MXPA00001040A - Polyvinyl alcohol based nonwoven articles with vivid colors and methods of producing same - Google Patents

Abstract

Vividly colored absorbent articles useful as wiping articles and a method for their manufacture. A preferred article is characterized by (a) a nonwoven web comprised of organic fibers having a plurality of pendant hydroxyl groups;(b) a binder comprising a cross-linked polyvinyl alcohol and a hydrophobic polymer coated on at least a portion of the fibers, (c) pigment distributed within the binder.

Description

NON-TUNED ARTICLES BASED ON POLYVINYL ALCOHOL WITH INTENSIVE COLORS AND PRODUCTION METHODS OF THE SAME The invention relates to non-woven, durable, absorbent and colored cleaning articles made with a polyvinyl alcohol based linker and to methods for the manufacture of said articles.

Background of the Invention Cleaning articles made of natural suede, a highly absorbent skin derived from the leather of goat-like antelopes (e.g., suede) or other animals, are commonly used in the polishing or drying of certain objects such as automobiles after washing. The absorbent properties of natural suede have also been emulated in "synthetic suede", and synthetic suede articles or cleansing articles are known and commercially available. These synthetic articles are formed, for example, by joining a non-woven web of fibers with a linker. The fibers can comprise, for example, polyvinyl alcohol (PVA) - based fibers linked with a PVA crosslinker. The published PCT Application WO 94/28223 discloses highly absorbent cleaning articles comprising a bonded non-woven network REF .: 32698 with PVA cross-linked binding resins. Other known synthetic suedes are made by joining non-woven fibers with an acrylic latex binder. Suitable acrylic linkers typically include functional groups to yield both the binder and the finished hydrophilic cleaning article. Although these acrylic based cleaning products are comparatively cheap to make, they often experience a high undesirable drag when used in many cleaning applications.

Linkers made with chemically crosslinked PVA provide some distinct advantages when incorporated into a synthetic cleanser. For example, PVA linkers increase and improve the properties of dry cleaning by the proportion of a clean, lint-free surface, good mechanical strength and desired hydrophilic properties. In addition, PVA linkers can be tanned in the presence of dyes to generate colored cleaning articles.

In the manufacture of synthetic suede or cleaning articles, the coloration of the cleaner is generally desirable 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 cleaner. Additionally, some countries have developed color coding systems for consumer items, including cleaning articles, wherein the color of the article designates an area predisposed to be used such as red for use in bathrooms, green for use in kitchens, and the like. In the coloring of these articles, the use of pigments is generally preferred over the dyes because the pigments offer greater resistance to the drop in the presence of cleaning chemicals.

Commercially available PVA-based cleaning articles are currently colored in pastel shades achieved either by the addition of the pigment or as a result of acid discoloration during its manufacture. The use of pigments to provide colored PVA-based cleaning articles more intensively, however, has generally been unsuccessful in that these cleaning articles have consistently experienced loss of pigment, referred to as "color bleeding," when the cleaner is exposed. to water, especially in the presence of soaps and detergents. The phenomenon of color bleeding is attributed to the loss of certain pigment particles that are not adequately retained by the resin binder, but are quickly released during the draining or soaking of the cleaner, especially in soapy water. The remarkable loss of the pigment of these articles is aesthetically undesirable, and the loss of the pigment from the article can damage (e.g., stain) the surface to be cleaned. Although the problem of color bleeding can be avoided by extensive washing of the cleaning article prior to packaging and use, this additional preparation is expensive and can damage the cleaner. Accordingly, there is a need to solve the problem of color bleeding in PVA-based cleaning articles by the proportion of means for pigment retention in the cleaner without prewash of the article prior to use.

It is desirable to provide a solution to the problem to come and fill a desired need by the proportion of PVA-based cleaning articles with bright and intense colors. It is desirable to provide these cleaning articles by a coloring process using pigments, which result in an article that does not experience noticeable color bleeding when exposed to water, including water containing soaps or detergents. It is also desirable to provide a method for the manufacture of these cleaning articles.

Brief Description of the Invention The present invention provides intensely colored absorbent articles particularly useful as cleaning articles and a method for their manufacture. The articles provide excellent cleaning performance, but do not experience significant color bleeding during use, even when exposed to soapy water or the like.

In one aspect, this invention is an absorbent article comprising a substrate comprised of organic fibers having a plurality of pendant hydroxyl groups; a binder protected in at least a portion of the fibers, the binder comprises a cross-linked polyvinyl alcohol and a hydrophobic polymer; a pigment discributed within the binder. Preferably, the substrate is a non-woven network of fibers selected from the group of rayon and polyvinyl alcohol. The polyvinyl alcohol (PVA) polymer can be derived from partially or fully hydrolyzed homopolymers and from vinyl acetate copolymers. Preferably, the PVA polymer is a modified silanol PVA. The hydrophobic polymer is derived from a hydrophobic latex emulsion. Preferably, the hydrophobic polymer is a cross-linked self-binding polymer. The pigment is preferably an organic pigment.

As used herein, the term "absorbent" refers to the ability of a material to absorb a liquid (e.g., water) and to retain a liquid until it is forced out; it also refers to the ability of a material to moisten quickly when exposed to a liquid. "Substrate" refers to a material, interlacing, weaving or non-interlacing. "Fiber" refers to a structure in the form of a strand (Referring to network fibers used to make the articles described herein, "linear density" or "fineness" refers to the weight in grams of a given length of a single fiber. ). "Cross-linking" refers to chemical reactions of monomers, prepolymers, or polymers (present, for example, in the precursor linker) in which the bonds are formed between polymer chains. "Cross-linking" refers to a polymer derived from reactants (e.g., monomers), a prepolymer or a polymer that is capable of traversing a cross-linking reaction without the addition of cross-linking agents. "Pigment" refers to an insoluble material (i.e., a coloring agent) suspended in a medium.

In another aspect, this invention is a method of making an absorbent article, the method by the proportion of a substrate comprising organic fibers having a plurality of pendant hydroxyl groups; covering at least a portion of the fibers with a mixture of a pigment and a precursor linker, the precursor linker comprises polyvinyl alcohol and a hydrophobic latex emulsion; and the tanning of the precursor linker to provide an absorbent article.

In yet another aspect, 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 impregnated with a mixture of a linker comprising a crosslinked polyvinyl alcohol and a hydrophobic polymer and a pigment distributed within the linker.

Brief Description of the Drawings In the description of the details of the preferred embodiment, reference is made to the various Figures, wherein: Figure 1 is a perspective view of a cleaning article made according to the invention; Figure 2 is a cross section along lines 2-2 of the article of Figure 1; Y Figure 3 is a schematic diagram of a preferred method of making articles of the invention.

Detailed Description of the Preferred Modalities The articles of this invention are preferably comprised of substrates comprising organic fibers having a plurality of pendant hydroxyl groups, wherein at least a portion of the fibers are impregnated with a mixture of pigment and binder. A mixture of PVA and a hydrophobic latex emulsion forms a precursor binder which is tanned to form the binder of the invention. PVA binds crosswise due to the presence of a cross-linking agent. The hydrophobic latex emulsion is preferably a cross-junction latex, which means that a cross-linking agent is not needed. Surprisingly, the combination of the cross-linked PVA and the hydrophobic polymer derived from the hydrophobic latex emulsion produces a binder that will retain the pigment within the finished cleaning article, maintain the color of the finished article, and prevent color bleeding.

The substrate of this invention may be an interlaced or non-interlaced material. The interlaced materials include factories made by interlacing and weaving. The non-interlaced materials are typically referred to as tufts or nets and are formed by techniques that include point joining, air rest, carting, spinning, melt blowing, and wet loosening.

Preferably, the substrate of this invention is a non-woven network. More preferably, the nonwoven web has entangled fibers. The entangled fibers are produced by methods such as hydroentanglement and needle fixation.

The substrate will typically 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 is preferably in the range of about 50 g / m2 to about 250 g / m2. Woven or woven nets can be produced to a desired thickness and a basis weight. The non-woven networks can be produced by some techniques in very thin, lightweight layers. Preferred thicknesses and base weights for non-woven networks can be achieved either by paperback and cross-lap operations or by air rest followed by fiber entanglement (e.g., hydro-tangle, fixed with needle and the like). Corresponded and cross-lap networks are preferred for use in the articles of the present invention.

Referring to the drawings, Figure 1 illustrates an absorbent cleaning article 10 according to the invention. Article 10 includes a non-woven web made of a plurality of fibers 12 with at least a portion of which is impregnated with a mixture of pigment and binder, as described hereinafter. As seen in Figure 2, article 10 (illustrated in exaggerated thickness) includes first and second major surfaces 14 and 16, respectively. Each of the surfaces 14 and 16 comprises a combination of organic fibers impregnated with fused linker and calendered. Further the non-woven web forms the middle portion 18 of article 10. Those skilled in the art will appreciate that an article can be prepared where only one of the larger surfaces (i.e., surface 14) is impregnated with a binder. The non-impregnated surface (i.e., surface 16) can be laminated, for example, to another article or a substrate such as sponge, urethane foam, or the like.

The non-woven web can be made of any of a variety of hydrophilic fibers, and can 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 types of fibers: cellulose-type fibers such as PVA (including hydrolyzed copolymers of vinyl esters, particularly hydrolyzed vinyl acetate copolymers), cotton, viscose rayon, cupramonium rayon and the like; as well as thermoplastics such as polyesters, polypropylene, polyethylene, nylon and the like. Preferred cellulose-type fibers are rayon and polyvinyl alcohol (PVA) and are commercially available as main fibers. Suitable rayon fibers are viscose rayon main fibers commercially available from Fibras Courtaulds Inc. of Axis, AL, under the designations 18552 and T2222. Other suitable rayon fibers are commercially available from Fibras Courtaulds, Inc. under the designation "Lyocell" and "Tencel". Suitable PVA fibers include those available under the change designations of VPB 152 and VPB 174 of Kuraray Co. of Tokyo, Japan.

Non-woven networks containing 100 percent PVA fibers, 100 percent rayon fibers, and mixtures 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 non-woven webs having PVA: rayon within the ratio of about 30:70 to about 70:30 are particularly preferred in this invention, because the resulting articles exhibit good hydrophilicity and strength, and are soft To contact. The fibers used to make subsequent nets typically have linear densities in the range of about 0.5 to about 10 denier (about 0.06 to about 11 dtex), although higher denier fibers can also be used. ("Denier" is a unit of linear density or fineness that indicates the weight in grams for a length of 9000 meters of fiber while "dtex" or "decitex" is another unit for linear density that indicates the weight in grams for a length of 10,000 meters of fiber.) Fibers that have linear densities of about 0.5 to 3 denier (0.06 to about 3.33 dtex) are preferred. Fibers having a length in the range of about 0.5 to about 10 cm can be used as a starting material for the non-woven web, and fiber lengths in the range of about 2 to about 8 cm are preferred.

The non-woven web suitable for use in the articles of the invention may be made according to well known methods including air rest, carting, seaming, wet or melt blowing and spinning techniques. A preferred nonwoven web is an open, high, non-interlaced, three-dimensional airlaid material described by Hoover, et al. In the U.S. Patent No. 2,958,593, incorporated herein by reference. An air placement network can readily be formed into commercially available equipment such as the "Rando Webber" machine (commercially available from the 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).

A greater portion of the fibers of the substrate are joined with a binder formed by tanning the precursor binder. Tanning refers to cross-linking reactions in the precursor linker that result in an insoluble linker. Suitable linkers in the practice of the present invention comprise a cross-linked PVA and a hydrophobic polymer derived from a hydrophobic latex emulsion. This hydrophobic polymer can also be crosslinked. Preferably, the polymer derived from the hydrophobic latex emulsion is chemically bound (e.g., by cross-linking) to the PVA in the tanned linker. Preferably the precursor linker is comprised of a mixture of dissolved PVA, a cross-linking agent, and a hydrophobic latex emulsion.

The PVA polymer can be derived from partially or fully hydrolyzed homopolymers and vinyl acetate copolymers. PVA polymers having varying degrees of hydrolysis, molecular weight, and comonomers are known and commercially available, for example, from E.l. DuPont de Nemours Co., Inc. (Wilmington, DE) under the name "Elvanol" change, from Air Products and Chemicals, Inc. (Allentown, PA) under the name of "Airvol" change, from Kuraray Chemical KK ( Tokyo, Japan) as K, C, HL, and HL series under the change designations "KL-118, KL-318, KL-506, KM-118, C-118, C-506, C-318, HL -12E, HL-1203, HL-75, HL-1108, R-1130, R-2105 and R-2130"of functional polymer. All these commercial compositions are suitable for use in the formulation of the precursor linker.

A preferred PVA is a partially or fully hydrolyzed homopolymer or copolymer derived from the copolymerization of first and second monomers. The first monomer can be selected from the group consisting of monomers within the general formula (I) R R C = C RJ (I) X where X is Si (OR4OR5OR6); Y the second monomer is selected from the group comprising monomers within the general formula (II) R? R "C = C RJ (II) Where Y is O (CO) R7; and R1, R2, R3, R4, R5, R6 and R7 are independently selected from the group consisting of hydrogen and organic radicals having from 1 to about 10 carbon atoms.

Modified silanol PVA is particularly preferred in the linker of the invention. The appropriate modified silanol PVA can be made by copolymerizing any of a number of ethylenically unsaturated monomers having hydrolyzable groups with an unsaturated ethylenically substituted alkoxysilane monomer. Non-limiting examples of ethylenically unsaturated monomers having hydrolyzable groups are vinyl acetate, acetoxyethyl acrylate, acetoxyethyl methacrylate, and various propyl acrylate and methacrylate esters. Examples of ethylenically substituted alkoxysilane-unsaturated monomers include vinyl trialkoxysilanes such as vinyl trimethoxysilane, vinyl triethoxysilane, vinyl tripropoxysilane, vinyl tributoxysilane and the like. Vinyl trimethoxysilane is preferred.

A particularly preferred modified silanol PVA can be produced from the copolymerization of vinyl acetate and vinyl trimethoxysilane, followed by direct hydrolysis of the copolymer in the alkaline solution (see below). A suitable and commercially available modified silanol PVA is that known under the "R1130" change designation (Kuraray Chemical KK, Japan), which is believed to contain from about 0.5 to about 1.0 per ^ molar 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 is about 99 percent or higher.

In the precursor linker, the PVA is mixed with an appropriate cross-linking agent compatible with the PVA. Suitable cross-linking agents include any of a variety of known cross-linking agents including, for example, aldehydes, diisocyanates, polyacrylic acid, and various metal complexes such as chelates of aluminum, titanium, silicon, zircon and the like. A variety of cross-linked PVA binders are described, for example, in Polyvinyl Alcohol Developinents, C.A. Finch, Ed., John Wiley and Sons, New York, 1992, pp 272-277, 282-285, incorporated herein by reference. The selection of an appropriate cross-linking agent is generally within the skill of those who practice the field. However, in the selection of an appropriate cross-link for the articles of the invention, consideration should be given to the desired final color of the article. Where intense colors are desired, crosslinkers that require strongly acidic catalysts are generally not desired. Accordingly, formaldehyde and other mono and dialdehydes are not generally preferred crosslinkers, especially at low pH.

Preferably, the PVA is cross-linked via secondary hydroxyl groups on the P.VA column using chelating organic titanates as the cross-linking agent. The resultant linker will theoretically react later with hydroxyl groups on the fibers when it is tanned at elevated temperatures. Particularly preferred are "dual" cross-linked PVA polymers wherein an amorphous metal oxide is also used as a cross-linking agent to coordinate with the silanol groups on the PVA column while the aforementioned titanates coordinate with the secondary hydroxyl groups, as mentioned. A particularly useful amorphous oxide metal is commercially available under the designation "Nalco 8676" (Nalco Chemical, Naperville, IL), an amorphous alumina sol with an average particle size of less than about 30 angstroms.

Particularly preferred PVA polymers are those which utilize the aforementioned amorphous metal oxide and a chelating organic titanate cross-linking agent comprising either dihydroxybis (ammonium lactate) titanium (commercially available under the designation "tyzor LA" from DuPont from Nemo? rs &Co., Inc., Wilmington, DE) or titanium orthoesters (commercially available under the "Tyzor 131" designation from DuPont de Nemours &Co., Inc.).

The theoretical crosslink density for a suitable PVA polymer may be in the range of 1 to about 40 mole percent based on moles of ethylenically unsaturated monomer.

Without being bound to a particular theory, it is believed that the bleeding of color may result primarily from the loss of the smallest pigment particles (typically less than about 0.1 micrometer). During the manufacture of articles comprising a linker PVA, precursor binders with a low solids content (e.g., less than 15 percent in water) are normally employed. In that precursor linker, it is believed that smaller pigment particles lose their proper surfactant, causing particle agglomeration. The resulting particle agglomerates are too large to be retained within the tanned linker. As a result, color bleeding results when the agglomerated pigment particles are re-dispersed in the water when the finished article is rinsed with soap and water. The known methods for mixing the pigment have been ineffective in reducing the phenomenon of color bleeding. It has been found that the presence of a hydrophobic cross-linking latex emulsion facilitates the association of pigment particles with the latex emulsion. Thus, the pigment particles are quickly incorporated into the binder of the finished article, greatly reducing the color bleeding. In addition, this large reduction in color bleeding is completed by the use of relatively small amounts of hydrophobic polymer.

There is a preferred hydrophobic latex emulsion which, when tanned, provides a polymer which is associated with the PVA and / or the substrate fibers in such a manner that it resists removal upon exposure to wet or damp conditions, (eg, exposure). to soapy water). Preferably, the latex emulsion is capable of being crosslinked to form a crosslinking polymer insoluble in water that is highly resistant to being washed from the finished article. More preferably, the latex emulsion is self-cross-linked and, even more preferably, the latex emulsion is both self-cross-linked and capable of covalently binding with the PVA. To establish whether a latex emulsion is hydrophobic, a latex emulsion is impregnated on a surface to form a film, then it is dried and tanned. The moisture tension of a surface is related to the hydrophobicity of a surface. This can be measured by using the surface tension of the water; or, more specifically, by measuring the angle formed by a drop of water in contact with a surface. For purposes of this invention, a latex is considered hydrophobic if, in a tanned film of the latex emulsion, the advancing contact angle of the water is greater than about 45 °.

The latex emulsion may be present in the precursor binder in amounts ranging from about 0.05 percent to about 20 percent by weight (based on dry solids). It is thought that concentrations above about 20 weight percent of the latex emulsion in the precursor linker adversely affect the absorption of the finished article.

Concentrations of less than about 0.05 percent are not effective for pigment retention in the binder. Preferably, the latex emulsion is present in the precursor binder in an amount of 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). In such a way that the hydrophobic polymer does not detract from the softness of the finished article, especially when wet, the hydrophobic polymer should have a glass transition temperature (Tg) of less than about 5 ° C, preferably less than about 0 ° C, and more preferably less than about -15 ° C.

Examples of hydrophobic latex emulsions suitable 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. Commercially available latex emulsions useful in the invention include acrylate emulsions available under the designation "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 87219", all available from Rohm Tech Inc. (Malden, MA). A variety of acrylic latex emulsions having physical characteristics suitable for the practice of this invention are commercially available under the "Rhoplex" designation of Rhom and Haas Co. of Philadelphia, PA. Ethylene / vinyl acetate latex emulsions having appropriate physical characteristics are available under the "Airflex" change designation and polyvinyl acetate homopolymers are available under the "Vinac" designation, both from Air Products and Chemicals, Inc. from Allentown, PA. Preferred hydrophobic latids include styrene-butyl acrylate available under the "Hycar T-278" designation of B.F. Goodrich Co. of Akron, OH, and the acrylic latisses available under the "Rhoplex E-2744" and "Rhoplex NW-1845" change designations from Rohm and Haas Co. It will be appreciated that other appropriate hydrophobic latex emulsions may be used in the preparation of the precursor linker.

The precursor linker comprises a solution, preferably aqueous, of dissolved PVA, a cross-linking agent and a hydrophobic latex emulsion. The precursor linker can 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 precursor linker is typically prepared first by dissolving the PVA in water, adding cross-linking agents and then adding a stirred hydrophobic latex.

The cross-linking of the PVA as well as the latex emulsion should be avoided until the tanning conditions (i.e., high temperatures) are present. When crosslinking titanate agents are used, organic acids such as citric acid can be added to the precursor linker to help stabilize the titanates (eg, dihydroxybis (ammonium lactate) titanium) in aqueous compositions until the precursor linkers are exposed to conditions of cross-linking and tanning. If activated acid cross-linking agents are employed (eg, aldehydes, or aminoplast resins), then it may be desirable to incorporate a latent acid such as diammonium phosphate in the precursor linker.

The pigments are mixed with the precursor linker. Pigments that are useful in the present invention include organic and inorganic pigments. The inorganic pigment generally refers to finely divided sulphides or metal oxides. Inorganic pigments are not soluble. They can 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 during the manufacture or use of articles of this invention.

Preferably, the pigments are added to the precursor linker as aqueous dispersions of finely divided particles. The particles typically fall within the sub-micrometer size range to about 10 micrometers. The dispersions facilitate the distribution of the pigment inside the binder. Suitable aqueous dispersions of organic pigments are available from commercial sources. These include pigment levels from textile arts and graphics from companies including Sun Chemical Co. (Fort Lee, NJ), Heucotech Ltd. (Fairless Hills, PA), Catawba Char-Lab (Charlotte, NC), Organic Dyestuffs Co. (Charlotte, NC), Penn Color (Doylestown, PA), and BASF Corp. (Wyandotte, MI ). The pigments can also be prepared according to methods well known in the state of the art.

Suitable pigments include, but are not limited to, organic pigments, for example, azo pigments such as soluble and insoluble azo pigments or fused azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, perylene-perinone pigments, dioxazine pigments, vat die pigments and basic pigments die, and inorganic pigments such as black carbon, titanium oxide, yellow chromium, yellow cadmium, red cadmium, red iron oxide, black iron, zinc flower, Prussian blue and ultramarine. In general, organic pigments are preferred, because they do not contain heavy metals, such as chromium, lead, aluminum and / or barium.

In addition to the components mentioned above, it may also be desirable to add optional ingredients to the precursor linker. Such 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). The inclusion of these ingredients and their relative proportions within the precursor linker will vary depending on the chemical identity of the ingredient and its predisposed function as will be readily appreciated by those practitioners in the field.

In the method of this invention, a substrate having the thickness and weight per unit area desired is provided. At least a portion of the substrate is impregnated with a mixture of precursor and pigment binder, dried, and heated to tan the precursor binder to form the binder and the pigment in at least a portion of the substrate.

Turning now to Figure 3, a method of producing a preferred substrate, a non-woven network, (as illustrated in Figures 1 and 2) is shown schematically. In the preparation of a non-woven web, the subject fibers are fed via vector 20 (or other means) into the mail station 22. A moving conductor carries a mail network 26 of the mail station 22, typically to a mail cross-over. turn, not shown, to form a layered network having fibers oriented at various angles relative to the machine direction of the mail network 26. The mail network 26 then passes through the needle fixing station 28 to entangle fibers, thus giving strength and consolidating the network, and resulting in the network with fixed needle 30. The entanglement of the network can be achieved alternatively by means other than the fixed needle, as by hydroentanglement.

The fixed needle net 30 may optionally pass through the calender station 32 to achieve a desired thickness, providing a calendered net 34 that is preferably no more than about 1.52 mm (60 mils) thick. The calendered net 34 then passes through an immersion bath 36 where a mixture of pigment and precursor linker 37 is applied. The network 34 passes under rollers 38 and emerges as the impregnated network 40. The impregnation of the network with the precursor linker can be achieved by immersion impregnation methods as well as by other impregnation methods known in the state of the art, including impregnation by rotation, impregnation by spray, impregnation by gravure, transfer of impregnation and the like. During impregnation, at least a portion of the fibers is impregnated, and preferably the network is impregnated in at least one of its first and second major surfaces with a mixture of pigment and precursor binder. In the preparation of articles to be used as manual cleaning articles or their like, the network is typically impregnated on both larger surfaces. The weight of the impregnation (i.e., added weight of drying linker) is reported as a percentage of the weight of the finished cleaning article. The weight of the impregnation falls within the range of about 1 percent to about 95 percent, preferably from about 10 percent to about 60 percent, more preferably from 20 percent to 40 percent.

The impregnated network 40 passes through the drying station 42 to form the dried network 44. While residing in the drying station 42, the network is typically and preferably exposed to an elevated temperature to remove water from the precursor linker and form the dried network 44. Drying can be completed using heating rollers (ie, "hot can"), a forced air oven, a radiant panel or other known means. Preferably, the drying is uniform throughout the thickness of the network. Depending on the composition of the precursor linker, the type of cross-linking agent used, the amount of water present and the like, the network 44 may be suitable for use without further tanning.

Typically and preferably, it is desirable to first dry and then tan the precursor linker. This two-stage process is achieved by drying the network as discussed above. The dried net 44 then passes through the final tanning station 46, which is maintained at a temperature higher than the temperature of the drying station 42. At the tanning station, the exposure to the elevated temperature curtains the binder to form the dried and tanned network 48. The drying and tanning of the precursor linker can be achieved by exposing the dried network 44 to more than two different temperatures by, for example, carrying out the drying and tanning steps in an oven that has more than two heating zones. Additionally, in the drying and tanning of the precursor binder, both larger surfaces of the tannery are preferably simultaneously exposed to a heat source. Alternatively, although less preferred, the first and second major surfaces of the impregnated network may be exposed in sequence to the heat source.

The net 48 can then pass through another group of calender rolls 50, which can be used to emboss a pattern and fuse the surfaces of the article. The net 52 generally has a thickness of no more than 1.52 mm (60 mils), and a weight that falls within the range of about 50 g / m to about 250 g / m. The calendering of the impregnated network of binder at temperatures of about 5 to about 40 ° C below the melting point of the fiber can reduce the likelihood that the lint will adhere to the surface of the articles and will generally provide a flat surface . The engraving of a texture pattern in the cleaning article can be carried out simultaneously with the calendering, or in a subsequent step.

The network 52 can then pass through a second optional needle fixing station 54 to pierce the network for decorative or other purposes, after which the network is torn and gouged before the turn to follow 56.

Alternatively, the network 52 can pass through a bath of (ie, from about 60 to about 80 ° C) hot water (not shown), and calendered and dried by means of heated rollers as described above, to produce a soft "hand" or feel before being torn and gnawed before the turn to follow 56. Another way to achieve a soft feel in the form of final packaging and to aid in processing is to apply a small amount of water or a fungicide solution to the article immediately prior to packaging. The tanned 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 tanned articles having a binder on only one of its larger surfaces, thus providing a larger untreated surface (i.e., a tanned binder-free surface) for the application of adhesives or the like.

The articles of this invention are particularly useful as "synthetic chamois" because of their absorbency and durability. These synthetic cleaning products are useful for cleaning various surfaces. The presence of pigment in the article produces a functional and aesthetically pleasing absorbent cleaning article for consumer use. Preferably, the articles are highly colored, producing rapidly recognizable colored articles which are used to clean certain areas (e.g., green for use in kitchens). The articles prepared according to this invention exhibit minimal color bleeding because the pigment is lost from the article during use.

The examples illustrate the preparation of nets impregnated with a linker and a pigment suitable for use as absorbent articles.

DESCRIPTION OF THE MATERIALS In the Examples, certain materials were used which are identified according to the following abbreviations and change designations.

PREPARATION PROCEDURES The following preparative procedures were used in the preparation of the articles identified in the Examples.

PROCEDURE A (SUBSTRATE PREPARATION) The non-woven web was prepared from 50 percent rayon fibers (3.0 dx 6.3 cm, T2222, Courtaulds Fibers Inc. (Axis, AL) and 50 percent polyvinyl alcohol fibers (1.7 dx 5.3 cm, VPB174, Kuraray Co KK (Tokyo, Japan).) The non-woven net was prepared by mail and cross-lap and was hit with a needle to provide a net with a basis weight of 162.9 g / m (4.8 oz / yd) and a thickness of 1.45. mm (57 mils.) For the following examples the network was impregnated as 30.5 cm x 38.1 cm (12 inches by .15 inches) dimension pieces.In the production of a non-woven web, there is orientation of the fibers depending on how they are produced, so the reference is made to the "machine", or network down, address, in contrast to the "cross-network" address, which is orthogonal to the machine's address.

PROCEDURE B (PVA SOLUTION) An impregnated solution was made by heating 9.3 parts of polyvinyl alcohol ("R1130" from Kuraray Co. KK) to boiling in 90.7 parts of un-ionized water to dissolve the PVA. An 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 of titanate ("Tyzor 131", commercially available from The DuPont de Nemours, Co. ., Inc., of Wilmington, DE). The resulting solution was cooled and then diluted with un-ionized water to achieve a solid content of 3.6 weight percent when dried at 121 ° C (250 ° F).

PROCEDURE (PRECURSOR LIGATOR AND CLEANING ITEMS) The latex emulsion and the pigment were added to the PVA solution in proportions described in the examples, together with additional un-ionized water as indicated in the examples. The PVA solution and the latex emulsion form the precursor linker. The mixture of pigment and precursor binder was poured into the substrate and evenly distributed by hand to make the substrate impregnated. Then the impregnated substrate was air dried at 65.6 ° C (150 ° F) until it was dried and heat-hardened at 149 ° C (300 ° F) for 10 minutes. The amount of the dried and tanned polymer (i.e., binder) in the substrate was about 18 weight percent.

TEST METHODS The following Test Methods were employed in the evaluation of the cleaning articles of the Examples.

COLORED BLEEDING Bleeding color was determined by taking a sample of material to be evaluated and placing it in 2 liters of water and allowing it to soak for 60 seconds. The sample was then squeezed by hand and the rinsed water was placed in a basin. The rinsing and squeezing steps were repeated twenty times for each sample material tested. Therefore, the intensity and hue of the color of the clarified solution and of the surface of the basin were observed and recorded, and the visible absorption spectrum of the clarified water was measured and recorded using a 10 cm path length cell in a UV-visible spectrophotometer.

The clarified solution was then discarded from the basin and replaced with 2 liters of fresh water. The sample was completely squeezed and 2 g of detergent (available under the "Liquinox" change designation from Alconox, Inc. of New York, New York) were placed in the sample and rubbed lightly over most of the sample surface. The thus treated sample was placed in fresh water. The sample was then squeezed by hand with the detergent / water mixture back into the tub. The sample was again rinsed and squeezed a second time and the visible absorption spectrum of the rinsed water was measured using a 10 cm path length cell, as previously described.

TENSIONING FORCE The samples were prepared for testing by rinsing them in water and squeezing them once with a mechanical juicer. The samples were cut to 2.54 x 15.24 cm (1 x 6 inches). Tension force measurements were made using a voltage tester (Instron Model "TM", obtained from Instron Corp. of Canton, MA), using a modified procedure from that of the test method described in ASTM D 5035-95, " Standard Test Method for the Breakdown of Strength and Elongation of Textile Factories (Strip Method) ". The thickness of the sample was also recorded. A constant rate of expression was employed, and the jaws were clamp type. The rate of separation of the jaw was 25.4 cm / min (10 inches / min). The sample was placed in the jaws, placed in a gap of 2.5 cm (1 inch), and the cycle was started. The tensile force (i.e., load) and the elongation to the break were measured. Tensioning force is an indication of the tension of the sample. The elongation to the break is a measure of the load which is applied and increased until the sample breaks. The measurements were made on the samples in the direction of the machine and the direction of the cross network, as the mechanical properties may vary depending on the direction on the orientation.

BLEACH STABILITY The cleaning articles were immersed for 8 hours in a mixture of 286 g of 5.25 weight percent chlorine bleach (household strength bleach chlorine, commercially available under the "Chlorides" designation of The Cloros 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.

PROOF OF TORN ELMENDORF The samples were prepared for the tear test by rinsing them for 5 minutes in warm water and then mechanically squeezing them.

The Elmendorf tear tests were carried out on samples of 6.35 x 27.94 cm (2.5 x 11 inches) cut, marked (20 mm), using a Elmendorf Tear Tester model number 60-32, of Thwing-Albert Co., with a pendulum of 6.4 kg. The procedure was modified from that of the test method described in ASTM D 1424-96, "Standard Test Method for the Force of Tearing Factories by Pendulum-Type Apparatus in Fall (Elmendorf)". An average of 4 measurements is reported. The samples were tested in both the machine direction and the transverse direction. Tear tests are indicative of the durability of the absorbent articles of this invention.

ABSORPTION TEST The water absorption was determined by rinsing a sample for 15 minutes in warm water in a basin or other container. The sample was then mechanically squeezed to remove most of the water. While still wet, 15.2 cm x 20.3 cm (6 inches x 8 inches) of square portions of the material were cut. The cut samples were placed again in a basin of warm water and they were allowed to rinse for 15 minutes. A screen was placed under one of the samples cut in the basin. After 30 seconds, the screen and the cut sample were lifted from the basin, and the sample was removed from the screen with tweezers and immediately placed on a scale with a quick and smooth movement. This operation requires some technique by the analysts and should be practiced until the reproducibility of ± 1 gram is achieved regularly. The reading of the balance was recorded in grams as the Total of H20 Absorbed / No. Drops (A). This procedure was repeated for the remaining cut samples.

The thus treated cut samples were rinsed in a basin of warm water for 5 minutes. Later, the samples were removed from the water with tweezers and then hung by a corner using a spring clamp attached to the ring. After 60 seconds, each sample was transferred to the scale with a quick and smooth movement. The reading of the balance in grams was recorded as the Total of H20 Absorbed with Drip (B). This procedure was repeated for the remaining cut samples.

The cut samples were placed again in a basin of warm water for 5 minutes. Later, each sample was removed from the water and passed through a mechanical juicer to a single thickness. The sample was transferred to the scale with a fast and smooth movement, and the reading of the scale in grams was recorded as the Weight of Moisture (C). This procedure was repeated for the remaining cut samples.

The cut samples were then placed in an open forced air oven maintained at 49 ° C (120 ° F) for at least 12 hours. Up to 6 samples were removed from the oven at one time and their weight in grams was immediately measured and recorded as the Dry Weight (D). This procedure was repeated for the remaining cut samples.

The Percentage of Water Loss, Absorption and Absorption Effective were then calculated according to the following formulas: Percentage of water loss = 100 * (A-B) / B; Absorption (water g / dry weight) = (A-D) / D; Effective Absorption (water g absorbed / m2) = 32.292 * (A-C).

PROOF OF WEAR The hydrophobic latex emulsion which is present in the dry precursor binder and tan to form a polymer which is generally expected to have poorer wear resistance, than that of the PVA polymer alone. To illustrate the effect of the added latex emulsion on the wear resistance, the wear test was carried out using an Abrasive Taber 503 model equipped with H22 Calibrated gears with 500 grams of weight. The samples were prepared for wear test by saturation of them in warm water and mechanically squeezing the samples 4 times to remove all excess water. The destruction was indicated to the point where a visible hole (0.3 cm (1/8 of an inch in diameter) appeared in the sample.

EXAMPLES The features and advantages of the articles of the invention are further illustrated in the following non-limited examples.

COMPARATIVE EXAMPLE A A red cleaning article using the substrate described above in PROCEDURE A. This was impregnated with 139 g of PVA solution (prepared as described in PROCEDURE B) mixed with 0.6 g of a red organic pigment (commercially available as "Orcobrite Red BRYN 6002"by Organic Dye Stuffs of Charlotte, NC) and 61 g of deionized water. The impregnated sample was dried and cured as described in PROCEDURE C.

COMPARATIVE EXAMPLE B A blue cleaning article was prepared using the substrate described above in PROCEDURE A. This was impregnated with 139 g of PVA solution (prepared as described in PROCEDURE B) mixed with 0.5 g of a blue organic pigment (commercially available as "Orcobrite"). Blue 3GN 2010") and 61 g of deionized water. The impregnated sample was dried and cured as described in PROCEDURE C.

COMPARATIVE EXAMPLE C A green cleaning article was prepared using the substrate described above in PROCEDURE A. This was impregnated with 139 g of PVA solution (prepared as described in PROCEDURE B) mixed with 0.3 g of a green organic pigment (commercially available as "Orcobrite"). Green YN 9") and 61 g of deionized water. The impregnated sample was dried and cured as described in PROCEDURE C.

EXAMPLE 1 This example demonstrates the preparation of a red cleaning article. The sample was prepared using the fiber network described in PROCEDURE A. This was impregnated with a precursor binder mixture prepared from 132 g of PVA solution (as described in PROCEDURE B), 0.45 g of latex emulsion ("Hycar T-278"), 0.6 g of a red organic pigment (" Orcobrite Red BRYN 6002") and 67 g of deionizing water. The impregnated sample was dried and cured as described in PROCEDURE C. The resulting cleaning article contained 5 percent of the polymer derived from the latex emulsion ("Hycar T-278") in the precursor binder in dry solids.

EXAMPLE 2 This example demonstrates the preparation of a red cleaning article. The sample was prepared using the fiber network described in PROCEDURE A. This was impregnated with a precursor binder mixture prepared from 125 g of PVA solution (as described in PROCEDURE B), 0. 91 g of latex emulsion ("Hycar T-278"), 0.6 g of a red organic pigment ("Orcobrite Red BRYN 6002") and 74 g of deionizing water. The impregnated sample was dried and cured as described in the PROCEDURE. C. The resulting cleaning article contained 10 percent of the polymer derived from the latex emulsion ("Hycar T-278") in the precursor binder in dry solids.

EXAMPLE 3 This example demonstrates the preparation of a red cleaning article. The sample was prepared using the fiber network described in PROCEDURE A. This was impregnated with a precursor binder mixture prepared from 118 g of PVA solution (as described in PROCEDURE B), 1.36 g of latex emulsion ("Hycar T-278"), 0.6 g of a red organic pigment (" Orcobrite Red BRYN 6002") and 80 g of deionizing water. The impregnated sample was dried and cured as described in PROCEDURE C. The resulting cleaning article contained 15 percent of the polymer derived from the latex emulsion ("Hycar T-278") in the precursor binder in dry solids.

EXAMPLE 4 This example demonstrates the preparation of a blue cleaning article. The sample was prepared using the fiber network described in PROCEDURE A. This was impregnated with a precursor binder mixture prepared from 125 g of PVA solution (as described in PROCEDURE B), 0.91 g of latex emulsion ("Hycar T-278"), 0.5 g of a blue organic pigment (" Orcobrite Blue 3 GN 2010") and 74 g of deionizing water. The impregnated sample was dried and cured as described in PROCEDURE C. The resulting cleaning article contained 10 percent of the polymer derived from the latex emulsion ("Hycar T-278") in the precursor binder in dry solids.

EXAMPLE 5 This example demonstrates the preparation of a green cleaning article. The sample was prepared using the fiber network described in PROCEDURE A. This was impregnated with a precursor binder mixture prepared from 125 g of PVA solution (as described in PROCEDURE B), 0.91 g of latex emulsion ("Hycar T-278"), 0.3 g of a green organic pigment (" Orcobrite Green YN 9") and 74 g of deionizing water. The impregnated sample was dried and cured as described in PROCEDURE C. The resulting cleaning article contained 10 percent of the polymer derived from the latex emulsion ("Hycar T-278") in the precursor binder in dry solids.

The detailed results of the analytical test of performance changes are given below in Table 1.

COMPARATIVE EXAMPLES A-C AND EXAMPLES 1-5 Tension test results: The tensile strength measurements were made as described above in the test method for 4 RESISTANCE TO TENSION. The tensile strength and elongation to the break was tested on the machine (Direction 1) and interweaved network direction (Direction 2) of the sample. A non-significant deterioration of the tension properties was observed, indicating that the detrimental effect caused by the incorporation of the hydrophobic latex emulsion ("Hycar T-278") was small.

Table 1 Stress Test Stability to Fading: The cleaning articles made according to Comparative Example A and Example 2 were tested for decolorization stability according to the above-mentioned Stability Test Method. When the comparative tests were removed from the bleaching solution, the immersed test of Comparative Example A had discolored in color level compared to non-immersed cleaning articles of Comparative Example A, while the immersed test of Example 2 remained vividly red, with less loss of apparent color. Non-negative effects were observed in stability, to be bleached using the latex additive.

The Stress Test was conducted on these samples, both before or after exposure to the bleaching solution. The data are reported in Table 2.

Table 2 Stress Test (Bleached Samples) Tear Test Results: The tear tests were conducted for the articles of Comparative Example-a and Examples 1-3 as described above in the ELMENDORF DISTORTION TEST. The data indicate that there is no deleterious effect on the tear resistance of the samples due to the presence of a polymer derived from a hydrophobic latex emulsion.

Table 3 Tear Test 4 Absorption Test: The absorption test according to the aforementioned ABSORPTION TEST Method did not indicate significant effects on absorption due to the presence of a polymer derived from a hydrophobic latex emulsion. The data is reported in table 4.

Table 4 Water absorption Wear Test: Samples were abraded according to the Abrasion Test Method with destruction of the indicated sample to the point where a visible hole (1/8 inch in diameter) appeared.The data are stated in Table 5. The data indicate that there is no deleterious effect on wear resistance due to the presence of a polymer derived from a hydrophobic latex emulsion.

Table 5 Wear test Bleeding Color The cleaning articles were subjected to the color bleed test as follows. In the case of red, blue, and green cleaning articles of Comparative Examples A, B and C, a heavy color bleeding was observed with squeezing in water, and severe color bleeding was observed in squeezing with detergent. In contrast, at most a faint color could be detected after squeezing with detergent in the case of cleansing articles added with 10 percent or more latex. The 5 results with 5 percent addition of latex "Hycar T-278" were intermediate for levels of 0 and 10 percent.

The data are reported in Table 6 to the length of 10 wave of maximum color absorption for each sample.

Table 6 Loss of color COMPARATIVE EXAMPLE D A red cleaning article was prepared using the substrates described above in PROCEDURE A. This was impregnated with 0.3 g of a red organic pigment (commercially available as "Orcobrite Red BRYN 6002") and 61 g of deionized water. The impregnated sample was dried and cured as described in the PROCEDURE C. The binder content of the resulting tanned article was 14 percent (based on dry solids).

EXAMPLE 6 A red cleaning article was prepared using the fiber network described in PROCEDURE A. This was impregnated with a precursor binder mixture prepared from 137 g of PVA solution (as described in PROCEDURE B), 1.2 g of latex emulsion ("Rhoplex NW-1845", a latex or unbound), 0.63 g of a red organic pigment ("Orcobrite Red BRYN 6002") and 61 g of deionizing water. The impregnated sample was dried and cured as described in PROCEDURE C. The binder content of the resulting tanned article was 15 percent. 5 EXAMPLE 7 A red cleaning article was prepared using the fiber network described in PROCEDURE A. This was impregnated with a precursor binder mixture prepared from 137 g of PVA solution (as described in PROCEDURE B), 1.2 g of latex emulsion ( "Rhoplex ST-954", an acrylic self-binding emulsion), 0.63 g of a red organic pigment ("Orcobrite Red BRYN 6002") and 61 g of deionizing water. The impregnated sample was dried and cured as described in PROCEDURE C. The binder content of the resulting tanned article was 15 percent.

EXAMPLE 8 A red cleaning article was prepared using the fiber network described in PROCEDURE A. This was impregnated with a precursor binder mixture prepared from 137 g of PVA solution (as described in PROCEDURE B), 1.2 g of a latex emulsion self-binding agent of styrene-butadiene ("Unocal 4170"), 0.64 g of a red organic pigment ("Orcobrite Red BRYN 6002") and 61 g of deionizing water. The impregnated sample was dried and cured as described in PROCEDURE C. The binder content of the resulting tanned article was 15 percent.

COMPARATIVE EXAMPLE D v EXAMPLES 6-8 The articles of Examples 6, 7, 8, and Comparative Example D were evaluated for color loss according to the above-mentioned Color Loss Testing method. The observed color loss of Examples 6, 7 and 8 was significantly less than that for Comparative Example D.

Although the preferred embodiments of the invention have been discussed and described in detail, it will be appreciated that changes and modifications for the described embodiment can be made by those skilled in the art without departing from the true spirit and scope of the invention, such as it is stated in the claims.

Having described the invention as above, the content of the following is claimed as property

Claims (43)

1. An absorbent article characterized in that it comprises: (a) a substrate comprised of organic fibers having a majority of pendant hydroxyl groups. (b) a linker impregnated in at least a portion of the fibers, the linker comprises a linked polyvinyl alcohol and a hydrophobic polymer; and (c) pigment distributed over the binder or agglutinator.

2. The absorbent article of claim 1, characterized in that the substrate comprises a non-woven network.

3. The absorbent article of claim 2, characterized in that the non-woven web has a weight range per unit area of about 50 g / m2 to about 250 g / m2.

4. The absorbent article of claim 1, characterized in that the organic fibers comprise materials selected from a group of polyvinyl alcohol and rayon.

5. The absorbent article of claim 4, characterized in that the ratio of polyvinyl alcohol fibers to rayon fibers ranges from 30:70 to 70:30.

6. The absorbent article of claim 1, characterized in that the polyvinyl alcohol is a silanol-modified polyvinyl alcohol.

7. The absorbent article of claim 6, characterized in that the silanol-modfied polyvinyl alcohol is bonded with a complex metal selected from the group of aluminum, titanium, silicon, and chelated zirconium and combinations of the foregoing.

8. The absorbent article of claim 1, characterized in that the hydrophobic polymer is derived from a self-crosslinking latex emulsion.

9. The absorbent article of claim 1, characterized in that the hydrophobic polymer is derived from a hydrophobic latex emulsion based on materials selected from a group of acrylate, acrylic acid, methacrylic acid, acrylonitrile, styrene, N-methylolacrylamide, polyurethane, polyester, and polyamide.

10. The absorbent article of claim 9, characterized in that the acrylate is selected from the group of butyl acrylate, ethyl acrylate, and methyl methacrylate.

11. The absorbent article of claim 1, characterized in that the hydrophobic polymer has a glass transition at a temperature of less than 0 ° C.

12. The absorbent article of claim 1 characterized in that the hydrophobic polymer has a glass transition at a temperature of less than -15 ° C.

13. The absorbent article of claim 1 characterized in that the hydrophobic polymer is present in the range of 1 to 15 weight percent of the binder or binder.

14. The absorbent article of claim 1, characterized in that the pigment is an organic pigment.

15. The absorbent article of claim 1, characterized in that the polyvinyl alcohol is a hydrolysed, bound homopolymer or copolymer derived from the copolymerization of first and second monomers, the first monomer consisting of monomers within the general formula (I) R¿ R RJ X Where X is Si (OR4OR5OR6) and The second monomer consisting of monomers within the general formula (II) R ' R R (n: Where Y is 0 (CO) R7; R1, R2, R3, R4, R5, R6 and R7 are independently selected from a group consisting of hydrogen and organic radicals having from 1 to about 10 carbon atoms.

16. The absorbent article of claim 15, characterized in that the polyvinyl alcohol is entangled with an interlacing agent selected from a group of aldehydes, diisocyanates, polyacrylic acid, metal complexes, and combinations of the foregoing.

17. The absorbent article of claim 16, characterized in that the metal complexes are selected from a group of chelated aluminum, titanium, silicon and zirconium and combinations of the foregoing.

18. The absorbent article of claim 15, characterized in that the polyvinyl alcohol is crosslinked by means of secondary hydroxyl groups on the polymer column using organic titanates as the crosslinking agent and silanol groups on the polymer column are entangled using metal oxides as another agent interlacing

19. A method of making an absorbent article characterized in that the method comprises: (a) Providing a substrate comprising organic fibers having a plurality of pendant hydroxyl groups; (b) covering at least a portion of the fibers with a mixture of a pigment and a precursor linker, the precursor linker comprising polyvinyl alcohol and a hydrophobic latex emulsion; and (c) tanning the precursor linker to provide an absorbent article.

20, The method of claim 19, characterized in that the step provides (a) further comprises providing the substrates in the form of a non-woven network interposed and carded.

21. The method of claim 19 characterized in that the step provides (a) further comprises providing the substrates in the form of a non-woven web having first and second major surfaces and entangling the organic fibers within the network not interwoven by needle-fixation.

22. The method of claim 21, characterized in that the non-woven net has a weight per unit area in the range of about 50 g / m2 to about 350 g / m2.

2. 3,. The method of claim 19 characterized in that the impregnation step (b) comprises impregnation of at least one of the first or second major surfaces of the network not interwoven with the precursor linker.

24. The method of claim 19, characterized in that the organic fibers comprise materials selected from a group of polyvinyl alcohol and rayon.

25. The method of claim 24 characterized in that the ratio of polyvinyl alcohol fibers to rayon fibers has a range of 30:70 to 70:30.

26. The method of claim 19, characterized in that the hydrophobic latex emulsion comprises a self-interlacing polymer.

27. The method of claim 19, characterized in that the hydrophobic latex emulsion is based on materials selected from a group of acrylate, acrylic acid, methacrylic acid, acrylonitrile, styrene, N-methylolacrylamide, polyurethane, polyester, and polyamide.

28. The method of claim 27 characterized in that the acrylate is selected from a group of butyl acrylate, ethyl acrylate and methyl methacrylate.

29. The method of claim 19, characterized in that the hydrophobic latex emulsion is present in the range of 1 to 15 weight percent of the binder.

30 The method of claim 19, characterized in that the pigment is an inorganic pigment.

31. The method of claim 19, characterized in that the polyvinyl alcohol in the linker precursor is a copolymer or copolymer derived from the copolymerization of first and second monomers, the first monomer consisting of monomers within the general formula (I) R¿ R "C RJ (I) X Where X is Si (OR4OR5OR6) and The second monomer consisting of monomers within the general formula (II) R¿R 'R "(II) Where Y is 0 (CO) R7; R1, R2, R3, R4, R5, R6 and R7 are independently selected from a group consisting of hydrogen and organic radicals having from 1 to about 10 carbon atoms.

32. The method of claim 31, characterized in that the precursor linker further comprises a cross-linking agent compatible with polyvinyl alcohol, the cross-linking agent selected from the group of aldehydes, diisocyanates, polyacrylic acid, metal complexes, and combinations of the previous

33. The method of claim 32, characterized in that the metal complexes are selected from the group of aluminum, titanium, silicon, and ferric chelates and combinations of the foregoing.

34. The method of claim 31, characterized in that the tanning step (c) comprises a cross-linking reaction characterized in that the polyvinyl alcohol is cross-linked via secondary hydroxyl groups on the polymer column using organic titanates as the cross-linking agent, and silanol groups in the polymer column are cross-linked using metal oxides as another cross-linking agent.

35. An absorbent article comprising a substrate having first and second major surfaces, the substrate comprising organic fibers having a plurality of pendant hydroxyl groups, characterized in that at least one of its first and second major surfaces is impregnated with a mixture comprising: (a) a linker comprises a crosslinked polyvinyl alcohol and a hydrophobic polymer; and (b) a pigment distributed within the linker.

36. The absorbent article of Claim 35, characterized in that the substrate comprises a non-woven network.

37. The absorbent article of Claim 36, characterized in that the non-woven net has a weight per unit area that falls within the range of about 50 g / m2 to about 250 g / m2.

38. The absorbent article of Claim 36, characterized in that the organic fibers comprise materials selected from the group of polyvinyl alcohol and rayon.

39. The absorbent article of Claim 36, characterized in that the polyvinyl alcohol is a modified silanol polyvinyl alcohol.

40. The absorbent article of Claim 39, characterized in that the modified polyvinyl silanol alcohol is cross-linked with a metal complex selected from the group of aluminum, titanium, silicon, and zirconium chelates and combinations of the foregoing.

41. The absorbent article of Claim 36, characterized in that the hydrophobic polymer is derived from a hydrophobic latex emulsion based on materials selected from the group of acrylate, acrylic acid, methacrylic acid, acrylonitrile, styrene, N-methyl acrylamide, polyurethane, polyester, and polyamide.

42. The absorbent article of Claim 36, characterized in that the hydrophobic polymer is present within the range of 1 to 15 weight percent of the binder.

43. The absorbent article of Claim 36, characterized in that the pigment is an organic pigment.