EP1000188A1 - Articles non tisses a base d'alcool polyvinylique a couleurs vives et techniques de production - Google Patents

Articles non tisses a base d'alcool polyvinylique a couleurs vives et techniques de production

Info

Publication number
EP1000188A1
EP1000188A1 EP97935260A EP97935260A EP1000188A1 EP 1000188 A1 EP1000188 A1 EP 1000188A1 EP 97935260 A EP97935260 A EP 97935260A EP 97935260 A EP97935260 A EP 97935260A EP 1000188 A1 EP1000188 A1 EP 1000188A1
Authority
EP
European Patent Office
Prior art keywords
absorbent article
polyvinyl alcohol
binder
group
fibers
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP97935260A
Other languages
German (de)
English (en)
Other versions
EP1000188B1 (fr
Inventor
Bradford B. Wright
Michael M. Rock, Jr.
Sy R. Shimabukuro
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
3M Co
Original Assignee
Minnesota Mining and Manufacturing Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Minnesota Mining and Manufacturing Co filed Critical Minnesota Mining and Manufacturing Co
Publication of EP1000188A1 publication Critical patent/EP1000188A1/fr
Application granted granted Critical
Publication of EP1000188B1 publication Critical patent/EP1000188B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • 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
    • 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
    • D04H1/425—Cellulose series
    • D04H1/4258—Regenerated cellulose 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
    • D04H1/58—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 applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives
    • D04H1/60—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 applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives the bonding agent being applied in dry state, e.g. thermo-activatable agents in solid or molten state, and heat being applied subsequently
    • 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
    • D04H1/58—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 applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives
    • D04H1/64—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 applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives the bonding agent being applied in wet state, e.g. chemical agents in dispersions or solutions

Definitions

  • the invention relates to durable, absorbent, colored, nonwoven wiping articles made with a polyvinyl alcohol based binder and to methods for the manufacture of such articles.
  • Wiping articles made of natural chamois a highly absorbent leather derived from the hides of goat-like antelopes (e.g., from chamois) or other animals, are commonly used in the polishing or drying of certain objects such as automobiles after washing.
  • the absorbent properties of natural chamois have also been emulated in "synthetic chamois", and synthetic chamois articles or wiping articles are known and are commercially available.
  • These synthetic articles are formed, for example, by binding a nonwoven web of fibers with a binder.
  • the fibers may comprise, for example, polyvinyl alcohol (PVA) — based fibers bound together with a crosslinked PVA binder.
  • PVA polyvinyl alcohol
  • Binders made with chemically crosslinked PVA provide some distinct advantages when incorporated in a synthetic wipe. For example, PVA binders increase and improve the properties of a dry wipe by providing a non-linting wipe surface, good mechanical strength, and desired hydrophilic properties. Moreover, PVA binders may be cured in the presence of colorants to generate colored wiping articles.
  • coloration of the wipe is generally desired for aesthetic reasons as well as for practical or functional reasons. Certain colors, for example, are effective in hiding stains on the surface of the wipe. Additionally, some countries have developed color coding systems for consumer items, including wiping articles, wherein the color of the article designates an intended area of use such as red for use in bathrooms, green for use in kitchens, and the like. In the coloration of these articles, the use of pigments is generally preferred over dyes because pigments offer greater resistance to fading in the presence of cleaning chemicals.
  • PVA based wiping articles are currently colored in pastel shades achieved either by the addition of pigment or as a result of acid discoloration during manufacture.
  • the use of pigments to provide more vividly colored PVA based wiping articles has generally been unsuccessful because these wiping articles have consistently experienced pigment loss, referred to as "color bleed", when the wipe is exposed to water, especially in the presence of soaps or detergents. .
  • the color bleed phenomenon is attributed to the loss of certain pigment particles that are not adequately retained by the binder resin, but are readily released during the wringing or soaking of the wipe, especially in soapy water.
  • the noticeable loss of pigment from these articles is aesthetically undesirable, and the pigment lost from the article may damage (e.g., stain) the surface being wiped.
  • this invention provides vividly colored absorbent articles particularly useful as wiping articles and a method for their manufacture.
  • the articles provide excellent wiping performance, but experience no significant color bleed during use, even when exposed to soapy water or the like.
  • this invention is an absorbent article comprising a substrate comprised of organic fibers having a plurality of pendant hydroxyl groups; a binder coated on at least a portion of the fibers, the binder comprising a crosslinked polyvinyl alcohol and a hydrophobic polymer; and pigment distributed within the binder.
  • the substrate is a nonwoven web of organic fibers selected from the group of rayon and polyvinyl alcohol.
  • the polyvinyl alcohol (PVA) polymer may be derived from partially or completely hydrolyzed homopolymers and copolymers of vinyl acetate.
  • the PVA polymer is a silanol modified PVA.
  • the hydrophobic polymer is derived from a hydrophobic latex emulsion.
  • the hydrophobic polymer is a self-crosslinking polymer.
  • the pigment is preferably an organic pigment.
  • the term "absorbent” refers to the ability of a material to absorb a liquid (e.g., water) and to retain the liquid until it is forced out; it also refers to the ability of a material to wet out quickly when exposed to a liquid.
  • Substrate refers to a woven, knitted, or nonwoven material.
  • Fiber refers to a threadlike structure (In referring to the fibers of webs used to make the articles herein, “linear density” or “fineness” refers to the weight in grams for a given length of a single fiber.).
  • Crosslinking refers to chemical reactions of monomers, prepolymers, or polymers (present, for example, in the binder precursor) in which linkages are formed between polymer chains.
  • Self- crosslinking refers to a polymer derived from reactants (e.g., monomers), a prepolymer or a polymer that is capable of undergoing a crosslinking reaction without the addition of crosslinking agents.
  • Polymer refers to an insoluble material (i.e., a coloring agent) suspended in a medium.
  • this invention is a method of making an absorbent article, the method by providing a substrate comprising organic fibers having a plurality of pendant hydroxyl groups; coating at least a portion of the fibers with a mixture of a pigment and a binder precursor, the binder precursor comprising polyvinyl alcohol and a hydrophobic latex emulsion; and curing the binder precursor to provide an absorbent article.
  • this invention is an absorbent article comprising a substrate having first and second major surfaces, the substrate comprising organic fibers having a plurality of pendant hydroxyl groups, wherein at least one of the first and second major surfaces is coated with a mixture of a binder comprising a crosslinked polyvinyl alcohol and a hydrophobic polymer and pigment distributed within the binder.
  • Figure 1 is a perspective view of a wiping article made in accordance with the invention.
  • Figure 2 is a cross-section along the lines 2-2 of the article of Figure 1;
  • Figure 3 is a schematic diagram of a preferred method of making articles of the invention.
  • the articles of this invention preferably are comprised of substrates comprising organic fibers having a plurality of pendant hydroxyl groups, wherein at least a portion of the fibers are coated with a mixture of pigment and binder.
  • a mixture of PVA and hydrophobic latex emulsion forms a binder precursor which is cured to form the binder of the invention.
  • the PVA crosslinks due to the presence of a crosslinking agent.
  • the hydrophobic latex emulsion is preferably a self-crosslinking latex, which means that a crosslinking agent is not needed.
  • the combination of the crosslinked PVA and the hydrophobic polymer derived from the hydrophobic latex emulsion produces a binder that will retain pigment within the finished wiping article, maintain the color of the finished article, and prevent color bleed.
  • the substrate of this invention may be a woven or nonwoven material.
  • Woven materials include fabrics made by weaving and knitting. Nonwoven materials typically are referred to as mats or webs and are formed by techniques including stitchbonding, air laying, carding, spin bonding, melt blowing, and wet laying.
  • the substrate of this invention is a nonwoven web. More preferably, the nonwoven web has entangled fibers. Entangled fibers are produced by methods such as hydroentangling and needletacking.
  • the substrate typically will have a thickness ranging from about 0.25 to 2.54 mm (10 to 100 mils), preferably 0.76 to 1.78 mm (30 to 70 mils), more preferably 1.02 to 1.52 mm (40 to 60 mils).
  • the weight per unit area of the substrate preferably ranges from about
  • Woven or knitted webs can be produced to a desired thickness and basis weight.
  • Nonwoven webs can be produced by some techniques in very thin, lightweight layers. Preferred thicknesses and basis weights for nonwoven webs may be achieved either by carding and crosslapping operations or by air laying followed by fiber entanglement (e.g., hydroentanglement, needletacking and the like). Carded and crosslapped webs may also be entangled. Carded and crosslapped webs are preferred for use in the articles of the present invention.
  • Figure 1 illustrates an absorbent wiping article 10 according to the invention.
  • Article 10 includes a nonwoven web made of a plurality of fibers 12 at least a portion of which are coated with a mixture of pigment and binder, as is further described herein.
  • the article 10 (illustrated in exaggerated thickness) includes first and second major surfaces 14 and 16, respectively.
  • Each of surfaces 14 and 16 comprise a combination of calendered and fused binder coated organic fibers.
  • More nonwoven web makes up the middle portion 18 of the article 10.
  • an article can be prepared wherein only one of the major surfaces (i.e., surface 14) is coated with binder.
  • the uncoated surface i.e., surface 16
  • the nonwoven web may be made from any of a variety of hydrophilic fibers, and may include a portion (e.g., less than about 50 percent) of hydrophobic fibers.
  • Hydrophobic fibers include polyolefin fibers such as polyester, polypropylene, and polyamide fibers.
  • Suitable hydrophilic fibers for use herein may be selected from the following fiber types: cellulosic-type fibers such as PVA (including hydrolyzed copolymers of vinyl esters, particularly hydrolyzed copolymers of vinyl acetate), cotton, viscose rayon, cuprammonium rayon and the like; as well as thermoplastics such as polyesters, polypropylene, polyethylene, nylons and the like.
  • the preferred cellulosic-type fibers are rayon and polyvinyl alcohol (PVA) and are commercially available as staple fibers.
  • Suitable rayon fibers are viscose rayon staple fibers commercially available from Courtaulds Fibers Inc. of Axis, AL, under the designations 18552 and T2222.
  • Other suitable rayon fibers are commercially available from Courtaulds Fibers, Inc. under the trade designation "Lyocell” and "Tencel”.
  • Suitable PVA fibers include those available under the trade designations VPB 152 and VPB 174 from Kuraray Co. of Tokyo, Japan.
  • Nonwoven webs containing 100 percent PVA fibers, 100 percent rayon fibers, and blends of PVA fibers and rayon fibers in the ratio of about 1 : 100 to about 100: 1 are considered within the scope of the invention, and those nonwoven webs having PVA:rayon within the ratio of about 30:70 to about 70:30 are particularly preferred in this invention, because resulting articles exhibit good hydrophilicity and strength, and are soft to the touch.
  • the fibers used to make the foregoing webs typically have linear densities ranging from about 0.5 to about 10 denier (about 0.06 to about 11 dtex), although higher denier fibers may also be employed.
  • Fibers having linear densities from about 0.5 to 3 denier (0.06 to about 3.33 dtex) are preferred. Fibers having a length ranging from about 0.5 to about 10 cm may be employed as a starting material for the nonwoven web, and fiber lengths ranging from about 2 to about 8 cm are preferred.
  • the nonwoven web suitable for use in the articles of the invention may be made according to well known methods including air-laying, carding, stitch-bonding, wet laying or melt blowing and spunbonded techniques.
  • a preferred nonwoven web is an open, lofty, three-dimensional air-laid nonwoven material described by Hoover, et al. in U.S. Patent No. 2,958,593, incorporated herein by reference.
  • An air laid web may readily be formed on commercially available equipment such as a "Rando Webber” machine (commercially available from Rando Machine Company, New York) or by other conventional means. (See, for example, Turbak, A. in "Nonwovens: An Advanced tutorial", Tappi Press, Atlanta, Georgia, 1989).
  • Binders suitable in the practice of the present invention comprise a crosslinked PVA and a hydrophobic polymer derived from a hydrophobic latex emulsion. This hydrophobic polymer may also be crosslinked.
  • the polymer derived from a hydrophobic latex emulsion is chemically bonded (e.g., by crosslinking) to the PVA in the cured binder.
  • the binder precursor is comprised of a mixture of dissolved PVA, crosslinking agent, and hydrophobic latex emulsion.
  • the PVA polymer may be derived from partially or completely hydrolyzed homopolymers and copolymers of vinyl acetate.
  • PVA polymers having varying degrees of hydrolysis, molecular weights, and comonomers are known and are commercially available, for example, from E.I. DuPont de Nemours Co., Inc. (Wilmington, DE) under the tradename "Elvanol", from Air Products and Chemicals, Inc.
  • a preferred PVA is a partially or completely hydrolyzed homopolymer or copolymer derived from the copolymerization of first and second monomers.
  • the first monomer may be selected from the group consisting of monomers within the general formula (I)
  • Y is O(CO)R 7 ; and R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are independently selected from the group consisting of hydrogen and organic radicals having from 1 to about 10 carbon atoms. Silanol modified PVA is particularly preferred in the binder of the invention.
  • Suitable silanol modified PVA may be made by the copolymerization of any one of a number of ethylenically unsaturated monomers having hydrolyzable groups with an alkoxysilane-substituted ethylenically unsaturated monomer.
  • ethylenically unsaturated monomers having hydrolyzable groups are vinyl acetate, acetoxyethyl acrylate, acetoxyethyl methacrylate, and various propyl acrylate and methacrylate esters.
  • alkoxysilane-substituted ethylenically unsaturated monomers include vinyl trialkoxysilanes such as vinyl trimethoxysilane, vinyl triethoxysilane, vinyl tripropoxysilane, vinyl tributoxysilane and the like. Vinyl trimethoxysilane is preferred.
  • silanol-modified PVA may be produced from the copolymerization of vinyl acetate and vinyl trimethoxysilane, followed by the direct hydrolysis of the copolymer in alkaline solution (see below).
  • a suitable commercially available silanol-modified PVA is that known under the trade designation "Rl 130" (Kuraray Chemical KK, Japan), believed to contain from about 0.5 to about 1.0 mole percent of the silyl groups as vinylsilane units, exhibit a degree of polymerization of about 1700, and the degree of hydrolysis of the vinyl acetate units being about 99 percent or higher.
  • the PVA is mixed with a suitable crosslinking agent compatible with the PVA.
  • suitable crosslinking agents include any of a variety of known crosslinking agents including, for example, aldehydes, diisocyanates, polyacrylic acid, and various metal complexes such as chelates of aluminum, titanium, silicon, zirconium and the like.
  • PVA crosslinkers are described, for example, in Polyvinyl Alcohol -
  • the PVA is crosslinked via secondary hydroxyl groups on the PVA backbone using chelating organic titanates as the crosslinking agent.
  • the resultant binder will theoretically further react with hydroxyl groups on the fibers when cured at elevated temperatures.
  • Particularly preferred are “dual" crosslinked PVA polymers wherein an amorphous metal oxide is also used as a crosslinking agent to coordinate with the silanol groups on the PVA backbone while the aforementioned titanates coordinate with secondary hydroxyl groups, as mentioned.
  • a particularly useful amorphous metal oxide is commercially available under the trade designation "Nalco 8676" (Nalco Chemical, Naperville, IL), an amorphous alumina sol with an average particle size less than about 30 angstroms.
  • Particularly preferred PVA polymers are those utilizing the aforementioned amorphous metal oxide and a chelating organic titanate crosslinking agent comprising either dihydroxybis(ammonium lactato)titanium (commercially available under the trade designation "Tyzor LA” from E. I. DuPont de Nemours & Co., Inc., Wilmington, DE) or titanium orthoesters (commercially available under the trade designation "Tyzor 131" from E. I. DuPont de Nemours & Co., Inc.).
  • a chelating organic titanate crosslinking agent comprising either dihydroxybis(ammonium lactato)titanium (commercially available under the trade designation "Tyzor LA” from E. I. DuPont de Nemours & Co., Inc., Wilmington, DE) or titanium orthoesters (commercially available under the trade designation "Tyzor 131" from E. I. DuPont de Nemours & Co., Inc.).
  • the theoretical crosslink density for a suitable PVA polymer may range from 1 to about 40 mole percent based on moles of ethylenically unsaturated monomer.
  • the binder comprises a polymer derived from a latex emulsion in the binder precursor.
  • the inclusion of the latex emulsion in the binder precursor has been shown to play an important role in the retention of pigment within the finished article to avoid color bleed when the finished articles are subsequently exposed to soapy water, for example.
  • retention of pigment within the binder is accomplished by the use of a polymer derived from a hydrophobic latex emulsion without sacrificing the desired absorbency of the finished article.
  • color bleed may result primarily from the loss of the smallest particles of pigment (typically less than about 0.1 micrometer).
  • binder precursors with low solids content e.g., less than 15 percent in water
  • the small pigment particles are believed to lose their associated surfactant, causing particle agglomeration.
  • the resulting particle agglomerates are too large to be retained within the cured binder.
  • color bleed results when the agglomerated pigment particles are redispersed into water when the finished article is rinsed with soap and water.
  • Known procedures for mixing pigment have been ineffective in reducing the color bleed phenomenon.
  • the preferred hydrophobic latex emulsion is one which, when cured, provides a polymer that is associated with the PVA and/or the fibers of the substrate in a manner that resists removal upon exposure to moist or wet conditions, (e.g., exposure to soapy water).
  • the latex emulsion is capable of being crosslinked to form a water insoluble crosslinked polymer that is highly resistant to being washed from the finished article.
  • the latex emulsion is self-crosslinking and, most preferably, the latex emulsion is both self-crosslinking and capable of covalently bonding with the PVA.
  • a latex emulsion is coated onto a surface to form a film, then dried and cured.
  • the wetting tension of a surface is related to the hydrophobicity of a surface. This can be measured by using the surface tension of water; or, more specifically, by measuring the angle formed by a drop of water in contact with a surface.
  • a latex is considered hydrophobic if, on a cured film of the latex emulsion, the advancing contact angle of water is greater than about 45°.
  • the latex emulsion may be present in the binder precursor in amounts ranging from about 0.05 percent up to about 20 percent by weight (based on dry solids). Concentrations above about 20 percent by weight of the latex emulsion in the binder precursor are thought to adversely affect the absorbency of the finished article. Concentrations less than about 0.05 percent are not effective for retaining the pigment in the binder.
  • the latex emulsion is present in the binder precursor in an amount from about 1 percent to about 15 percent by weight (based on dry solids). More preferably, the latex emulsion is present in an amount of about 3 percent to about 10 percent by weight (based on dry solids).
  • the hydrophobic polymer should have a glass transition temperature (T g ) of less than about 5° C, preferably less than about 0° C, and more preferably less than about -15° C.
  • hydrophobic latex emulsions for use in this invention include, but are not limited to, those based on acrylates such as copolymers of butyl acrylate, ethyl acrylate, acrylic acid, methacrylic acid, methyl methacrylate, acrylonitrile, styrene, N- methylolacrylamide, etc.; polyurethanes; polyesters; and polyamides.
  • acrylates such as copolymers of butyl acrylate, ethyl acrylate, acrylic acid, methacrylic acid, methyl methacrylate, acrylonitrile, styrene, N- methylolacrylamide, etc.
  • polyurethanes polyesters
  • polyamides polyamides
  • Latex emulsions useful in the invention include acrylate emulsions available under the trade designations "Rohamere 132", “Rohamere 1878”, “Rohamere 1900-D”, “Rohamere 1970-D”, “Rohamere 3045", “Rohamere 31-130”, “Rohamere 4096D”, “Rohamere 587”, “Rohamere 84116", “Rohamere 8437”, “Rohamere 8464”, “Rohamere 8478”, “Rohamere 8662” and “Rohamere 8721 “, all available from Rohm Tech Inc. (Maiden, MA).
  • acrylic latex emulsions having suitable physical characteristics for the practice of this invention are commercially available under the trade designation "Rhoplex” from Rohm and Haas Co. of Philadelphia, PA.
  • Vinyl acetate/ethylene latex emulsions having suitable physical characteristics are available under the trade designation “Airflex” and polyvinyl acetate homopolymers are available under the trade designation “Vinac”, both from Air Products and Chemicals, Inc. of Allentown, PA.
  • Preferred hydrophobic latices include styrene -butyl acrylate available under the trade designation "Hycar T-278" from B.F. Goodrich Co.
  • the binder precursor comprises a solution, preferably aqueous, of dissolved PVA, crosslinking agent and hydrophobic latex emulsion.
  • the binder precursor may be from about 1 percent to about 60 percent solids by weight, preferably from about 2 percent to about 20 percent solids by weight.
  • the binder precursor is typically prepared by first dissolving the PVA in water, adding crosslinking agents and then adding a hydrophobic latex with stirring.
  • Crosslinking of the PVA as well as of the latex emulsion should be avoided until curing conditions (i.e., high temperatures) are present.
  • organic acids such as citric acid may be added to the binder precursor to help stabilize the titanates (e.g., dihydroxybis(ammonium lactato) titanium) in aqueous compositions until the binder precursors are exposed to crosslinking and curing conditions.
  • acid activated crosslinking agents for example, aldehydes, or aminoplast resins
  • Pigments that are useful in the present invention include inorganic and organic pigments.
  • Inorganic pigment generally refers to a finely divided metallic oxides or sulfides. Inorganic pigments are not soluble. They may be highly colored for use as coloring agents or, for example, white, for use as an opacifying agent.
  • Organic pigment generally refers to highly colored materials which are carbon-based, rather than metal-based. For the purposes of this invention, an organic compound is a pigment when it imparts a desired color to the article and is not soluble in the solvents used while making or using the articles of this invention.
  • pigments are added to the binder precursor as aqueous dispersions of finely divided particles.
  • the particles typically range in size from sub-micrometer to about 10 micrometers.
  • the dispersions facilitate distribution of pigment within the binder.
  • Suitable aqueous dispersions of organic pigments are available from commercial sources . These include textile and graphic arts pigment grades from companies including Sun Chemical Co. (Fort Lee, NJ), Heucotech Ltd. (Fairless Hills, PA), Catawba Char-Lab (Charlotte, NC), Organic Dyestuffs Co. (Charlotte, NC), Perm Color ( Doylestown, PA), and BASF Corp. (Wyandotte, MI). Pigments also may be prepared according to methods well known in the art.
  • Suitable pigments include, but are not limited to, organic pigments, for example, azo pigments such as soluble or insoluble azo pigments or condensed azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, perylene- perynone pigments, dioxazine pigments, vat dye pigments and basic dye pigments, and inorganic pigments such as carbon black, titanium oxide, chrome yellow, cadmium yellow, cadmium red, red iron oxide, iron black, zinc flower, Prussian blue and ultramarine.
  • organic pigments are preferred, because they do not contain heavy metals, such as chromium, lead, tin and/or barium.
  • optional ingredients include softeners (such as ethers and alcohols), fragrances, fillers (such as for example silica, alumina, and titanium dioxide particles), and bactericidal agents (e.g., quaternary ammonium salts).
  • softeners such as ethers and alcohols
  • fragrances such as for example silica, alumina, and titanium dioxide particles
  • bactericidal agents e.g., quaternary ammonium salts.
  • a substrate having the desired thickness and weight per unit area is provided. At least a portion of the substrate is coated with a mixture of binder precursor and pigment, dried, and heated to cure the binder precursor to form binder and pigment on at least a portion of the substrate.
  • FIG 3 a method of producing a preferred substrate, a nonwoven web, (as illustrated in Figures 1 and 2) is shown schematically.
  • staple fibers are fed via hopper 20 (or other means) into carding station 22.
  • a moving conveyer transports carded web 26 from carding station 22, typically to a crosslapper, not shown, to form a layered web having fibers oriented at various angles relative to the machine direction of carded web 26.
  • Carded web 26 then passes through needle tacking station 28 to entangle the fibers, thus strengthening and consolidating the web, and resulting in needle tacked web 30. Entanglement of the web may alternatively be achieved by means other than needle tacking, such as by hydroentanglement.
  • Needle tacked web 30 may optionally pass through calender station 32 to achieve a desired thickness, providing calendered web 34 that preferably is not more than about 1.52 mm (60 mils) thick.
  • Calendered web 34 then passes through an immersion bath 36 where a mixture of pigment and binder precursor 37 is applied. Web 34 passes under rollers 38 and emerges as coated web 40.
  • Coating of the web with binder precursor may be accomplished by immersion coating methods as well as by other coating methods known in the art including roll coating, spray coating, gravure coating, transfer coating and the like. During coating, at least a portion of the fibers are coated, and preferably the web is coated on at least one of its first and second major surfaces with a mixture of pigment and binder precursor.
  • the web In the preparation of articles to be used as hand wiping articles or the like, the web is typically coated on both of its major surfaces.
  • the coating weight i.e., dry binder add-on weight
  • the coating weight ranges from about 1 percent to about 95 percent, preferably from about 10 percent to about 60 percent, more preferably 20 percent to 40 percent.
  • Coated web 40 passes through drying station 42 to form dried web 44. While resident in drying station 42, the web is typically and preferably exposed to an elevated temperature to remove water from the binder precursor and form dried web 44. Drying may be accomplished using heated rollers (i.e., "hot can"), a forced air oven, a radiant panel or other known means.
  • drying is uniform throughout the thickness of the web.
  • web 44 may be suitable for use without further curing.
  • Drying and curing of the binder precursor may be accomplished by exposing dried web 44 to more than two different temperatures by, for example, performing the drying and the curing steps in an oven having more than two heating zones. Additionally, in drying and curing the binder precursor, both major surfaces of the uncured web preferably are simultaneously exposed to a heat source. Alternatively, although less preferred, the first and second major surfaces of the coated web may be exposed in sequence to the heat source.
  • Web 48 may then be passed through another set of calender rollers 50, which may used to emboss a pattern and fuse the surfaces of the article.
  • Web 52 generally has a thickness of no more than 1.52 mm (60 mils), and a weight ranging from about 50 g/m 2 to about 250 g/m 2 .
  • Calendering of the binder coated web at temperatures from about 5 to about 40°C below the melting point of the fiber may reduce the likelihood of lint attaching to the surface of the articles and will generally provide a smooth surface.
  • Embossing of a textured pattern onto the wiping article may be performed simultaneously with calendering, or in a subsequent step.
  • Web 52 may then pass through an optional second needling station 54 to perforate the web for decorative or other purposes, after which the web is slit and wound onto take- up roll 56.
  • web 52 may pass through a hot water (i.e., from about 60 to about 80°C) bath (not shown), and calendared and dried by means of heated rollers as described above, to produced a soft "hand" or feel before being slit and wound up onto take-up roll 56.
  • a hot water bath i.e., from about 60 to about 80°C
  • Another way to achieve a soft feel in final packaged form and to aid in processing is to apply a small amount of water or fungicide solution to the article immediately prior to packaging.
  • the cured article may be laminated or otherwise affixed to another substrate, if desired, such as a sponge, a urethane foam backing or the like. It may be desirable in the applications to use cured articles having a binder on only one of the major surfaces, thus providing an untreated major surface (i.e., a surface free of cured binder) for the application of adhesives or the like.
  • the articles of this invention are particularly useful as "synthetic chamois" due to their absorbency and durability. These synthetic wiping articles are useful for cleaning various surfaces.
  • the presence of pigment in the article produces an aesthetically pleasing and functional absorbent wiping article for consumer use.
  • the articles are highly colored, producing readily recognizable colored articles which are used for cleaning certain areas (e.g., green for use in kitchens).
  • the articles prepared according to this invention exhibit minimal color bleed due to pigment being lost from the article during use.
  • the examples illustrate the preparation of webs coated with a binder and a pigment suitable for use as absorbent articles.
  • the nonwoven web was prepared from 50 percent rayon fibers (3.0 d x 6.3 cm, T2222, Courtaulds Fibers Inc. (Axis, AL) and 50 percent polyvinyl alcohol fibers (1.7 d x 5.3 cm, VPB 174, Kuraray Co. KK (Tokyo, Japan)).
  • the nonwoven web was prepared by carding and crosslapping and was needlepunched to provide a web with a basis wt. of 162.9 g/m 2 (4.8 oz / yd 2 ) and a thickness of 1.45 mm (57 mils).
  • the web was coated as pieces of dimension 30.5 cm x 38.1 cm (12 inches by 15 inches).
  • a coating solution was made by heating 9.3 parts polyvinyl alcohol ("Rl 130" from Kuraray Co. KK) to boiling in 90.7 parts deionized water to dissolve the PVA.
  • Amorphous alumina sol (0.44 parts, "Nalco 8676” from Nalco Chemical Co.) was added to the PVA solution followed by the addition of 4.4 parts titanate ("Tyzor 131, commercially available from E.I. DuPont de Nemours, Co., Inc., of Wilmington, DE).
  • the resultant solution was cooled and then diluted with deionized water to achieve a solids content of 3.6 weight percent when dried at 121°C (250°F).
  • PROCEDURE C (BINDER PRECURSOR AND WIPING ARTICLES)
  • Latex emulsion and pigment were added to the PVA solution in proportions described in the examples, along with additional deionized water as indicated in the examples.
  • the PVA solution and the latex emulsion form the binder precursor.
  • the mixture of pigment and binder precursor was poured onto the substrate and evenly distributed by hand to make a coated substrate. Then the coated substrate was air dried at 65.6 °C (150° F) until dry and heat cured at 149 °C (300° F) for 10 minutes.
  • the amount of the dried and cured polymer (i.e., binder) on the substrate was about 18 weight percent.
  • COLOR BLEED Color bleed was determined by first taking a sample of material to be evaluated and placing it in 2 liters of water and allowed to soak for 60 seconds. The sample was then wrung out by hand and the rinse water was collected in a dishpan. The soak and wringing steps were repeated twenty times for each material sample tested. Thereafter, the color hue and intensity of the rinse solution and the dishpan surface were observed and recorded, and the visible abso ⁇ tion spectrum of the rinse water was measured and recorded using a 10 cm path length cell on a UV-visible spectrophotometer.
  • the rinse solution was then discarded from the dishpan and replaced with 2 liters of fresh water.
  • the sample was wrung out completely and 2 g of detergent (available under the trade designation "Liquinox" from Alconox, Inc. of New York, New York) was placed on the sample and rubbed in lightly over the majority of sample surface. The thus treated sample was placed in the fresh water.
  • the sample was then wrung out by hand with the detergent/water mixture returned to the dishpan.
  • the sample was again soaked and wrung out a second time and the visible absorption spectrum of the rinse water was measured using a 10 cm path length cell, as previously described.
  • TENSILE STRENGTH Samples were prepared for testing by wetting them in water and wringing them out once with a mechanical wringer. Samples were die cut to 2.54 x 15.24 cm (1 x 6 inch). Tensile strength measurements were made using a tensile tester (Instron Model "TM', obtained from Instron Co ⁇ . of Canton, MA), using a procedure modified from that of the test method described in ASTM D 5035-95, "Standard Test Method for Breaking Force and Elongation of Textile Fabrics (Strip Method)". The sample thickness also was recorded. A constant rate of extension was employed, and jaws were clamp-type. Rate of jaw separation was 25.4 cm/min (10 inches/min).
  • the sample was placed into the jaws, set at a 2.5 cm (1 inch) gap, and the cycle was started.
  • the tensile strength (i.e., load) and the elongation at break were measured.
  • the tensile strength is an indication of the stiffness of the sample.
  • Elongation at break is a measure of a load which is applied and increased until the sample breaks. Measurements were done on the samples in machine direction and the cross web direction, as mechanical properties may vary depending upon the direction of orientation.
  • Wiping articles were immersed for 8 hours in a mixture of 286 g of 5.25 weight percent chlorine bleach (household strength chlorine bleach, commercially available under the trade designation "Clorox" from The Clorox Co. of Oakland, CA) in 14 liters of tap water. When the samples were removed from the bleach solution, they were visually evaluated for color fading.
  • chlorine bleach household strength chlorine bleach, commercially available under the trade designation "Clorox” from The Clorox Co. of Oakland, CA
  • Samples were prepared for tear testing by soaking them for 5 minutes in tepid water and then mechanically wringing them. Elmendorf tear tests were conducted on 6.35 x 27.94 cm (2.5 x 11 inch) die-cut, notched (20 mm) samples, using an Elmendorf Tear Tester model number 60-32, from Thwing-Albert Co., with a 6.4 kg pendulum. The procedure was modified from that of the test method described in ASTM D 1424-96, "Standard Test Method for Tearing Strength of Fabrics by Falling-Pendulum Type (Elmendorf) Apparatus". An average of four measurements is reported. Samples were tested in both the machine direction and the transverse direction. The tear tests are indicative of the durability of the absorbent articles of this invention.
  • each sample was removed from the water and passed through a mechanical wringer at single thickness.
  • the sample was transferred onto the weighing pan with one quick smooth motion, and the balance reading in grams was recorded as Damp Weight (C). This procedure was repeated for the remaining cut samples.
  • the cut samples were then placed into a vented forced air oven maintained at 49°C
  • the hydrophobic latex emulsion which is present in the binder precursor dries and cures to form a polymer which generally is expected to have poorer abrasion resistance than that of PVA polymer alone.
  • abrasion testing was performed using a Taber Abraser Model 503 equipped with H22 Calibrade wheels with 500 g weights. Samples were prepared for abrasion testing by saturating them in tepid water and mechanically wringing the samples 4 times to remove all excess water. Destruction was recorded at the point where a visible hole (0.3 cm (1/8 inch) diameter) in the sample appeared.
  • a red wiping article using the substrate described above in PROCEDURE A It was coated with 139 g of PVA solution (prepared as described in PROCEDURE B) mixed with 0.6 g of an organic red pigment (commercially available as "Orcobrite Red BRYN 6002" from Organic Dye Stuffs of Charlotte, NC) and 61 g deionized water. The coated sample was dried and cured as described in PROCEDURE C.
  • a blue wiping article was prepared using the substrate described above in PROCEDURE A. It was coated with 139 g of PVA solution (prepared as described in PROCEDURE B) mixed with 0.5 g of an organic blue pigment (commercially available as "Orcobrite Blue 3GN 2010") and 61 g deionized water. The coated sample was dried and cured as described in PROCEDURE C.
  • a green wiping article was prepared using the substrate described above in PROCEDURE A. It was coated with 139 g of PVA solution (prepared as described in PROCEDURE B) mixed with 0.3 g of an organic green pigment (commercially available as "Orcobrite Green YN 9") and 61 g deionized water. The coated sample was dried and cured as described in PROCEDURE C.
  • This example demonstrates the preparation of a red wiping article.
  • the sample was prepared using the fiber web described in PROCEDURE A. It was coated with a binder precursor mixture prepared from 132 g PVA solution (as described in PROCEDURE B), 0.45 g of a latex emulsion ("Hycar T-278"), 0.6 g of an organic red pigment (“Orcobrite Red BRYN 6002”) and 67 g deionized water. The coated sample was dried and cured as described in PROCEDURE C.
  • the resultant wiping article contained 5 percent of the polymer derived from the latex emulsion ("Hycar T-278") in the binder based on dry solids.
  • This example demonstrates the preparation of a red wiping article.
  • the sample was prepared using the fiber web described in PROCEDURE A . It was coated with a binder precursor mixture prepared from 125 g PVA solution (as described in PROCEDURE B), 0.91 g of a latex emulsion ("Hycar T-278"), 0.6 g of an organic red pigment (“Orcobrite Red BRYN 6002”) and 74 g deionized water. The coated sample was dried and cured as described in PROCEDURE C.
  • the resultant wiping article contained 10 percent of a polymer derived from the latex emulsion ("Hycar T-278") in the binder based on dry solids.
  • This example demonstrates the preparation of a red wiping article.
  • the sample was prepared using the fiber web described in PROCEDURE A. It was coated with a binder precursor mixture prepared from 118 g PVA solution (as described in PROCEDURE B), 1.36 g of latex emulsion ("Hycar T-278"), 0.6 g of an organic red pigment (“Orcobrite Red BRYN 6002”) and 80 g deionized water.
  • the coated sample was dried and cured as described in PROCEDURE C.
  • the resultant wipe contained 15 percent of polymer derived from the latex emulsion ("Hycar T-278") in the binder based on dry solids.
  • This example demonstrates the preparation of a blue wiping article.
  • the sample was prepared using the fiber web described in PROCEDURE A. . It was coated with a binder precursor mixture prepared from 125 g PVA solution (as described in PROCEDURE B), 0.91 g of latex emulsion ("Hycar T-278"), 0.5 g of an organic blue pigment (“Orcobrite Blue 3GN 2010”) and 74 g deionized water. The coated sample was dried and cured as described in PROCEDURE C. The resultant wipe contained 10 percent of polymer derived from the latex emulsion ("Hycar T-278") in the binder based on dry solids.
  • This example demonstrates the preparation of a green wiping article.
  • the sample was prepared using the fiber web described in PROCEDURE A. It was coated with a binder precursor mixture prepared from 125 g PVA solution (as described in PROCEDURE B), 0.91 g of latex emulsion ("Hycar T-278"), 0.3 g of an organic green pigment (“Orcobrite Green YN 9”) and 74 g deionized water.
  • the coated sample was dried and cured as described in PROCEDURE C.
  • the resultant wipe contained 10 percent of polymer derived from the latex emulsion ("Hycar T-278") in the binder based on dry solids.
  • Wiping articles made according to Comparative Example A and Example 2 were tested for bleach stability according to the above Bleach Stability Test Method.
  • the immersed sample from Comparative Example A had faded in color level compared to non-immersed wiping articles from Comparative Example A, while the immersed sample from Example 2 remained vividly red, with less apparent color fading. No negative effects were observed on bleach stability using the latex additive.
  • Wiping articles were subjected to the color bleed test as follows. In the case of red, blue, and green wiping articles of the Comparative Examples A, B and C, heavy color bleed was observed with wringing in water, and severe color bleed was observed on wringing with detergent. In contrast, at most a faint color could be detected after wringing with detergent in the case of the wiping articles with 10 percent or more added latex. The results with 5 percent addition of the "Hycar T-278" latex were intermediate to the 0 and 10 percent levels.
  • a red wiping article was prepared using the substrate described above in PROCEDURE A. It was coated with 152 g of PVA solution prepared as described in PROCEDURE B mixed with 0.3 g of an organic red pigment (commercially available as "Orcobrite Red BRYN 6002") and 61 g deionized water. The coated sample was dried and cured as described in PROCEDURE C. The binder content of the resultant cured wiping article was 14 percent (based on dry solids).
  • a red wiping article was prepared using the fiber web as described in PROCEDURE A. It was coated with a binder precursor mixture prepared from 137 g PVA solution (as described in PROCEDURE B), 1.2 g of latex emulsion ("Rhoplex NW- 1845", a non-crosslinking latex), 0.63 g of an organic red pigment (“Orcobrite Red BRYN 6002”) and 61 g deionized water. The coated sample was dried and cured as described in PROCEDURE C. The binder content of the resultant cured wipe was 15 percent.
  • a red wiping article was prepared using the fiber web described in PROCEDURE A. It was coated with a binder precursor mixture prepared from 137 g PVA solution (as described in PROCEDURE B), 1.2 g of latex emulsion ("Rhoplex ST-954", an acrylic self- crosslinking emulsion), 0.63 g of an organic red pigment (“Orcobrite Red BRYN 6002”) and 61 g deionized water. The coated sample was dried and cured as described in PROCEDURE C. The binder content of the resultant cured wipe was 15 percent.
  • a red wiping article was prepared using the fiber web described in PROCEDURE A. It was coated with a binder precursor mixture prepared from 137 g PVA solution (as described in PROCEDURE B), 1.2 g of a styrene-butadiene self-crosslinking latex emulsion ("Unocal 4170"), 0.64 g of an organic red pigment (“Orcobrite Red BRYN 6002”) and 61 g deionized water. The coated sample was dried and cured as described in PROCEDURE C. The binder content of the resultant cured wipe was 15 percent.

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dispersion Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Nonwoven Fabrics (AREA)
  • Cleaning Implements For Floors, Carpets, Furniture, Walls, And The Like (AREA)
  • Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
  • Laminated Bodies (AREA)

Abstract

Cette invention a trait à des articles absorbants, vivement colorés, des plus utiles comme torchons, ainsi qu'à leur technique de production. L'un des articles préférés se caractérise par le fait qu'il comporte, (a), un voile non tissé constitué de fibres organiques possédant plusieurs groupes hydroxyles pendants, (b), un liant composé d'un alcool polyvinylique et d'un polymère hydrophobe enrobant une partie, au moins, des fibres et, (c), un pigment réparti dans le liant.
EP97935260A 1997-07-31 1997-07-31 Articles absorbants a base d' alcool polyvinylique a couleurs vives et techniques de production Expired - Lifetime EP1000188B1 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US1997/013577 WO1999006622A1 (fr) 1997-07-31 1997-07-31 Articles non tisses a base d'alcool polyvinylique a couleurs vives et techniques de production

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EP1000188A1 true EP1000188A1 (fr) 2000-05-17
EP1000188B1 EP1000188B1 (fr) 2002-10-30

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EP (1) EP1000188B1 (fr)
JP (1) JP2001512190A (fr)
AU (1) AU734446B2 (fr)
CA (1) CA2296490A1 (fr)
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WO (1) WO1999006622A1 (fr)

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US6110588A (en) 1999-02-05 2000-08-29 3M Innovative Properties Company Microfibers and method of making
US6630231B2 (en) 1999-02-05 2003-10-07 3M Innovative Properties Company Composite articles reinforced with highly oriented microfibers
US6420024B1 (en) 2000-12-21 2002-07-16 3M Innovative Properties Company Charged microfibers, microfibrillated articles and use thereof
US6692823B2 (en) 2001-12-19 2004-02-17 3M Innovative Properties Company Microfibrillated articles comprising hydrophillic component
EP1394294A1 (fr) * 2002-08-30 2004-03-03 Kuraray Co., Ltd. Fibres d'alcool polyvinylique à pouvoir absorbant élevé et tissus non-tissés les comprenant.
WO2004021848A1 (fr) 2002-09-05 2004-03-18 Novalabs L.L.C. Appareil de nettoyage pour toilettes et boite de rangement
DE102008024943B4 (de) * 2007-08-22 2017-10-26 Eswegee Vliesstoff Gmbh Verfahren zur Herstellung eines Grundvliesstoffes als Beschichtungsträger
DE102011010136A1 (de) 2011-02-03 2012-08-09 Rolf Siegel Verfahren zur Hydrophilierung von Flächengebilden aus niederenergetischen Materialien
GB202101624D0 (en) * 2021-02-05 2021-03-24 Nonwovenn Ltd Nonwoven fabric for oral pouched product, and methods of manufacturing a nonwoven fabric
WO2022167621A1 (fr) 2021-02-05 2022-08-11 Nonwovenn Ltd Tissu non tissé, produit en sachet et procédés associés
CN115637532A (zh) * 2022-09-08 2023-01-24 浙江鹏辰造纸研究所有限公司 一种工业单晶硅炉用擦拭纸及其制备方法

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WO1994028223A1 (fr) * 1993-06-02 1994-12-08 Minnesota Mining And Manufacturing Company Articles non-tisses et leurs procedes de production

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DE69716773D1 (de) 2002-12-05
AU3824497A (en) 1999-02-22
EP1000188B1 (fr) 2002-10-30
JP2001512190A (ja) 2001-08-21
AU734446B2 (en) 2001-06-14
CA2296490A1 (fr) 1999-02-11
WO1999006622A1 (fr) 1999-02-11
DE69716773T2 (de) 2003-07-03

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