  • fiber grade resin polypropylene was fed into the extrader on an Alex James & Associates multifilament fiber extrusion line as noted above in FIG. 1 along with a 10% color concentrate including the required liquid polymeric colorants.
  • Yam was produced with the extrusion line conditions shown in Table 1 using a 68 hole spinneret, giving a yarn of nominally 150 denier.
  • the godet roll temperatures were 67°C (for 38, 40 in FIG. 1), 85°C (for 42, 44), and 125°C (for 46, 48), respectively, with a nominal winder speed of about 1300 m/min.
  • Pigmented fibers were also made for comparative purposes.
  • the extruder and cooling conditions were as follows:
  • Winder take-up speeds of 1290 m min with draw ratios of approximately 3.5 were utilized and deniers between 150 and 200 were produced.
  • a minimum of 3 samples were produced with concentrations of l A and or 1 % color in the Amoco 7550 for each of the colors. Extrusion conditions and physical properties of these samples are detailed in the following tables. Additionally, comparative pigmented samples were produced with three pigments provided by Standridge Color Concentrate 86600 blue 25% GSP, fade red HUV and yellow HG 25% which are identified in the table below as blue, red and yellow pigment, respectively.
  • the above samples have similar physical properties to those of fibers spun with pigments (solution dyed) in the same polypropylene resin, however the luster of the colors is significantly different. It is also important to note that the polymeric colorants are generally non-nucleating and will, under the same processing conditions have similar physical properties while the pigments (specifically the blue pigment - Sample 20) generally are nucleating which often requires the fiber spimring equipment to be operated under different conditions to obtain similar physical properties - note the higher elongation of sample 20 in comparison to samples 21 and 22.
  • Example 2 Polymeric Colorant Fibers with TiO 2 and Pigments
  • a series of polypropylene samples was produced under the standard fiber spinning conditions described in Example 1 to test the ability to combine both solid pigments and liquid polymeric colorants in the same fibers.
  • the drawing conditions for these example yams are detailed in the following table.
  • the polymeric colorants in these example experiments are identified as PP Green 5720, PP Red 5718, and PP Smoke 5719 for the green, red and black liquid polymeric colorant respectively (all available under the tradename CLEARTINT® from Milliken & Company). Fiber Additives Table #2
  • Example 3 Polymeric Colorant Fibers with Nucleators
  • MDBS polypropylene nucleator
  • Example 4 Polymeric Colorant Fibers with UV Absorbers
  • 10 samples using a 10% concentrate of Yellow 485 polymeric colorant and various UV stabilizers were generated.
  • the 10 samples were spun under standard sampling conditions as described in Example 2 above.
  • the table below details the combinations and amounts of UV stabilizers with two different concentrations of the yellow colorant from the COLORANT TABLE, above.
  • Example 5 Textured Polymeric Colorant Fibers Yarns containing 1% of the polymeric colorants PP Orange 9802 and PP Violet 9804 were air jet textured.
  • the starting yams were 150 denier, 72 filament yarns with standard physical properties produced in the same manner as those fibers described in Example #1 above.
  • Two orange yarns were air jet textured with one violet yam to produce a collaged air jet textured yarn.
  • Example 6 Polymeric Colorant Fibers from Liquid Colorant Injection
  • a second set of filament yarns was produced by directly injecting the liquid colorant into the feed throat of the extrader of the fiber spinning equipment.
  • Basell PDC-1302 a 35 MFI HPP
  • the polymeric colors were then injected directly into the hopper of the extrasion line using a peristaltic pump (Maguire, Model MPA-6-18). hi each case the pump was set to the lowest possible setting, due to the size of the extrasion line and the throughput of the melt pump.
  • the two colorants used were 10% concentrates of the violet and red colorants from the COLORANT TABLE, above. All yams were produced under the spinning conditions described in Table 5 below. Procedural Conditions Table #5
  • Example 7 Polymeric Colorant Monofilament Polymeric colorant concentrates were let down into two PP resins: the first with an MFI of 12-18 g/10 min (Exxon 1154) and the second with an MFI of 4 g/10 min (Exxon 2252) at a level of 10% to give 1% colorant in the final polymer fiber.
  • This mixture consisting of PP resin and the polymeric colorant additive, was extruded using a single screw extrader through monofilament spinnerets with 60 holes. The PP melt throughput was adjusted to give a final monofilament denier of approximately 520 g/9000m.
  • the molten strands of filament were quenched in room temperature water (about 25°C), and then transferred by rollers to a battery of airs knives, which dried the filaments.
  • the filaments, having been dried, were ran across the first of four sets of large rolls, all rotating at a speed of between 49 and 126 ft/min (dependent on draw ratio), before entering an oven approximately 14 ft long set to a temperature of 360°F.
  • the filaments were transferred to the second set of large rollers running at a speed of 524 ft/min (dependent on draw ratio) and then into second oven, set at a temperature of 360°F.
  • the final two sets of rolls were both set at 630 ft/min and the oven between them was set at a temperature of 300°F.
  • the individual monofilament fibers were then traversed to winders where they were individually wound. These final fibers are thus referred to as the PP monofilaments.
  • Several monofilament fibers were made in this manner with the following PP Red 9803, PP Violet 9804, PP Blue 9805, and PP Green 9807.
  • Example 8 - Melt Blown Non-woven with Polymeric Colorants A colored melt blown non-woven fabric was produced using a Nordson Fiber systems pilot melt blown system.
  • the equipment consisted of a %" single screw extrader (24:1) L:D ratio manufactured by J/M Laboratories - Model DTMB.
  • the airflow was set to 30 scfin with a max temperature of 625F.
  • Example 9 Polyester Polymeric Colorant Fibers from Liquid Color Injection
  • a set of experiments similar to Example #6 was conducted using a low IV (0.62) PET resin.
  • Example 10 - BCF Fibers Including Liquid Polymeric Colorants Cyan 9806 (from Milliken & Company) polymeric colorant was used to produce a colored bulk continuous filament (BCF) textured PP yam.
  • BCF bulk continuous filament
  • a three ply BCF 300 denier 72 filament yam was produced using standard BCF equipment.
  • a single ply BCF 250 denier 72 filament textured yam was also produced using standard BCF equipment.
  • the colorant was added to the extrasion line using a 10% concentrate to give a final color level of 1% in the yams. Emitted stractures (socks) of the above Examples (except for Example #8 which was already made into a non-woven fabric) were then produced.

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  • General Chemical & Material Sciences (AREA)
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  • Artificial Filaments (AREA)

Abstract

L'invention concerne une fibre thermoplastique ayant un colorant liquide qui présente une structure de type barre (fig. 5).
PCT/US2004/024154 2003-08-30 2004-07-26 Fibres thermoplastiques presentant des caracteristiques durables d'intensite de couleur elevee WO2005024104A1 (fr)

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US10/651,776 2003-08-30
US10/651,444 US20050048281A1 (en) 2003-08-30 2003-08-30 Thermoplastic fibers exhibiting durable high color strength characteristics
US10/651,776 US20050046065A1 (en) 2003-08-30 2003-08-30 Thermoplastic fibers exhibiting durable high color strength characteristics
US10/651,777 US6849330B1 (en) 2003-08-30 2003-08-30 Thermoplastic fibers exhibiting durable high color strength characteristics
US10/651,444 2003-08-30
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WO2008122986A2 (fr) * 2007-04-10 2008-10-16 Reliance Industries Limited Procédé efficace et économique de production de polymère thermoplastique coloré
WO2010133531A1 (fr) * 2009-05-18 2010-11-25 Rieter Technologies Ag Moquette touffetée pour applications automobiles
US10465320B2 (en) 2012-05-12 2019-11-05 Autoneum Management Ag Needle punched carpet

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US6444313B1 (en) * 2001-01-05 2002-09-03 The Pilot Ink Co., Ltd. Thermochromic acrylic synthetic fiber, its processed article, and process for producing thermochromic acrylic synthetic fiber
US6528564B1 (en) * 2001-10-12 2003-03-04 Milliken & Company Articles comprising novel polymeric blue anthraquinone-derivative colorants
US6541554B2 (en) * 2001-05-17 2003-04-01 Milliken & Company Low-shrink polypropylene fibers

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US6444313B1 (en) * 2001-01-05 2002-09-03 The Pilot Ink Co., Ltd. Thermochromic acrylic synthetic fiber, its processed article, and process for producing thermochromic acrylic synthetic fiber
US6541554B2 (en) * 2001-05-17 2003-04-01 Milliken & Company Low-shrink polypropylene fibers
US6528564B1 (en) * 2001-10-12 2003-03-04 Milliken & Company Articles comprising novel polymeric blue anthraquinone-derivative colorants

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008122986A2 (fr) * 2007-04-10 2008-10-16 Reliance Industries Limited Procédé efficace et économique de production de polymère thermoplastique coloré
WO2008122986A3 (fr) * 2007-04-10 2009-12-30 Reliance Industries Limited Procédé efficace et économique de production de polymère thermoplastique coloré
WO2010133531A1 (fr) * 2009-05-18 2010-11-25 Rieter Technologies Ag Moquette touffetée pour applications automobiles
CN102459737A (zh) * 2009-05-18 2012-05-16 欧拓科技公司 用于汽车应用的簇绒地毯
CN104074005A (zh) * 2009-05-18 2014-10-01 欧拓管理公司 用于汽车应用的簇绒地毯
CN102459737B (zh) * 2009-05-18 2015-07-08 欧拓管理公司 用于汽车应用的簇绒地毯
US10465320B2 (en) 2012-05-12 2019-11-05 Autoneum Management Ag Needle punched carpet
US11313063B2 (en) 2012-05-12 2022-04-26 Autoneum Management Ag Needle punched carpet

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