EP0761846B1 - Fibre discontinue cardable hydrophobique avec lubrifiant interne et son procédé et utilisation - Google Patents

Fibre discontinue cardable hydrophobique avec lubrifiant interne et son procédé et utilisation Download PDF

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Publication number
EP0761846B1
EP0761846B1 EP96305779A EP96305779A EP0761846B1 EP 0761846 B1 EP0761846 B1 EP 0761846B1 EP 96305779 A EP96305779 A EP 96305779A EP 96305779 A EP96305779 A EP 96305779A EP 0761846 B1 EP0761846 B1 EP 0761846B1
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EP
European Patent Office
Prior art keywords
fiber
polysiloxane
polyolefin
fibers
carbon atoms
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Expired - Lifetime
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EP96305779A
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German (de)
English (en)
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EP0761846A3 (fr
EP0761846A2 (fr
Inventor
Rakesh Kumar Gupta
James H. Harrington
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FIBERVISIONS, L.P.
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FiberVisions LP
FiberVisions Inc
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Priority to US08/715,130 priority Critical patent/US5763334A/en
Publication of EP0761846A2 publication Critical patent/EP0761846A2/fr
Publication of EP0761846A3 publication Critical patent/EP0761846A3/fr
Priority to US09/025,890 priority patent/US6177191B1/en
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Publication of EP0761846B1 publication Critical patent/EP0761846B1/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
    • 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
    • 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
    • D04H1/42—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 characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4382—Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
    • D04H1/43825—Composite fibres
    • D04H1/43832—Composite fibres side-by-side
    • 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
    • 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
    • D04H1/42—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 characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4282—Addition polymers
    • D04H1/4291—Olefin series
    • 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
    • D04H1/42—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 characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4326—Condensation or reaction polymers
    • D04H1/435—Polyesters
    • 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
    • D04H1/42—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 characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4382—Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
    • D04H1/43825—Composite fibres
    • D04H1/43828—Composite fibres sheath-core
    • 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
    • D04H1/42—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 characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4382—Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
    • D04H1/43825—Composite fibres
    • D04H1/4383—Composite fibres sea-island

Definitions

  • This invention pertains to hydrophobic polyolefin fibers, their fabrication, and to nonwoven fabrics made therefrom.
  • Synthetic, polymeric fibers have found a wide range of applications, from textiles for clothing to reinforcement for tires. The particular application to which the fiber is put will dictate the physical and chemical properties required. Synthetic fibers are particularly useful in absorbent products, especially coverstock fabrics for diapers and other incontinence and hygiene products, such as sanitary napkins, tampons, underpants, and the like. Polyolefin and other fibers used in coverstock and similar fabrics that permit liquid to flow through them are hydrophobic. To facilitate the flow of liquid through them, they generally comprise a hydrophilic finish so that the liquid flows at a sufficiently high rate. The associated portions of such products, such as leg-cuffs, waist bands, and medical barriers, are also used to manage the flow of liquid as barriers rather than as channels. Accordingly, it is desirable for certain fibers used in these associated portions not only to be hydrophobic but also to have a fiber/finish surface that is hydrophobic.
  • silicone fluids are conventionally added to the fiber surface by using such devices as a sprayer or a roller
  • Silicone fluids are also conventionally applied as a surface lubricant; thus, application of these fluids to the surface of the fiber provides a lubricated, hydrophobic fiber.
  • silicone fluids When silicone fluids are used as a hydrophobic finish, they must first be diluted in a solvent to allow for their application to the fiber surface in a controlled manner.
  • silicone fluids used on conventional hydrophobic polypropylene fibers are emulsified in an aqueous solution with the aid of wetting agents.
  • emulsified silicones One problem encountered with the use of emulsified silicones is a reduction in the hydrophobicity imparted by the silicone to the fiber surface due to the presence of the wetting agents used in the emulsion.
  • Another problem in using topically applied silicone fluids is that a certain amount of necessary friction is lost because of the lubricity of the silicone fluid.
  • Certain typical fiber processing operations, such as crimping and carding require a minimum degree of friction between the fiber and parts of the processing equipment in order for the apparatus to manipulate the fiber.
  • the topically applied silicone lubricant interferes with the frictional properties required for these operations. To compensate for the reduced friction, such operations must be performed at lower line speeds, and so the entire process must be slowed down to compensate.
  • Nohr and MacDonald in US 4,923,914, describe a fiber or film forming polyolefin composition having a particular polysiloxane additive; these additives are generally hydrophilic.
  • the additive is compatible with the polyolefin at melt extrusion temperatures but is incompatible at temperatures therebelow, and is comprised of two moieties, provided in the same additive or in separate additives; if provided as separate additives, both are incompatible with the polyolefin at all temperatures.
  • the moieties are both alkoxy groups, in one case the groups capping the end of the siloxane chain, and in the other case the groups being pendant from the backbone.
  • the additive has a concentration within the fiber that increases from the fiber axis to its surface.
  • the siloxane includes pendant from its polymer backbone a monovalent organic radical containing at least one ethylene oxide group, a vicinal epoxy group, or an amino group.
  • Steklenski in US 4,473,676, describes incorporating a cross-linked silicone polycarbinol into film-forming compositions to make polymer compositions having a low coefficient of friction and useful for protective layers in photographic elements.
  • Hansen et al. in US 5,456,982, describe incorporating a surface active agent, such as an emulsifier, surfactant, or detergent, into the sheath component of a sheath-and-core type bicomponent fiber to render the fiber hydrophobic.
  • a surface active agent such as an emulsifier, surfactant, or detergent
  • Silicone additives such as described by Nohr and MacDonald (noted above), which are incompatible with the bulk polymer at ambient temperatures but compatible at spinning temperatures, take advantage of a problem with such additives. Higher molecular weight for such additives render the additive less soluble in polypropylene (and in other polyolefins). However, using a lower molecular weight silicone decreases the thermal stability of the lubricating additive.
  • Aqueous lubricants applied as a surface finish, provide advantages over non-aqueous suface lubricants (such as silicon oils) in their facility in being applied and removed, their lower toxicity, and their case of dispersion (and thus uniformity of the lubricant coating after having been applied to the fiber surface).
  • Yet another benefit would be to provide a hydrophobic fiber intrinsically lubricated effective to allow processing of the fiber into a carded, nonwoven article without the application of a lubricating finish.
  • a hydrophobic fiber intrinsically lubricated effective to allow processing of the fiber into a carded, nonwoven article without the application of a lubricating finish.
  • such a fiber would provide an improvement in conventional processing by eliminating one or more lubricating finish application steps.
  • Still a further benefit would be to provide such a hydrophobic fiber with a thermally stable intrinsic lubricant.
  • Yet another benefit would be to provide an as-spun polyolefin-containing fiber having a contact angle, especially an advancing contact angle, greater than the intrinsic contact angle of such a polyolefin.
  • this invention provides a fiber-formable melt composition useful for melt spinning a fiber which, as spun, has an improved hydrophobicity and an improved lubricity.
  • This novel polymer melt comprises an intimate admixture of a fiber-forming polyolefin, especially having ethylene and/or propylene units, with a polysiloxane.
  • this invention provides an internally lubricated polyolefin fiber, preferably also hydrophobic, having an essentially non-extractable internal lubricant.
  • This invention also provides a novel as-spun polyolefin fiber comprising an internal polysiloxane and having a contact angle greater than a comparable polyolefin fiber without the internal polysiloxane.
  • the increased contact angle means that that the novel as-spun fiber is more hydrophobic than that without the internal polysiloxane.
  • the present fibers preferably have an intrinsic contact angle of at least 95°, more preferably at least about 96°, even more preferably at least about 100°, still more preferably at least about 105°, and most preferably at least about 110° or more.
  • the present invention provides a hydrophobic fiber having an internal lubricant (i.e., it can be processed without an applied topical lubricating finish composition).
  • the fiber can be provided with a topically applied hydrophilic antistatic finish. In either case, the fiber is processable into a carded nonwoven article, at commercial speeds, while maintaining hydrophobicity.
  • this invention provides a polyolefin-containing fiber or a polyolefin-containing fiber-formable composition, depending upon whether the composition is in a molten or a solidified state, which comprises an internal polysiloxane of the general formula X-[Si(R 1 )(R 2 )-O-] z -Y, in which X, Y, R 1 , R 2 , are independently selected from hydrophobic and non-polar groups, preferably hydrocarbyl groups, more preferably alkyl, alkenyl, alkynyl, cycloalkyl, and/or aralkyl groups, and/or aryl substituted with any of the foregoing groups, having up to about twenty two, and more preferably up to about sixteen carbon atoms, and ethers thereof, R 1 and R 2 can also be independently selected from hydrophobic and non-polar alkyl, aryl, and heterocyclic groups, and z is a positive number sufficiently high that the polys
  • the fiber is "polyolefin-containing" when at least half, preferably at least about 75%, more preferably at least about 90%, and even more preferably at least about 95% of the weight of the structural component of the fiber ( i.e., exclusive of additives) is polyolefinic.
  • the polysiloxane is "hydrophobic" in the common sense of having no affinity for water, and functionally, with respect to certain preferred embodiments of this invention, provides a hydrophobic fiber surface, especially for the above-mentioned hydrophobic fibers useful in barrier devices.
  • R 1 and R 2 are independently selected from unsubstituted and substituted hydrophobic straight and branched chain alkyl groups having not more than about sixteen carbon atoms, more preferably not more than about eight carbon atoms, and aryl groups (e.g., phenyl) optionally substituted with up to three hydrophobic alkyl groups.
  • X and Y are lower alkyl groups having not more than about sixteen carbon atoms, and more preferably not more than about eight carbon atoms.
  • z ranges from about 10 to about 50 or more.
  • This invention also provides an as-spun polyolefin fiber having an intrinsic contact angle of at least about 95°, more preferably at least about 100°, still more preferably at least about 105°, and most preferably at least about 110° or more.
  • intrinsic contact angle is meant the contact angle of the as-spun fiber prior to the application of any topical finish.
  • the novel as-spun fiber of this invention has a contact angle after having been spun, and without the application of a topical lubricant, greater than a comparable as-spun fiber without an internal lubricant.
  • this invention provides a polyolefin fiber having an essentially non-extractable lubricant.
  • the novel fibers of this invention having an internal lubricant, are not susceptible of having the lubricant removed from the surface of the fiber, in contrast to fibers having only a topically applied lubricant
  • the invention provides a novel process for using these fibers, especially in the production of nonwoven articles and products therefrom, which preferably comprises providing a fiber-forming composition including a major portion of polyolefin and a compatible polysiloxane intimately admixed therewith, spinning the fiber-forming composition into one or more fibers, drawing the fibers, crimping the fibers, cutting the crimped fibers into staple lengths, and carding and consolidating the fibers to produce a nonwoven article.
  • the nonwoven article is preferably further processed into a hygeine product, such as a diaper.
  • a topical hydrophobic finish preferably aqueous based, may optionally be applied to the fibers if necessary or desirable.
  • the present invention concerns a polyolefin-containing, lubricated, fiber-forming composition, the fibers made therefrom, and intermediate and final articles made therefrom.
  • fiber-forming composition is meant a composition that is spinnable into fibers, preferably by melt spinning.
  • the lubricant is a hydrophobic polysiloxane
  • the fiber-forming compositions useful in this invention preferably include melt spinnable polyolefins derived from straight and branched chain olefinic, preferably alkene, monomers having at least two carbon atoms, preferably from about two to about eight carbon atoms or more, more preferably from about two to about four carbon atoms, and most preferably two or three carbon atoms (including polyethylene and polypropylene).
  • the polyolefin may be a homopolymer or a copolymer (e.g., terpolymer), used alone or mixed or blended in various proportions with other polyolefin-containing homopolymers or copolymers.
  • polystyrene examples include, without limitation, polyethylene, polypropylene, poly(1-butene), poly(4-methyl-1-pentene), poly( ⁇ -methylstyrene), poly( o -methylstyrene), polybutadiene, and the like, and compatible mixtures and blends thereof.
  • the most preferred composition is polypropylene, especially propylene homopolymer or a copolymer derived from at least 50% by weight, more preferably at least 75% by weight, and most preferably at least 90% by weight of propylene with the remainder derived from ethylene, butene, hexene, and mixtures thereof.
  • spinnable blends or mixtures of polymers comprising at least 50%, more preferably at least 75%, and most preferably at least 90% by weight of propylene homopolymer.
  • the fiber-forming composition thus may include one or more fiber-forming polymers compatible with the polyolefin present therein. It is preferred that the fiber-forming composition have at least 90% by weight of polyolefin, although at least 75% polyolefin content can be suitable for certain applications, with the minimum quantity of polyolefin being not less than about 50% by weight.
  • Suitable polymers for blending or alloying with the polyolefin can be selected from polyesters, polyamides, and polyaramides, and the like that are compatible with the other constituents.
  • a preferred blend comprises poly(ethylene terephthalate) ("PET”) and polypropylene.
  • Preferred polyolefins include polyethylene homopolymer, polypropylene homopolyer, and ethylene-propylene copolymer, and mixtures thereof.
  • a mixture of polyethylene:polypropylene ranging from about 19:1 to about 1:19, from about 10:1 to about 1:10, from about 6:1 to about 1:6, and in approximately equal weight proportions of about 1: 1; essentially any amount from pure ethylene or propylene homopolyer to approximately equal amounts of the two homopolymers (one of which can be substituted with an ethylene-propylene copolymer).
  • At least one polysiloxane of the formula X-[Si(R 1 )(R 2 )-O-] z -Y is added.
  • X and Y may be the same or different and are independently chosen from hydrophobic and non-polar groups, preferably hydrocarbyl groups, more preferably aliphatic groups such as alkyl, alkenyl, alkynyl, and cycloalkyl groups, preferably C 1-22 , more preferably C 1-16 , even more preferably C 1-8 , and most preferably C 1-3 , and ethers thereof; for example, an octyl or octylsiloxy ether thereof.
  • hydrocarbyl groups more preferably aliphatic groups such as alkyl, alkenyl, alkynyl, and cycloalkyl groups, preferably C 1-22 , more preferably C 1-16 , even more preferably C 1-8 , and most preferably C 1-3 , and ethers thereof; for example, an octyl or octylsiloxy ether thereof.
  • R 1 and R 2 which may also be the same or different, are also aliphatic hydrophobic groups preferably selected from alkyl, alkenyl, alkynyl, and cycloalkyl groups, straight or branched chain, having not more than about twenty two carbon atoms, more preferably not more than about sixteen carbon atoms, even more preferably not more than about eight carbon atoms, and most preferably one to three carbon atoms, with one carbon atom being especially preferred, and are also preferably selected from arene groups, preferably phenyl, optionally substituted with up to three aliphatic groups (e.g.
  • R 1 and R 2 are are selected from unsubstituted C 1-3 alkyl and unsubstituted phenyl groups.
  • the various aliphatic groups are preferably straight chained, although branched chains can also be suitable.
  • R 1 and R 2 are preferably selected from alkyl, alkenyl, alkynyl, cycloalkyl, araliphatic, aryl, and any of the foregoing substituted with any of the foregoing ( e.g., aralkyl phenyl), and, hydrophobic, preferably non-polar derivatives thereof.
  • Preferred non-polar derivatives include the ethers thereof, such as methoxy, ethoxy, ethoxymethoxy, benzoxy, and the like.
  • the general formula for the polysiloxanes may be written as X-A 1 -[Si(A 2 R 1 )(A 3 R 2 )-O-] z -A 4 -Y in which A 1 , A 2 , A 3 , and A 4 are independently selected from a bond or oxygen, the other variables being as defined previously.
  • the chain length z is a positive number sufficiently high that the polysiloxane is hydrophobic and preferably renders the polysiloxane compatible with the polymer in both the melted and the solidified states; z is generally on the order of 10-50 or more.
  • suitable polysiloxanes for incorporating into the fiber-forming compositions of this invention include those used for finishes for fibers as described by Schmalz in U.S. Pat. No. 4,938,832, U.S. Pat. Applns. Ser. Nos. 07/614,650 and 07/914,213, and European Pat. Appln. No. 486,158, and by Johnson et al. in U.S. Pat. Applns. Ser. Nos.
  • the preferred polysiloxanes are poly(dialkylsiloxane)s and poly(alkylarylsiloxane)s, particularly poly(dimethylsiloxane) and poly(methylphenylsiloxane).
  • the preferred molecular weight for the poly(dialkylsiloxane) is at least about 15,000, more preferably in the range of from about 60,000 to about 450,000, more preferably from about 75,000 to about 275,000.
  • the preferred molecular weight range is from about 1500 to about 3500, more preferably in the range of from about 2000 to about 3000, with poly(methylphenylsiloxane) preferably having a molecular weight of about 2600, although significantly higher molecular weights can be used.
  • the molecular weight of the polysiloxane can be number average or weight average molecular weight.
  • Suitable polysiloxanes for the present invention are those that are miscible with the polyolefin-containing spinnable composition at ambient temperatures and preferably also during conditions suitable for spinning.
  • low molecular weight alkylsiloxanes typically incorporated into engineering resins are immiscible therewith and migrate (bloom) to the surface of the part due to their immiscibility with the bulk polymer at ambient conditions.
  • the spinnable melts of this invention and the fibers spun therefrom are lubricated with a polysiloxane tailored so that there is significantly less migration of the polysiloxane to the surface of the fiber, as evidenced by minimal surface extraction of the internal polysiloxane after the passage of more than two years.
  • the use of poly(alkylarylsiloxane)s in this invention also provides improved thermal stability of the polysiloxane at high spinning temperatures due to the presence of the aryl groups.
  • the relatively high molecular weights for the poly(dialkylsiloxanes) also provide the benefit of improved thermal stability at higher spinning temperatures.
  • the polysiloxane is selected from (a) those having at least one of R 1 and R 2 selected from an arene group and (b) those as otherwise defined and having a molecular weight of at least about 15,000.
  • the internal polysiloxane is provided generally as an additive in amounts typically not more than about 10% by weight of the fiber and generally of at least about 0.01% by weight, more preferably in the range of about 0.05% to about 5% by weight, and most preferably in the range of about 0.1% to about 1.0% by weight of the fiber.
  • polysiloxane lesser amounts are preferred as its molecular weight increases.
  • a certain polyolefin composition comprising 1% by weight of a poly(dialkylsiloxane) having a molecular weight of about 100,000 is suitable in a particular application
  • the use of a poly(dialkylsiloxane) having a molecular weight of about 200,000 will preferably accomplish the same suitable result employing a lesser amount of the additive.
  • the amount of the polysiloxane used is effective to increase the hydrophobic nature of the polyolefin fiber surface beyond that of the as-spun fiber without the polysiloxane. It is also preferred that the amount of polysiloxane used is effective to lubricate (decrease the surface friction of) the as-spun fiber over that without the additive.
  • one embodiment of the present invention includes a novel spinnable melt comprising a major portion of a polyolefin and a polysiloxane of the formula X-A 1 -[Si(A 2 R 1 )(A 3 R 2 )-O-] z -A 4 -Y, as defined hereinabove, preferably in amounts of about 0.01% to about 10% by weight of the spinnable composition.
  • the melt spinnable, fiber-forming composition can be processed into a unitary fiber, or a bicomponent fiber or biconstituent fiber in such configurations as side-by-side, sheath-and-core, matrix with multiple cores ( e.g. , islands-in-the-sea), and multilobal.
  • Exemplary compositional configurations can include a polyolefin side-by-side with the same or a different polyolefin (e.g., polyethylene/polypropylene, or both polypropylene with different molecular weights); when such fibers are heated, the different polyolefin portions undergo different shrinkages, whereby the fiber curves or curls (e.g., a self-crimping fiber).
  • exemplary sheath/core configurations include polyalkylene/polyalkylene or polyalkylene/polyester, such as polyethylene/polypropylene, polyethylene/PET, and polypropylene/PET.
  • the present fibers may be provided individually, as a monofilament fiber, as a multifilament yarn, a spin bonded nonwoven, a meltblown nonwover, or as a tow, bundle, or the like, or as a woven fabric.
  • novel fibers of this invention so made, and woven and nonwoven articles made therefrom, are preferably hydrophobic.
  • fibers of this invention desirably have a hydrostatic head of at least about 30, more preferably at least about 62, even more preferably at least about 102, and still more preferably at least about 150 mm of water.
  • nonwoven fabrics preferably have a hydrostatic of at least about 25, more preferably at least about 50, still more preferably at least about 75, and even more preferably at least about 100 mm (at a bond area pattern of about 15%).
  • Average nonwoven fabric runoff is preferably at least about 30%, more preferably at least about 50%, still more preferably at least about 70%, even more preferably at least about 90%, and most preferably at least about 95% or more.
  • the as-spun fiber has a contact angle greater than an as-spun fiber of the same polymeric composition that lacks the polysiloxane additive of this invention.
  • the contact angle of an as-spun fiber will be defined herein as the “instrinsic contact angle.”
  • the intrinsic contact angle of an as-spun polypropylene homopolymer fiber is generally less than 95°.
  • the intrinsic contact angle of as-spun fibers according this invention, having the internal polysiloxane as described above, is at least 95°, more preferably is at least about 96°, even more preferably it is at least about 100°, and still more preferably the intrinsic contact angle is at least about 105° or more.
  • F w the wetting force
  • P the perimeter of the fiber
  • ⁇ the surface tension of the liquid.
  • a force balance is used to solve for the wetting force and thus the contact angle; alternatively, other methods, such as microscope measurement (i.e., actually viewing the fiber under a microscope to see the contact angle) are readily known and suitable.
  • the fibers of this invention are inherently- or internally-modified, in contrast to fibers that are surface-modified. Accordingly, the fibers of this invention provide the advantage of having an improved hydrophobicity.
  • Prior art fibers achieve hydrophobicity by applying a hydrophobic finish composition to the surface of the fiber and by adding a hydrophobic agent that blooms to the surface of the fiber.
  • the prior art hydrophobic additives are present at the surface in a form that is subject to removal by the various processes typically encountered in commercial operations, including contact with guides, rollers, and various forming ( e.g. , twisting, carding) apparatus, as well as contact with steam or other agents.
  • novel fibers of this invention are provided with an essentially non-removable, essentially non-extractable, and essentially non-blooming lubricant at their surface.
  • the lubricant is essentially non-removable and non-extractable at room temperature using non-polar solvents.
  • a surface finish is typically applied to fibers at a level of about 0.1-0.2% by weight of the fiber; after application, this surface finish can be extracted almost totally by an organic solvent.
  • novel fibers of this invention when subjected to the same extaction process, yield their lubricant to a significantly lesser degree, preferably at least about 50% less, and more preferably at least about 60% less, than that extracted from topically lubricated fibers; the less the internal lubricant that can be extracted from the fiber surface, the more preferrable.
  • the fibers of this invention also provide a lubricated fiber that is essentially free of emulsifier (or other surface active agents typically used with external finishes) on its surface.
  • this invention provides a melt suitable for spinning into fibers that comprises a spinnable polyolefin-containing polymer composition and a lubricanting composition, preferably a polysiloxane, the melt being substantially free of any solvent or emulsifier for the lubricant.
  • the fibers may also contain such conventional additives as antacids (e.g. , calcium stearate), antioxidants, degrading agents, and pigments and/or colorants (such as titanium dioxide), and the like.
  • antacids e.g. , calcium stearate
  • antioxidants e.g. , Irgafos 168
  • calcium stearate e.g. , calcium stearate
  • titania e.g. , calcium stearate
  • Fibers of this invention may also preferably include biocides or antimicrobials. These additives can be present individually in individually varying amounts; typically, 0.01% to 3% of the composition may include one or more of these conventional additives.
  • the polysiloxane is preferably added to the fiber-forming composition prior to melting; the additive can be mixed into the melt if desired.
  • the fiber-forming composition is then spun into the novel continuous length fibers of this invention.
  • the fiber may be further drawn to orient the fiber to a particular degree, if desired, by techniques known in the art.
  • Staple fibers may be prepared according to this invention by extrusion, spinning, drawing, crimping, and cutting, by such processes as described by Kozulla, in U.S. Pat. Applns.
  • a hydrophilic spin finish composition is applied to the fibers to aid in processing and handling.
  • a water-soluble hydrophilic spin finish to reduce various processing problems such as occur during crimping.
  • a benefit of the internal siloxane is facilitating removal of the hydrophilic finish, i.e. , maintaining the hydrophobicity of the fiber.
  • Hydrophilic finishes which have both lubricating and antistatic properties are especially preferred; an exemplary finish of this type comprises a mixture of polyethylene glycol 400 monolaurate and polyoxyethylene(5)tridecylphosphate neutralized with diethanolamine (available as LUROL PP-912 from George A. Goulston Co., Monroe, NC).
  • the present invention empowers one to use a proportionally or relatively more hydrophilic antistatic surface finish composition (e.g. , sodium oleate) because of the improved ease of removal from the fiber surface due to the presence of the internal lubricant.
  • a proportionally or relatively more hydrophilic antistatic surface finish composition e.g. , sodium oleate
  • Crimping is typically accomplished by funnelling a tow of fibers into a conduit through which the fibers are drawn. Steam and water are typically circulated in the conduit, whereby the fibers are effectively stuffed into a steam-heated box and crimped. The steam and water act as lubricants which help to impart crimp to the fiber, and this hot humid environment in the box typically acts to remove most if not essentially all of the hydrophilic finishing composition.
  • a preferred crimping process and apparatus is disclosed by Sibal et al. in U.S. Pat. Appln. Ser./No. 08/235,306, filed April 29, 1994 (the disclosure of which is incorporated herein by reference).
  • a hydrophobic finish may be applied to the fiber.
  • an antistatic composition such as any of those described by the aforementioned Harrington applications, EP 0 557 024 A1 and U.S. Pat. Appln. Ser. No. 08/016,346 (filed 2/11/93, a continuation of 07/835,895, filed 02/14/92), Schmalz patent US 4,938,832 and application EP 0 486 158 A2 (corresponding to U.S. Pat. Appln. No. 914,213, filed July 15, 1992), and Johnson and Theyson, in US 5,403,426 and EP 0 516 412 A2 (the disclosures of all of such patents and applications being incorporated herein by reference), is also applied to the fiber.
  • Suitable hydrophobic finishing compositions include an antistatic agent in combination with a lubricant such as a polysiloxane; more specific examples include potassium C 4 - or C 6 -alkyl phosphate with poly(dimethylsiloxane)s, and potassium C 10 -alkyl phosphate with hydrogenated polybutene.
  • a lubricant such as a polysiloxane
  • the present invention includes a lubricant intimately admixed with the fiber component, a suitable choice for the amount of lubricant in the fiber can obviate the need to use a lubricant in the finishing compositions.
  • the invention provides the benefit of enabling the significant reduction, if not the elimination, of the amount of lubricant applied to the fibers in addition to an antistatic agent.
  • the novel fibers of this invention allow for the application of any of a variety of overfinishes, antistatic finishes, and the like, without compromising the inherent hydrophobicity of the fibers of
  • the fibers are then chopped into staple lengths typically in the range of about 5-350 mm long; preferred lengths are about 25-250 mm., more preferably about 25-75 mm., and most preferably about 30-50 mm.
  • the fibers are preferably of a uniform denier, in ranges as described previously, although mixed deniers can be used if desired for a particular application.
  • Hydrostatic head testing (e.g., performed as described in Example 6, below) on these staple fibers preferably provides a value of at least about 100 mm, more preferably at least about 135 mm, and even more preferably at least about 170 mm if not even higher.
  • the crimped staple length fibers are then carded, formed into a nonwoven web, and consolidated using any one of various techniques known in the art, including thermal bonding, needle punching, hydroentangling, and the like. Carding is preferably done using a continuous belt and bonding is preferably effected by contact with a heated calendering roll. Other methods for thermal bonding include other typical heat sources (e.g., hot air, heat lamps), sonic (ultrasonic), and laser bonding.
  • the nonwoven fabric has a basis weight of about 6-108 g/m 2 and a cross-directional strength of at least about 1.93 N/5 -cm (Newtons per five centimeters; 150 g/in) with a bond area of at least about 10%.
  • the fibers are capable of being formed into a nonwoven fabric having a basis weight of about 12-36 g/m 2 and having a directional strength of at least about 3.86 N/5 -cm with a thermal bond area of 15-45%; and most preferably the fibers are capable of being formed into a nonwoven fabric having a basis weight of about 18-36 g/m 2 and having a directional strength of at least about 6.755 N/5 -cm with a thermal bond area of about 18-30%.
  • the present fibers in the form of crimped staple fibers, provide nonwoven articles having a higher strength because, in contrast to other fibers, they do not have a hydrophobic silicone on the fiber surface that would interfere with fiber-fiber bonding to create the nonwoven article.
  • the internally lubricated fibers of this invention are lubricated so that processing speeds are increased, provide nonwoven articles having higher bond strengths, and have an improved hydrophobicity, leading to improved nonwoven hydrophobic articles.
  • the fiber preferably has a sink time (ASTM D-1117-79) of at least about 0.8 hours and the nonwoven fabric has a percent runoff value (described below) of at least about 80%. More preferably, the fiber has a sink time of at least about 4 hours and the nonwoven fabric has a percent runoff value of at least about 85%. Most preferably, the fiber has a sink time of at least about 20 hours and the nonwoven fabric has a percent runoff value of at least about 90%.
  • ASTM D-1117-79 the percent runoff value of at least about 0.8 hours and the nonwoven fabric has a percent runoff value (described below) of at least about 80%. More preferably, the fiber has a sink time of at least about 4 hours and the nonwoven fabric has a percent runoff value of at least about 85%. Most preferably, the fiber has a sink time of at least about 20 hours and the nonwoven fabric has a percent runoff value of at least about 90%.
  • the fibers of this invention can be processed under typically commercial processing conditions.
  • the production of fiber is preferably at least about 200 lb/hr, more preferably at least about 1000 lb/hr, and most preferably at least about 1500 lb/hr.
  • this invention provides a normally hydrophobic polyolefin fiber, especially one comprised of polypropylene, having improved hydrophobicity.
  • This improved property especially when achieved with a lubricating composition such as the present siloxanes, improves the liquid barrier properties of the fiber and articles (both woven and nonwoven) made therefrom.
  • This improved property also enables the use of aqueous (e.g., hydrophilic) and more environmentally friendly finishes for imparting antistatic, lubricant, and other properties to the fiber surface.
  • the present fibers can be processed into woven and nonwoven articles of manufacture. During various stages of such processing, these fibers are suitable for treatment with spin finishes, intermediate processing finishes, and over finishes as described in the various aforementioned patents and applications incorporated herein by reference, and as may be desirable for a particular processing scheme to achieve a desired article. These fibers are also useful for
  • Polypropylene resin (melt flow rate of 12 g per 10 min, available from Himont, Inc., Wilmington, DE) was admixed with 0.05% (Ex. 1A) and 0.30% (Ex. 1B) by weight of poly(dimethylsiloxane) having a molecular weight of 17,250 and a viscosity of 500 cS (centistokes). The mixture was melted and spun into fine denier, multifilament fibers. A spin finish comprising poly(ethylene glycol) 400 monolaurate and polyoxyethylene-5-tridecylphosphate neutralized with diethanolamine (available as LUROL PP-912, from G.A.
  • Goulston Co., Monroe, NC was applied to the fibers in an amount of about 0.3 wt.% based on the weight of the fiber. These fibers were drawn to 2.42 dtex and then crimped. After crimping, a hydrophobic finish comprising a neutralized phosphoric acid ester (designated LUROL® AS-Y, available from G.A. Goulston, Co., Monroe, NC)- and poly(dimethylsiloxane) (available from Union Carbide Chemical Co., Danbury, CT) was applied and the fibers were cut into 37.5 mm staple fibers.
  • LUROL® AS-Y available from G.A. Goulston, Co., Monroe, NC
  • poly(dimethylsiloxane) available from Union Carbide Chemical Co., Danbury, CT
  • the staple was then carded at a line speed of 76.2 m/min. into a nonwoven web, and then bonded using a heated calender (approximately 15% bond area pattern) into a fabric web having a basis weight of 24 g/m 2 ; the line speed and fabric weight were typical for commercial operations.
  • polypropylene resin was admixed with 0.50% and 1.0% by weight, respectively, of poly(dimethylsiloxane) having a molecular weight of 62,700 and a viscosity of 10,000 cS, and processed into staple fibers.
  • polypropylene resin was admixed with 0.1%, 0.3%, 0.5%, and 1.0% by weight, respectively, of poly(dimethylsiloxane) having a molecular weight of 139,000 and a viscosity of 100,000 cS, and processed into staple fibers.
  • polypropylene resin was admixed with 0.1%, 0.3%, and 0.5% by weight, respectively, of poly(methylphenylsiloxane) having a molecular weight of 2,600 and a viscosity of 500 cS, and processed into staple fibers.
  • control fiber was prepared by mixing polypropylene flakes with an antioxidant and calcium stearate and processed into staple fibers.
  • Lurol PP-912 composition was applied to the fiber as a spin finish prior to crimping. These fibers are characterized as shown in Table 1.
  • Example Composition Polysiloxane in fiber (wt. %) Hydrophilic Spin Finish (wt.% based on fiber) 1A 0.05 0.30 1B 0.30 0.30 2A 0.50 0.30 2B 1.00 0.30 3A 0.10 0.27 3B 0.30 0.25 3C 0.50 0.30 3D 1.00 0.30 4A 0.10 0.20 4B 0.30 0.20 4C 0.50 0.33 5 0.00 0.30
  • the various fibers produced in these examples were then tested for sink times and fabric runoff, the results of which are shown in Table 2.
  • the Sink Time Test (ASTM D-1117-79) is used to characterize the degree of wetting of fibers by determining the time for five grams of sample contained in a three gram basket to sink below the surface of water.
  • the fabric runoff test is conducted as follows: place a 27.5 cm x 12.5 cm sample of nonwoven fabric, with the rough side (i.e., pattern-side) face up over two sheets of Eaton-Dikeman #939 paper 12.5 x 26.9 cm long; the fabric and two sheets of paper are placed on a board with an incline of 10°; the tip of a separatory funnel is placed 2.5 cm from the top of the fabric and 2.5 cm above the center of the fabric sample; a weighed paper towel is place across and 0.625 cm from the bottom of the sample; the separatory funnel is filed with 25 ml of synthetic urine; the funnel stopcock is opened and the runoff is collected on the previously weighed paper; the wet paper is weighed to the nearest 0.1 g and the runoff percentage is calculated; the test is performed five times and the average is determined.
  • Example Composition Polysiloxane in Fiber (wt. %) Overfinish Level (wt.%) Sink Time (hours)
  • Avg. Fabric Runoff (%) 1A 0.05 0.40 > 2 96 1B 0.30 0.40 > 2 97 2A 0.50 0.40 > 2 97 2B 1.00 0.30 > 2 98 3A 0.10 0.37 > 2 95 3B 0.30 0.30 > 2 98 3C 0.50 0.20 > 2 90 3D 1.00 0.25 > 2 97 4A 0.10 0.30 > 2 95 4B 0.30 0.34 > 2 96 4C 0.50 0.29 > 2 97 5 0.00 0.47 0.04 0
  • the staple fiber of this invention did not wet after two hours exposure in water (i.e., sink times greater than two hours); additionally, the fabric gave runoff values greater than 90%, typically greater than 95% runoff of synthetic urine.
  • staple and fabric samples from the control gave poor hydrophobicity as noted by sink times and runoff data from Table 2.
  • the following ingredients were mixed in a Henschel mill: polypropylene resin (noted above, having a melt flow rate of 12 grams per ten minutes); 1.3 wt.% poly(dimethylsiloxane) having a viscosity of 10,000 cst and a molecular weight of about 62,700; 0.02 wt.% antioxidant (IRGAFOS 168, available from Ciba Geigy Corp., Additive Division, Ardsely, NY); 0.05 wt.% calcium stearate; and 0.20 wt.% titanium dioxide.
  • the resulting mixture was melt extruded through a spinnerette into fine denier multiple as-spun fibers.
  • a spin finish comprising 2.0% neutralized phosphoric acid ester (LUROL AS-Y) in water was applied to the as-spun fibers at a level of 0.05% based upon the dried fiber having the finish thereon.
  • the fiber were drawn to 2.2 dpf (2.4 dtex), crimped, and an antistatic overfinish of LUROL AS-Y (as described above) was applied to the crimped fiber at a level of 0.08%.
  • the fibers were then cut into 37.4 mm staple lengths. No topical lubricant (as a finish or otherwise) was applied to the fibers.
  • the staple fibers were carded at a commercial line speed of 76.2 M/min. into a nonwoven web, and then bonded (approximately 15% bond area pattern) using a heated calender into a fabric web having a basis weight of 24 g/m 2 .
  • the line speed and fabric weight were typical of commercial operations.
  • the fibers were processed (e.g., spun, drawn, crimped, and carded) at commercial speeds and without difficulty.
  • the fibers and the nonwoven fabric had excellent hydrophobicity characteristics: a sink time of greater than 24 hours; an average fabric runoff of 98%; and a hydrostatic head of 100 mm for the fabric, and 175 mm for the fibers. Fabric runoff and sink times were determined as described above.
  • Hydrostatic head was determined with a modified "Suter" apparatus as an alternative method to AATCC 1952-18 British Standard 2823 apparatus.
  • the hydrostatic pressure was applied to the top of the carded staple fiber and was controlled by a rising column of water at a rate of 290 cc/min.
  • the staple fiber holder was 3.7 cm (I.D.) by 3.0 cm long with a screen in the top and a cap with multiple holes to allow water to flow through.
  • the diameter of the exposed fiber sample was 3.7 cm. A mirror was fixed so that the underside of the fiber sample could be observed.
  • the water column height above the sample screen is 60.0 cm by 3.7 cm (I.D.) and water was added to the column through a 0.5 cm diameter vertical hole 2.0 cm above the sample screen.
  • a 0.50 cm diameter hole was placed 0.5 cm above the sample screen of the column to remove the water after each test.
  • the column drain hole is plugged and 5 g. of carded fibers were placed in the sample holder and compressed tightly therein. Water was pumped into the column until leakage occurred through the sample. The test was repeated five (5) times. Additionally, carded and bonded fabric was tested using a fabric sample holder having the same dimensions as the fiber sample holder. For testing fabric, a 10 cm by 10 cm piece of fabric was placed in the sample holder and clamped to the base of the column.
  • the fine denier as-spun fibers made as described in Example 6A were tested to determine their contact angle with reference to control fibers.
  • the subject fibers included 1.3 wt.% internal poly(dimethylsiloxane).
  • the control fibers were made by melt spinning a polypropylene homopolymer composition including 0.03 wt.% Irgafos 168 antioxidant, 0.1 wt.% calcium stearate antacid, and 0.06 wt.% titania.
  • a solution was prepared from water to which 1 wt.% Zonyl solution; Zonyl is a trademark for a fluorosurfactant wetting agent available from E.I. DuPont de Nemours & Co. (Wilmington, DE).
  • the water was deionized water with a minimum surface tension of about 71 dynes/cm.
  • the literature value for the surface tension of a 1% aqueous Zonyl surfactant solution is 17.4 dynes/cm.
  • the system in which these parameters are measured includes a fiber sample to be tested and a bath of fluid in which the fiber partially resides; as the fiber and fluid are moved relative to each other in the direction of gravity, the total force on the fiber F T is equal to the sum of the wetting force F W and the bouyant force F B .
  • the apparatus used comprised a motor-driven movable stage on which a container of the wetting fluid was moved and above which the prepared fiber (glued to the hook) was suspended; this apparatus was located in a cage isolating the materials from air currents.
  • the fiber was suspended from a balance communicating with an electrobalance, the communication interface also connecting with a desktop computer, a printer therefor, and a chart recorder.
  • the surface tension of the water and the surfactant solution were both measured; the average value for the surface tension of the water was 72 dynes/cm and the literature value was used for the surfactant. Then, with the fiber suspended above the container of wetting fluid, the stage is raised to immerse the fiber in the wetting fluid until the plumb is just immersed, and the apparatus is then zeroed.
  • the stage with the wetting liquid is moved further upwards, and the new fiber weight is recorded as the stage moves (this is handled by the automated electrobalance, available from Cahn Instrument Company); since the fiber is thus being immersed into the wetting fluid, this is a measurement of the advancing contact angle (as opposed to a retreating contact angle if the fiber were being withdrawn from the wetting fluid).
  • the wetting force F W can be determined algebraically. Measurements of the fiber perimeter and the surface tension of the wetting liquid, combined with the Wilhelmy equation, yield the advancing contact angle.
  • control fibers had an advancing contact angle equal to or greater than about 95°, whereas the fibers of this invention always presented an advancing contact angle equal to or greater than about 95°.
  • the average advancing contact angle for the present fibers is about 15% greater than that for the controls. Further, it can be seen that the instrinsic hydrophobicity of the control fibers is increased by the present invention.
  • these fibers were compared with control fibers to determine the amount, if any, of the lubricant that is extracted.
  • the inventive fibers were compared with a commercially available T-190TM polypropylene fiber (available from Hercules Incorporated, Wilmington, DE) having a typical polysiloxane topical finish composition applied to the surface of the fiber.
  • inventive fibers containing 1.3 wt.% internal poly(dimethylsiloxane) lubricant were about 21 ⁇ 2 years old ( i.e. , about 21 ⁇ 2 years since having been spun) and the control fibers were a little over one year old.
  • a 4 g sample of the fiber was weighed to the nearest 0.0001 g and placed in an extraction thimble.
  • About 50 ml of methylene chloride (CH 2 Cl 2 ) was poured into the thimble and allowed to drip into an aluminum cup disposed below the thimble; after gravity dripping was stopped, pressure (about 40 psi) was applied until all dripping had stopped.
  • CH 2 Cl 2 methylene chloride
  • the fiber was then removed from the thimble, placed on a sheet of aluminum foil, and heated on a steambath to dryness.
  • the extract in the cup was heated on the steambath to dryness. This extract residue was dissolved by mixing with 1.5 ml m- xylene , three times, and then brought to a total volume of 10 ml by the addition of m -xylene.
  • the absorbance at 1260 cm -1 between the peak maximum measurement and the baseline (between 1300 and 1200 cm -1 ; the SiCH 3 band is generally between 1260 and 1265 cm -1 ) was measured, and then plotted against the volume PDMS values (0.0004, 0.0008, etc.).
  • a linear regression analysis was used to calculate the slope and intercept of this standardization curve; the slope was determined to be 0.02292.
  • the present invention provides polyolefin fibers having an essentially non-extractable internal lubricant, preferably of the formula X-A 1 -[Si(A 2 R 1 )(A 3 R 2 )-O-] z -A 4 -Y as herein defined.

Claims (55)

  1. Fibre contenant une polyoléfine, formée à partir d'un mélange comprenant une polyoléfine et un polysiloxane de formule X- [Si (R1) (R2)-O-]z-Y, dans laquelle X et Y sont choisis indépendamment entre des groupes aliphatiques n'ayant pas plus de 22 atomes de carbone et leurs éthers, z a une valeur de 10 à 50 ou plus de 50, et (a) R1 et R2 sont choisis indépendamment parmi des groupes aliphatiques n'ayant pas plus de 22 atomes de carbone et le polysiloxane a un poids moléculaire d'au moins 15 000, ou (b) un des groupes R1 et R2 représente un groupe arène et l'autre représente un groupe arène ou répond à la définition en (a) .
  2. Fibre suivant la revendication 1, dans laquelle la polyoléfine est le polyéthylène, le polypropylène, un copolymère éthylène-propylène, ou un de leurs mélanges.
  3. Fibre suivant la revendication 2, dans laquelle la polyoléfine est le polypropylène.
  4. Fibre suivant la revendication 2, dans laquelle la polyoléfine comprend 5 à 95 % en poids de polypropylène et 95 à 5 % en poids de polyéthylène.
  5. Fibre suivant la revendication 4, comprenant des quantités approximativement égales de polyéthylène et de polypropylène.
  6. Fibre suivant la revendication 4, comprenant 75 à 95 % de polyéthylène et 25 à 5 % de polypropylène.
  7. Fibre suivant l'une quelconque des revendications 1 à 6, dans laquelle R1 et R2 sont choisis indépendamment dans le groupe consistant en (i) des groupes aliphatiques, substitués ou non substitués, ayant 1 à 8 atomes de carbone, et (ii) des groupes arène facultativement substitués avec jusqu'à 3 groupes aliphatiques ayant chacun indépendamment 1 à 3 atomes de carbone.
  8. Fibre suivant la revendication 7, dans laquelle R1 et R2 sont choisis indépendamment dans le groupe consistant en (i) des groupes aliphatiques ayant 1 à 3 atomes de carbone et (ii) des groupes arène.
  9. Fibre suivant la revendication 8, dans laquelle R1 représente un groupe méthyle et R2 représente un groupe phényle.
  10. Fibre suivant la revendication 7, dans laquelle R1 et R2 sont choisis indépendamment parmi des groupes aliphatiques ayant 1 à 3 atomes de carbone.
  11. Fibre suivant l'une quelconque des revendications 1 à 10, dans laquelle le polysiloxane a un poids moléculaire compris dans l'intervalle de 15 000 à 450 000.
  12. Fibre suivant l'une quelconque des revendications 1 à 11, sous forme d'une fibre coupée.
  13. Fibre suivant l'une quelconque des revendications 1 à 12, comprenant en outre un revêtement de finition hydrophile.
  14. Fibre suivant l'une quelconque des revendications 1 à 12, comprenant en outre un revêtement de finition antistatique.
  15. Fibre suivant l'une quelconque des revendications 1 à 14, fournie sous forme d'une fibre monofilament ou d'un fil multifilament ou d'un non-tissé lié par filage ou non-tissé soufflé en masse fondue ou d'un câble de filaments.
  16. Fibre suivant la revendication 15, fournie sous forme d'un article non-tissé comprenant des fibres coupées, cardées et liées suivant la revendication 1.
  17. Fibre contenant une polyoléfine telle que produite par filage, à lubrification interne, ayant un angle de contact intrinsèque supérieur à celui d'une fibre de la même composition contenant une polyoléfine sans ledit lubrifiant interne, ladite fibre à lubrification interne comprenant, comme lubrifiant interne, jusqu'à 10 % en poids d'un polysiloxane répondant à la formule générale X-[Si(R1)(R2)-O-]z-Y, dans laquelle X et Y sont choisis indépendamment entre des groupes aliphatiques n'ayant pas plus de 22 atomes de carbone et leurs éthers, z a une valeur suffisamment grande pour rendre le polysiloxane hydrophobe, et
    (a) R1 et R2 sont choisis indépendamment parmi des groupes aliphatiques n'ayant pas plus d'environ 22 atomes de carbone et le polysiloxane a un poids moléculaire d'au moins environ 15 000, ou
    (b) un des groupes R1 et R2 représente un groupe arène et l'autre représente un groupe arène ou répond à la définition en (a).
  18. Fibre suivant la revendication 17, dans laquelle la polyoléfine est une polyoléfine suivant l'une quelconque des revendications 2 à 6.
  19. Fibre suivant la revendication 17 ou 18, dans laquelle le polysiloxane est un polysiloxane suivant l'une quelconque des revendications 7 à 11.
  20. Fibre suivant l'une quelconque des revendications 1 à 19, dans laquelle la surface de la fibre est pratiquement dépourvue d'émulsionnants et de solvants.
  21. Fibre suivant l'une quelconque des revendications 1 à 20, ayant une tête hydrostatique d'au moins 62 mm.
  22. Fibre suivant la revendication 21, ayant une tête hydrostatique d'au moins 102 mm.
  23. Masse polymère fondue filable comprenant un polymère contenant une polyoléfine et un polysiloxane de formule X-[Si (R1) (R2)-O-]z-Y, dans laquelle X et Y sont choisis indépendamment entre des groupes aliphatiques n'ayant pas plus de 22 atomes de carbone et leurs éthers, z a une valeur de 10 à 50 ou plus de 50, et (a) R1 et R2 sont choisis indépendamment parmi des groupes aliphatiques n'ayant pas plus de 22 atomes de carbone et le polysiloxane a un poids moléculaire d'au moins 15 000, ou (b) un des groupes R1 et R2 est un groupe arène et l'autre est un groupe arène ou répond à la définition en (a).
  24. Procédé pour la production d'un article manufacturé, comprenant les étapes consistant :
    A. à fournir une masse polymère fondue filable suivant la revendication 23, et
    B. à filer ladite masse fondue en une fibre telle qu'obtenue par filage.
  25. Procédé suivant la revendication 24, comprenant en outre l'étirage de ladite fibre telle que produite par filage pour produire une fibre étirée.
  26. Procédé suivant la revendication 25, comprenant en outre la coupe de la fibre étirée en fibres coupées.
  27. Procédé suivant la revendication 26, comprenant en outre le frisage de la fibre étirée pour produire des fibres coupées frisées.
  28. Procédé suivant la revendication 27, comprenant en outre le cardage des fibres coupées frisées en une bande et la liaison de la bande pour produire un article non-tissé.
  29. Procédé suivant la revendication 28, dans lequel l'article non-tissé a un écoulement moyen d'au moins 50 %.
  30. Procédé suivant la revendication 28, comprenant en outre les étapes de fabrication de l'article non-tissé sous forme d'une partie d'un dispositif d'hygiène choisi entre des couches jetables, des tampons pour incontinents et des dispositifs cataméniaux.
  31. Procédé suivant la revendication 30, dans lequel l'article non-tissé a un écoulement moyen d'au moins 90 %.
  32. Fibre à constituants multiples, comprenant au moins deux constituants distincts disposés en une configuration désirée, au moins un desdits constituants comprenant : une composition contenant une polyoléfine formée à partir d'un mélange comprenant un polymère contenant une polyoléfine et jusqu'à 10 % en poids de ladite composition d'un polysiloxane hydrophobe de formule X- [Si (R1) (R2) -O-]z-Y, dans laquelle X et Y sont choisis indépendamment entre des groupes aliphatiques n'ayant pas plus de 22 atomes de carbone et leurs éthers, z a une valeur de 10 à 50 ou plus de 50, et (a) R1 et R2 sont choisis indépendamment entre des groupes aliphatiques n'ayant pas plus de 22 atomes de carbone et le polysiloxane a un poids moléculaire d'au moins 15 000, ou (b) un des groupes R1 et R2 est un groupe arène et l'autre est un groupe arène ou répond à la définition en (a).
  33. Fibre à constituants multiples suivant la revendication 32, dans laquelle la fibre est une fibre à deux constituants fournie sous une configuration à gaine et coeur.
  34. Fibre à deux constituants suivant la revendication 33, dans laquelle le constituant de gaine comprend ladite polyoléfine et ledit polysiloxane.
  35. Fibre à deux constituants suivant la revendication 34, dans laquelle la polyoléfine est choisie entre le polyéthylène, le polypropylène, des copolymères éthylène-propylène et leurs mélanges.
  36. Fibre à deux constituants suivant la revendication 35, dans laquelle le constituant de coeur comprend du poly(téréphtalate d'éthylène).
  37. Fibre suivant l'une quelconque des revendications 32 à 36, sous forme d'une fibre coupée.
  38. Dispositif d'hygiène choisi entre des couches jetables, des tampons pour incontinents et des dispositifs cataméniaux, ledit dispositif comprenant un article non-tissé consistant essentiellement en une bande liée de fibres sous forme coupée, lesdites fibres étant des fibres contenant une polyoléfine, formées à partir d'un mélange comprenant une polyoléfine et jusqu'à 10 % en poids d'un polysiloxane répondant à la formule générale X-[Si(R1)(R2)-O-]z-Y, dans laquelle X et Y sont choisis indépendamment entre des groupes aliphatiques n'ayant pas plus de 22 atomes de carbone et leurs éthers, z a une valeur de 10 à 50 ou plus de 50, et (a) R1 et R2 sont choisis indépendamment parmi des groupes aliphatiques n'ayant pas plus de 22 atomes de carbone et le polysiloxane a un poids moléculaire d'au moins 15 000, ou (b) un des groupes R1 et R2 représente un groupe arène et l'autre répond à la définition en (a).
  39. Article manufacturé choisi parmi des articles non-tissés et articles tissés, ledit article comprenant des fibres contenant une polyoléfine, formées à partir d'un mélange comprenant une polyoléfine et jusqu'à 10 % en poids d'un polysiloxane répondant à la formule générale X-[Si(R1)(R2)-O-]z-Y, dans laquelle X et Y sont choisis indépendamment entre des groupes aliphatiques n'ayant pas plus de 22 atomes de carbone et leurs éthers, z a une valeur de 10 à 50 ou plus de 50, et (a) R1 et R2 sont choisis indépendamment parmi des groupes aliphatiques n'ayant pas plus de 22 atomes de carbone et le polysiloxane a un poids moléculaire d'au moins 15 000, ou (b) un des groupes R1 et R2 représente un groupe arène et l'autre représente un groupe arène ou répond à la définition en (a) .
  40. Fibre filée en masse fondue, telle qu'obtenue par filage, formée à partir d'un mélange comprenant une polyoléfine et un polysiloxane, ladite fibre ayant un angle de contact intrinsèque supérieur à celui d'une fibre filée en masse fondue, telle qu'obtenue par filage, dépourvue dudit polysiloxane, et ladite fibre étant pratiquement dépourvue d'émulsionnants et d'agents tensioactifs sur sa surface, ledit polysiloxane répondant à la formule générale X- [Si (R1) (R2)-O-]z-Y, dans laquelle X et Y sont choisis indépendamment entre des groupes aliphatiques n'ayant pas plus de 22 atomes de carbone et leurs éthers, z a une valeur de 10 à 50 ou plus de 50, et (a) R1 et R2 sont choisis indépendamment parmi des groupes aliphatiques n'ayant pas plus de 22 atomes de carbone et le polysiloxane a un poids moléculaire d'au moins 15 000, ou (b) un des groupes R1 et R2 représente un groupe arène et l'autre représente un groupe arène ou répond à la définition en (a).
  41. Fibre suivant la revendication 40, dans laquelle la polyoléfine comprend au moins 50 % en poids de polypropylène ou polyéthylène.
  42. Fibre suivant la revendication 40 ou 41, sous forme d'une fibre à deux constituants choisie entre (a) des configurations côte à côte, dans laquelle chaque côté comprend ladite polyoléfine et le polysiloxane, et (b) des configurations à gaine et coeur dans lesquelles au moins ladite gaine comprend ladite polyoléfine et ledit polysiloxane.
  43. Fibre suivant l'une quelconque des revendications 40 à 42, dans laquelle la fibre, telle que produite par filage, donne une valeur de test de Suter modifié (colonne d'eau montante) d'au moins 30.
  44. Fibre suivant l'une quelconque des revendications 1-22, 32-37 ou 40-43, ayant une valeur en deniers de fibre de 0,11 dtex à 44 dtex.
  45. Fibre suivant la revendication 43, dans laquelle la valeur en deniers va de 0,55 dtex à 6,6 dtex.
  46. Fibre suivant la revendication 45, dans laquelle la valeur en deniers va de 1,1 dtex à 3,3 dtex.
  47. Fibre suivant l'une quelconque des revendications 1-22, 32-37 ou 40-46, la fibre étant une fibre frisée.
  48. Fibre suivant la revendication 47, dans laquelle la fibre est liée à une autre telle fibre.
  49. Article manufacturé comprenant une étoffe non-tissée comprenant des fibres coupées, cardées et liées, lesdites fibres coupées comprenant un mélange intime d'une polyoléfine et d'un polysiloxane compatible avec celle-ci, la surface desdites fibres étant pratiquement dépourvues d'émulsionnants et d'agents tensioactifs, l'étoffe non-tissée ayant un écoulement moyen d'étoffe d'au moins 30 %, lesdites fibres étant des fibres suivant l'une quelconque des revendications 1-22, 32-37 ou 40-48.
  50. Article suivant la revendication 49, dans lequel ladite étoffe a un écoulement moyen d'au moins 50 %.
  51. Article suivant la revendication 50, dans lequel ladite étoffe a un écoulement moyen d'au moins 70 %.
  52. Article suivant la revendication 51, dans lequel ladite étoffe a un écoulement moyen d'approximativement 90 %.
  53. Article suivant l'une quelconque des revendications 48-52, dans lequel l'étoffe non-tissée a un grammage de 6 à 108 g/m2.
  54. Article suivant la revendication 53, dans lequel le grammage est compris dans l'intervalle de 12 à 36 g/m2.
  55. Article suivant la revendication 54, dans lequel le grammage est compris dans l'intervalle de 18 à 32 g/m2.
EP96305779A 1995-08-08 1996-08-06 Fibre discontinue cardable hydrophobique avec lubrifiant interne et son procédé et utilisation Expired - Lifetime EP0761846B1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US08/715,130 US5763334A (en) 1995-08-08 1996-09-17 Internally lubricated fiber, cardable hydrophobic staple fibers therefrom, and methods of making and using the same
US09/025,890 US6177191B1 (en) 1996-08-06 1998-02-18 Internally lubricated fiber, cardable hydrophobic staple fibers therefrom, and methods of making and using the same

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US51235195A 1995-08-08 1995-08-08
US512351 1995-08-08

Publications (3)

Publication Number Publication Date
EP0761846A2 EP0761846A2 (fr) 1997-03-12
EP0761846A3 EP0761846A3 (fr) 1997-11-05
EP0761846B1 true EP0761846B1 (fr) 2004-01-21

Family

ID=24038735

Family Applications (1)

Application Number Title Priority Date Filing Date
EP96305779A Expired - Lifetime EP0761846B1 (fr) 1995-08-08 1996-08-06 Fibre discontinue cardable hydrophobique avec lubrifiant interne et son procédé et utilisation

Country Status (5)

Country Link
EP (1) EP0761846B1 (fr)
JP (1) JPH09170112A (fr)
DE (1) DE69631359T2 (fr)
DK (1) DK0761846T3 (fr)
MX (1) MX9603248A (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9296174B2 (en) 2011-01-12 2016-03-29 Compagnie Chomarat Composite laminated structures and methods for manufacturing and using the same
US11491057B2 (en) 2014-11-06 2022-11-08 The Procter & Gamble Company Crimped fiber spunbond nonwoven webs / laminates

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6762137B2 (en) 2000-12-21 2004-07-13 Kimberly-Clark Worldwide, Inc. Water repellant meltblown webs and laminates
DE602005024924D1 (de) * 2004-02-11 2011-01-05 Procter & Gamble Hydrophobe oberflächenbeschichtete saugfähige artikel
EP1819850B1 (fr) * 2004-12-03 2009-04-01 Dow Global Technologies Inc. Methode pour l'amelioration de caracteristiques de liberation des fibres polyolefines elastiques
US8328782B2 (en) * 2005-02-18 2012-12-11 The Procter & Gamble Company Hydrophobic surface coated light-weight nonwoven laminates for use in absorbent articles
JP5089123B2 (ja) * 2005-10-07 2012-12-05 花王株式会社 吸収性物品
JP6408320B2 (ja) * 2014-09-19 2018-10-17 花王株式会社 親水性不織布及び不織布用繊維処理剤
CA2967001A1 (fr) 2014-11-06 2016-05-12 The Procter & Gamble Company Bandes a ouvertures a motifs, stratifies, et leurs procedes de fabrication
JP6611323B2 (ja) * 2015-11-16 2019-11-27 花王株式会社 吸収性物品並びに不織布及びその製造方法
EP4335420A2 (fr) 2017-02-16 2024-03-13 The Procter & Gamble Company Articles absorbants avec substrats ayant des motifs répétitifs d'ouvertures comprenant une pluralité d'unités récurrentes

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4472556A (en) * 1982-12-20 1984-09-18 Dow Corning Corporation Method for enhancing one or more mechanical properties of partially crystalline thermoplastics
JPH0791760B2 (ja) * 1986-10-17 1995-10-04 チッソ株式会社 不織布及びその製造方法
DE486158T1 (de) * 1990-11-15 1993-12-16 Hercules Inc Kardierbare hydrophobe Polyolefinfaser, Material und Verfahren zu ihrer Herstellung.
CA2069269C (fr) * 1991-05-28 1998-09-15 Roger W. Johnson Fibre de polypropylene hydrophobe cardable
US5545481A (en) * 1992-02-14 1996-08-13 Hercules Incorporated Polyolefin fiber

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9296174B2 (en) 2011-01-12 2016-03-29 Compagnie Chomarat Composite laminated structures and methods for manufacturing and using the same
US11491057B2 (en) 2014-11-06 2022-11-08 The Procter & Gamble Company Crimped fiber spunbond nonwoven webs / laminates

Also Published As

Publication number Publication date
DE69631359T2 (de) 2004-12-09
EP0761846A3 (fr) 1997-11-05
DE69631359D1 (de) 2004-02-26
JPH09170112A (ja) 1997-06-30
EP0761846A2 (fr) 1997-03-12
MX9603248A (es) 1997-03-29
DK0761846T3 (da) 2004-05-24

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