KR20020091265A - Salt-Sensitive, Water-Dispersible Polymer Composition - Google Patents

Abstract

The present invention relates to ion sensitive, water dispersible polymers. The present invention also relates to methods of making ion sensitive, water dispersible polymers and their applications as binder compositions. The present invention further relates to fiber-containing fabrics and webs containing ion sensitive, water dispersible binder compositions and their applications in water dispersible personal care products.

Description

Salt-Sensitive, Water-Dispersible Polymer Composition

For many years, the issue of disposability has been a problem in the industry producing disposable products such as diapers, wet wipes, incontinence garments and feminine hygiene products. While many advances have been made in solving this problem, one of the weak linkages is that they can easily dissolve or decompose in water, but cannot produce an economical adhesive fibrous web with sufficient in-use strength. U.K. Patent Publication Nos. 2,241,373 and U.S. Pat. See patent 4,186,233. Without such a product, the user's ability to flow the product out of the toilet and process the product is greatly reduced (unless completely removed). In addition, the ability of a product to decompose in landfills is very limited, which is encapsulated in, or bound by, plastics that decompose over time even if a significant portion of the biodegradable or photodegradable product components are degraded. Because it is. Thus, if the plastic decomposes in the presence of water, the internal components may decompose as a result of rupture of the plastic encapsulation or bonding.

Disposable products such as diapers, feminine hygiene products and adult incontinence hygiene products can be made to flow out of the toilet to be treated. In general, such products include bodyside liners that quickly pass bodily fluids such as urine or menses so that bodily fluids can be absorbed by the product's absorption cores. In general, the bodyside liner may be an adhesive fibrous web, which preferably retains a number of features, such as flexibility and flexibility. The fibrous web of bodyside liner material typically wets or drys (air) lays a plurality of random fibers and combines them to form an adhesive fibrous web containing the binder composition. Past binder compositions have played this role well. However, fibrous webs containing these compositions tend to be non-dispersible and cause problems in general household sanitation.

Recent binder compositions have been developed to be more dispersible and more environmentally reliable than past binder compositions. One type of binder composition comprises a polymeric material with reverse solubility in water. These binder compositions are insoluble in warm water, but water soluble in cold water such as that seen in toilets. It is well known that many polymers exhibit solubility properties of cloud point or inverse in water soluble media. These polymers are described in numerous literature for various applications as (1) evaporation retardants (JP 6207162); (2) As a temperature sensitive composition useful as a temperature indicator due to a sudden color change associated with a corresponding temperature change (JP 6192527); (3) a thermally sensitive material that is opaque at a specific temperature and becomes transparent when cooled below the specified temperature (JP Nos. 51003248 and JP No. 81035703); (4) Wound bandages with good absorption properties and easily removable (JP 6623809); And (5) flushable personal hygiene products (US Pat. No. 5,509,913; registered April 23, 1996, by Richard S. Yeo as patent holders, and by Kimberly-Clark Corporation. Assigned).

Other important recent binders include those that are ion sensitive. Many US and European patents assigned to Lion Corporation (Tokyo, Japan) disclose ion sensitive polymers including acrylic acid and alkyl or aryl acrylates. See US Pat. Nos. 5,312,883, 5,317,063 and 5,384,189 and European Patent 608460A1, incorporated herein by reference. US Pat. No. 5,312,883 discloses terpolymers as suitable binders for flushable nonwoven webs. The disclosed acrylic acid based terpolymers, including partially neutralized acrylic acid, butyl acrylate and 2-ethylhexyl acrylate, are suitable binders for use in nonwoven webs that may be flushed to some extent. However, due to the presence of small amounts of sodium acrylate in partially neutralized terpolymers, these binders fail to disperse in water containing at least about 15 ppm Ca ²⁺ and / or Mg ²⁺ . When placed in water containing at least about 15 ppm Ca ²⁺ and / or Mg ²⁺ , nonwoven webs using the binders described above maintain tensile strengths in excess of 30 g / in, which is the "minute Acidity "has a negative effect. The proposed mechanism for this failure is that each calcium ion binds two carboxylate groups within or between molecules. Bonding within the molecule causes the polymer chains to twist, which eventually leads to polymer precipitation. Bonding between molecules causes crosslinking. Either intramolecular or intermolecular bonds occur, terpolymers are insoluble in water containing at least about 15 ppm Ca ²⁺ and / or Mg ²⁺ . Due to the strong interaction between the calcium ions and the carboxylate groups of the terpolymer, the decomposition of the complex is difficult to occur because the bonds are irreversible. Thus, the above-described polymers exposed to high concentrations of Ca ²⁺ and / or Mg ²⁺ solutions do not disperse in water even if the calcium concentration decreases. This limits the application of the polymer as a binder material that can be flushed because most regions in the United States have hard water containing at least 15 ppm Ca ²⁺ and / or Mg ²⁺ .

The co-pending application assigned to Kimberly-Clark, ie, US Patent Application Serial No. 09 / 223,999, filed Dec. 31, 1998, is incorporated herein by reference of Lion Corporation, supra. Modifications of acrylic acid terpolymers are disclosed. Specifically, US Patent Application Serial No. 09 / 223,99 has improved dispersibility in relatively hard water, eg, Ca ²⁺ and / or Mg ²⁺ , relative to unmodified Ryan's polymer. , Sulfonate anion modified acrylic acid terpolymers are disclosed. However, the ion sensitive polymers of Ryan Corporation of the above-mentioned patents and the sulfonate anion modified acrylic acid terpolymers of co-pending applications are generally used (eg, as wet wipes) when used as a binder for personal care products. With reduced sheet wetting, increased sheet stiffness, increased sheet tack, reduced binder spraying and relatively high production costs.

Another solution to dispersible personal care products is described in US Pat. No. 5,281,306 to Kao Corporation, Tokyo, Japan. This document describes a water degradable cleansing sheet comprising a water dispersible fiber treated with a water-soluble binder containing a carboxyl group, ie a wet wipe. The cleaning sheet was treated with a detergent containing 5% -95% water soluble organic solvent and 95% -5% water. The cleaning sheet maintains wet strength and is not dispersed in the organic solvent based cleaning agent, but is dispersed in water.

Although a number of patents disclose various ionic and temperature sensitive compositions for materials that can be water dispersible or flushed, flexibility, flexibility, three-dimensionality and elasticity; Wicking and structural integrity in the presence of body fluids (including feces) at body temperature; And there is a need for a dispersible product having an adequate degree of fiber dispersion after flushing in a toilet such that the fibers are not entangled by tree roots or in sewer pipes. In addition, known ion sensitive polymers, such as the ion-sensitive polymers of co-pending applications of Lion Corporation and Kimberly-Clark, have relatively high viscosities at high shear rates to render applications impossible or impossible to achieve by spraying. In addition, there is a need in the art for flushable products that are water dispersible in all regions, soft and hard water regions. There is also a need for water dispersible binders that can be used for simple and uniform applications and that can be dispersed and do not reduce the wettability of the product that penetrates into the product. Finally, there is a need for water-dispersible, wet wipes that are stable upon storage, maintain a desired level of wet strength in use, and are wetted with relatively organic solvent-free or substantially organic solvent-free wet compositions. do. Such products are required at reasonable prices without compromising product stability and environmental interests that previous products have failed to achieve.

The present invention relates to ion sensitive, water dispersible polymer formulations. The present invention also relates to methods of making ion sensitive, water dispersible polymer formulations and their application as binding compositions for disposable products. In addition, the present invention relates to disposable products such as wet wipes containing ion sensitive, water dispersible binding compositions.

Summary of the Invention

The present invention relates to ion sensitive polymer formulations which have been developed to solve the problems described above, as well as to the currently available ion sensitive polymers and other polymers described in the literature. The ion sensitive polymer formulations of the present invention have "trigger properties" such that the polymer is insoluble in wet compositions containing ions of a particular type and concentration, such as monovalent salt solutions at concentrations of 0.3% to 10%, but 200 ppm (parts per million). It becomes water-soluble when diluted with water containing a divalent salt solution such as hard water containing the following calcium and magnesium ions. Unlike some ion sensitive polymer formulations that lose dispersibility in hard water due to ion crosslinking by calcium ions, the polymer formulations of the present invention are relatively refractory to calcium and / or magnesium ions. As a result, flushable products containing the polymer formulations of the present invention maintain dispersibility in hard water. In addition, the ion sensitive polymer formulations of the present invention may have improved properties of sprayability or reduced high shear viscosity, improved product wettability or reduced product stiffness and tack.

The polymer formulations of the present invention are useful as binders or structural components for airlaid and wet nonwoven fabrics such as bodyside liners, body fluid dispensing materials, body fluid absorbing materials (surges) or cover materials in various personal care products. The polymer formulations of the present invention are particularly useful as binding materials for personal hygiene products that can be flushed, and include wipes, including cleaning agents, disinfectants and the like, particularly for individuals such as skin cleansing and treatment, makeup removal, nail polish removal, medical products Useful as wet wipes for use and hard surface cleaning, wipes for automotive protection. Products that can be flushed maintain integrity or wet strength during storage and use, and are separated or dispersed after disposal in the toilet when the salt concentration drops below the critical level. Suitable substrates for treatment include tissues such as creped or uncreped tissue, coform products, fluid binding webs, aerated mats, downy pulp, nonwoven webs, and composites thereof. Methods of making uncreped tissue and shaped three-dimensional tissue webs of the present invention are described in US Patent Application Serial No. 08 / 912,906, "Wet Resilient Webs and Disposable Articles Made Therewith," (F.-J. Chen et al. , Filed Aug. 15, 1997); US Patent No. 5,429,686 (registered July 4, 1995); US Patent No. 5,399,412, registered on S. J. Sudall and S. A. Engel March 21, 1995; US Patent No. 5,672,248, registered at Wentt et al. Sep. 30, 1997; And US Pat. No. 5,607,551, registered to Farrington et al. March 4, 1997. All of which are incorporated herein by reference in their entirety. The molded tissue structure of the above patents can be particularly useful for providing good cleaning in wet wipes. In addition, good cleaning can be facilitated by embossing, forming, wetting and through-air drying, etc., on the textured fabric, while providing some texture of other substrates.

The airlaid material may be formed by metering an air stream containing fibers and any other material on a wire forming screen that moves generally horizontally under substantially dry conditions. Suitable systems and devices for air laying mixtures of fibers and thermoplastics are described, for example, in US Pat. No. 4,157,724 (Persson, registered on June 12, 1979 and published on December 25, 1984, published in US Pat. No. 31,775). Enrollment); US Patent No. 4,278,113 (registered July 14, 1981); US Patent No. 4,264,289 (Day, Apr. 28, 1981); U.S. Patent No. 4,352,649 to Jacobsen et al. Oct. 5, 1982; US Patent No. 4,353,687 to Hosler, et al., Filed Oct. 12, 1982; US Patent No. 4,494,278 (Kroyer, et al., Registered on January 22, 1985); US Patent No. 4,627,806 (Johnson, registered December 9, 1986); U.S. Patent 4,650,409, registered on Nistri, et al., March 17, 1987; And US Patent 4,724,980 (Farley, registered February 16, 1988); And US Pat. No. 4,640,810 (Laursen et al., Registered on Feb. 3, 1987).

In addition, the present invention provides a cover material that is stable in a liquid containing a first ionic composition, such as monovalent ions, at a substantially higher concentration than that found in ordinary hard water, using the unique polymer formulation described above as a binding composition. Liner), absorbent (surge) materials and wet wipes are disclosed. The resulting nonwovens can be flushed and water dispersible due to the adjusted ion selectivity, which can be triggered regardless of the hardness of the water found in toilets in the US and around the world. Preferred products according to the invention may also have flexibility and flexibility of improved properties. In addition, such products have reduced adhesion. In some embodiments, the polymer formulations to which such products are treated may have an improved degree of spraying, which enhances polymer dispensing on the product and polymer penetration into the product, while also facilitating application, which leads to reduced costs. .

In addition, the present invention discloses improved wet compositions for wet wipes. Wet wipes using the polymer formulations of the present invention are stable upon storage, retain the desired level of wet strength in use, and are wetted with a wet composition or detergent that is relatively free or substantially free of organic solvents.

These features and advantages of the present invention will become apparent upon review of the described embodiments and the following detailed description of the accompanying drawings and claims.

Brief description of the drawings

1 depicts the wet strength data for three binder formulations as a function of ionic environment and soak time.

FIG. 2 shows how wet tensile strength can change over time when a fabric comprising 68 gsm softwood airlaid web and ion sensitive binder is immersed in a solution containing calcium ions (per 2.54 cm over immersion time range). A chart showing CDWT (grams),

3 shows Dur-O-Set at a ratio of 75/25 Comparison of two data sets of sulfonated salt sensitive binder blended with RB polymer and Lion SSB-3b product (labeled code 3300) obtained in FIG. 2.

Detailed description of the invention

To be an efficient ion sensitive formulation that can be flushed or suitable for use in a water dispersible personal care product, it is desirable to (1) maintain wet strength under functional, ie controlled conditions, and in toilets or sewers around the world. Quickly dissolves or disperses in soft or hard water as found; (2) stable (non-toxic); And (3) be relatively economical. In addition to the above factors, when the ion-sensitive formulation is used as a binder composition for nonwoven substrates such as wet wipes, it should preferably be able to be processed (4) on a commercial basis, ie it can be applied relatively quickly on a large scale basis. There must be (eg by spraying), thus requiring a binder composition having a relatively low viscosity at high shear rates; (5) provide an acceptable level of sheet or substrate wettability; (6) Provide improved product feel, for example improved product flexibility and reduced tack. Wet compositions treating the wet wipes of the present invention may provide some of the above benefits, and may also provide (7) improved skin protection, eg, reduced skin irritation or other benefits, (8) improved tactile properties, and (9) Providing a balance between friction on skin and smoothness (skin slide) can provide one or more of promoting good cleansing. Wet wipes comprising the ion-sensitive polymer formulations of the present invention and products made therefrom, especially the wetting compositions described below, can meet many or all of the above criteria. Of course, not all of the advantages of the preferred embodiments of the present invention should be met in order to fall within the scope of the present invention.

The polymer formulations of the present invention can be prepared from a single triggerable polymer, such as an ion sensitive polymer, or from a combination of two or more different polymers, such as a triggerable polymer and a co-binder. Preferably, at least one polymer of the polymer formulation of the present invention is an ion sensitive polymer. Ion sensitive polymers are known in the art and include any polymer whose water solubility varies with the type and amount of ions present in the water. Ion-sensitive polymers useful in the present invention include, but are not limited to, those of Lion's polymers discussed above, such as Lion Acrylic Acid Terpolymers, Co-pending Application No. 09 / 223,99 assigned to Kimberly Clark Worldwide Inc. Sulfonate anion modified acrylic acid terpolymers; Co-pending US patent serial application (filed May 4, 2000; name of invention "Ion-Sensitive Hard Water Dispersible Polymers and Applications Therefor"; KC No. 15851; J & A No. 11302-0481; Express Mail Label No. EL498682165US Which is also assigned to Kimberly-Clark Worldwide Inc.); And other ionic and chemical sensitive polymers, including polymers of U.S. Pat. These disclosures are incorporated herein by reference in their entirety.

Other known triggerable polymers are temperature sensitive and thermally sensitive polymers and dispersion aids added to toilet toilets or other water sources (a pamphloun that has discovered that there are other ways to allow the polymer to degrade in water using temperature changes). (Pomplun) et al., Dated Sep. 9.7, 1999 and referred to in US Pat. No. 5,948,710 assigned to Kimberly Clark Worldwide Inc.). Certain polymers exhibit cloud point temperatures. As a result, these polymers will precipitate out of solution at a certain temperature, which is the cloud point. These polymers can be used to form fibers, which are insoluble in water above a certain temperature, but can become water soluble at low temperatures and degrade in water. As a result, in a body fluid such as urine, a polymer is selected that does not decompose at body temperature (37 ° C.) or close to body temperature, but decomposes when placed in water at a temperature lower than body temperature, eg, room temperature (23 ° C.) or Or it is possible to blend. An example of such a polymer is polyvinyl methyl ether (blur point 34 ° C.). When this polymer is exposed to body fluids such as urine at 37 ° C., it will not decompose because its temperature is above the cloud point (34 ° C.). However, when the polymer is placed at room temperature (23 ° C.), it is exposed to water at a temperature below the cloud point, so the polymer returns to solution over time. Thus, the polymer begins to degrade. The same is considered to be the blend of polyvinyl methyl ether and the copolymer. Other cold water soluble polymers are poly (vinyl alcohol) graft copolymers (code names Ecomaty AX2000, AX10000 and AX300G, supplied by Nippon Synthetic Chemical Company Ltd., Osaka, Japan). It includes.

Ion sensitive polymer

Ion-sensitive lion polymers and the co-pending applications and U.S. patented ion-sensitive polymers of Kimberly Clark Worldwide Inc., referenced above, are useful in the present invention. Preferred are sulfonate anion modified acrylic acid terpolymers of co-pending patent application No. 09 / 223,99 (assigned to Kimberly Clark Worldwide Inc.), which are different from the polymers of Lion Corporation and other polymers cited in the technical literature. This is because the polymer of patent application 09 / 223,99 dissolves in water containing from about 10 ppm Ca ²⁺ and / or Mg ²⁺ to about 200 ppm Ca ²⁺ and / or Mg ²⁺ . The polymers of the co-pending application are prepared to minimize the strong interactions that may exist between the anions and cations of the polymer in water. The strong interactions are described in Pearson, RG Pearson, Journal of the Americal Chemical Society, vol. 85, pg. 3533 (1963) or in the text of NS Issacs [Physical Organic Chemistry, published by Longman Scientific and Technical with John Wiley & Sons, Inc.]. New York (1987)] can be explained by the firm acid-soft acid-base theory proposed. Hard anions and hard cations interact strongly with each other. In addition, the soft anion and the soft cation interact strongly with each other. However, soft anions and hard cations, on the contrary, weakly interact with each other. Among the Lion's polymers, the carboxylate anion of sodium acrylate is a hard anion, which strongly interacts with moderate hard water and hard cations, Ca ²⁺ and / or Mg ²⁺ present in hard water. By replacing the carboxylate anion with a soft anion such as a sulfonate anion, the interaction of a hard cation, Ca ²⁺ and / or Mg ²⁺ , present in moderate hard water with the anion of the polymer that can be triggered by the ion Is reduced.

As used herein, the term "soft water" refers to water containing a divalent ion content of less than about 10 ppm. As used herein, the term "moderate hard water" refers to water containing a divalent ion content of about 10 to about 50 ppm. The term "hard water" as used herein refers to water containing a divalent ion content of about 50 ppm to about 200 ppm. By adjusting the hydrophobic / hydrophilic balance of the polymer and the combination of the polymer forming the formulation as well as the composition, an ionic sensitive formulation with a bond strength and water dispersion in water for the desired use is produced. The ion sensitive polymer may be a copolymer such as a terpolymer.

The ion sensitive acrylic acid copolymers of the present invention may comprise any combination of acrylic acid monomers and acrylic ester (alkyl acrylate) monomers capable of free radical copolymerization with copolymers, particularly terpolymers. Suitable acrylic acid monomers include, but are not limited to, acrylic acid and methacrylic acid. Suitable acrylic acid monomers include, but are not limited to, acrylic esters and methacrylic esters having alkyl groups having 1 to 18 carbon atoms or cycloalkyl groups having 3 to 18 carbon atoms, and alkyl groups having 1 to 12 carbon atoms or having 3 to carbon atoms. Preference is given to acrylic acid esters and / or methacrylic acid esters having twelve cycloalkyl groups used alone or in combination. Other suitable monomers are acrylamide and methacrylamide based monomers such as acrylamide, N, N-dimethyl acrylamide, N-ethyl acrylamide, N-isopropyl acrylamide and hydroxymethyl acrylamide, N-vinyl Pyrrolidinone, N-vinylformamide, hydroxyalkyl acrylates and hydroxyalkyl methacrylates such as hydroxyethyl methacrylate and hydroxyethyl acrylate. Other suitable acrylic acid monomers and acrylic ester monomers are disclosed in US Pat. No. 5,317,063, assigned to Lion Corporation, Tokyo, Japan, which is hereby incorporated by reference in its entirety. A particularly preferred acrylic acid terpolymer is LION SSB-3b (commercially available from Lion Corporation) (in other embodiments, the ion sensitive polymer is made from monomers other than acrylic acid or derivatives thereof, or acrylic acid, methacrylic acid and salts thereof Relatively lacking).

The relative amounts of monomers in acrylic acid of the copolymers of the present invention may vary depending on the properties desired in the resulting polymer. The mole% of acrylic acid in the copolymer is about 70 mole% or less. More specifically, the mole percent of acrylic acid monomers in the copolymer is about 15 mole percent to about 50 mole percent. More specifically, the mole% of acrylic acid monomer in the copolymer is about 25 to about 40 mole%.

More specifically, examples of acrylic acid copolymers useful in the present invention are 90% to 10% by weight, preferably 10% to 90% by weight, preferably 20% to 70% by weight of acrylic acid and / or methacrylic acid. Preferably a copolymer of 80% to 30% by weight of acrylic esters and / or methacrylic acid esters having alkyl groups having 1 to 18 carbon atoms or cycloalkyl groups having 3 to 18 carbon atoms, wherein 1 to 60 moles %, Preferably 5 to 50 mole% of acrylic acid and / or methacrylic acid are neutralized to form a salt); Or 30% to 75% by weight, preferably 40% to 65% by weight of acrylic acid and 5% to 30% by weight, preferably 10% to 25% by weight of acrylic ester and / or methacrylic acid Esters (with alkyl groups having 8 to 12 carbon atoms) and 20% to 40% by weight, preferably 25% to 35% by weight of acrylic esters and / or methacrylic acid esters with 2-4 carbon atoms Copolymers of alkyl groups having atoms, wherein 1 to 50 mol%, preferably 2 to 40 mol%, of acrylic acid is neutralized to form salts.

The acrylic acid copolymers of the present invention may have an average molecular weight that depends on the end use of the polymer. The acrylic acid copolymers of the present invention have an average molecular weight in the range of about 10,000 to about 5,000,000. More specifically, the acrylic acid copolymers of the present invention have an average molecular weight in the range of about 25,000 to about 2,000,000, more specifically about 200,000 to about 1,000,000.

The acrylic acid copolymer of the present invention may be prepared according to various polymerization methods, preferably according to solution polymerization methods. Suitable solvents for the polymerization process include lower alcohols such as methanol, ethanol and propanol; Mixed solvents of water and one or more lower alcohols mentioned above; And a mixed solvent of water and one or more lower ketones such as acetone or methyl ethyl ketone.

Any polymerization initiator may be used in the polymerization method of the present invention. The choice of particular initiator may depend on a number of factors, including but not limited to the polymerization temperature used, solvent and monomers. Suitable polymerization initiators for use in the present invention are 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), 2,2'-azobis (2,4 -Dimethylvaleronitrile), 2,2'-azobis (2-amidinopropane) dihydroxychloride, 2,2'-azobis (N, N'-dimethyleneisobutylamidine), potassium persulfate , Ammonium persulfate and aqueous hydrogen peroxide solution. The amount of polymerization initiator may preferably range from about 0.01 to 5 weight percent based on the total weight of monomers present.

The polymerization temperature may vary depending on the polymerization solvent, monomer and initiator used, but generally ranges from about 20 ° C to about 90 ° C. Polymerization times generally range from about 2 to about 8 hours.

Sulfate anion-modified acrylic acid copolymers according to the present invention include hydrophilic monomers, such as acrylic acid or methacrylic acid, incorporated into the acrylic acid copolymer of the present invention together with one or more sulfate-containing monomers. The sulfonate anion of these monomers is softer than the carboxylate anion because the negative charge of the sulfonate anion is delocalized over three oxygen atoms and a large sulfur atom as opposed to only two oxygen atoms and small carbon atoms in the carboxylate anion. to be. These monomers containing soft sulfonate anions react less with polyvalent ions, especially Ca ²⁺ and Mg ²⁺ ions, present in hard water. Suitable sulfonate containing monomers are organic or inorganic salts of 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS) and 2-acrylamido-2-methyl-1-propanesulfonic acid, for example 2- Alkaline earth metal and organic amine salts of acrylamido-2-methyl-1-propanesulfonic acid, especially sodium salts of 2-acrylamido-2-methyl-1-propanesulfonic acid (NaAMPS). Further suitable sulfonate-containing monomers are 2-methyl-2-propene sulfonic acid, vinyl sulfonic acid, styrene sulfonic acid, 2-sulfopropyl methacrylate and 3-sulfopropyl acrylate and their organic or inorganic salts such as alkalis Earth metal and organic amine salts, such as, but not limited to, alkyl ammonium hydroxides with alkyl groups C ₁ -C ₈ . In order to maintain the hydrophobic / hydrophilic balance of the ion sensitive polymer, one or more hydrophobic monomers are added to the polymer.

The ion sensitive sulfonate anion modified acrylic acid copolymers of the present invention can be prepared from monomers comprising the following monomers; Acrylic acid, methacrylic acid or combinations thereof; 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS) and their organic or inorganic salts, such as their sodium salts (NaAMPS); Butyl acrylate; And 2-ethylhexyl acrylate. Preferably, the ion sensitive sulfonate anion modified acrylic acid copolymer of the present invention is acrylic acid; AMPS; NaAMPS or a combination thereof; Butyl acrylate; and 2-ethylhexyl acrylate. Preferably, the monomer is present in the following mole percent in the sulfonate anion modified acrylic acid copolymer; Acrylic acid, less than about 35 to 80 mol%; AMPS or NaAMPS, greater than 0 and up to about 20 mol%; Butyl acrylate greater than 0 and up to about 65 mole%; And 2-ethylhexyl acrylate, greater than 0 and up to about 45 mol%. Most specifically, the monomer is present in the following mole percent in the sulfonate anion modified acrylic acid copolymer; Acrylic acid, about 50 to about 67 mole%; AMPS or NaAMPS, greater than 0 and up to about 10 mol%; Butyl acrylate about 15 to about 28 mole%; And about 7 to about 15 mole% 2-ethylhexyl acrylate. More specifically, the monomer is present in the following mole percent in the sulfonate anion modified acrylic acid copolymer; Acrylic acid, about 57 to about 66 mole%; AMPS or NaAMPS, about 1 to about 6 mole%; Butyl acrylate about 15 to about 28 mole%; And about 7 to about 13 mole% 2-ethylhexyl acrylate; In particular, about 60 mole% acrylic acid, about 5 mole% AMPS or NaAMPS, about 24.5 mole% butyl acrylate and about 10.5 mole% 2-ethylhexyl acrylate.

If AMPS is used as one of the monomers, it is preferred to neutralize at least part of the acid component. Any inorganic base or organic base may be used as the neutralizing agent to neutralize the acid component. Examples of neutralizing agents include inorganic bases such as sodium hydroxide, potassium hydroxide, lithium hydroxide and sodium carbonate and amines such as monoethanolamine, diethanolamine, diethylaminoethanol, ammonia, trimethylamine, triethylamine , Tripropylamine, morpholine, but is not limited thereto. Preferred neutralizing agents include sodium hydroxide, potassium hydroxide or combinations thereof.

In addition, sulfonate modified copolymers with salt sensitivity can be produced by sulfonation of existing syntheses, such as copolymers or acrylic acid derived terpolymers. Methods of sulfonating polymers are well known in the art. Sulfonated or sulfated polymers are described in the following patent documents [US Pat. No. 3,624,069 to Schwelger, registered November 11, 1971]; US Patent No. 4,419,403 (Varona, 1096. 12. 6 registered); US Patent No. 522,967 (Shet, June 4, 1996); US Patent No. 4,220,739 (Walles, registered on September 2, 1980); US Patent No. 5,783,200 (Motley et al., Registered July 21, 1998), as well as the following patent documents: US Patent No. 2,400,720; 2,937,066; 2,786,780; 2,786,780; 2,832,696; US Pat. 3,613,957 and 3,740,258, all of which are incorporated herein by reference. The principles of sulfation and sulfonation reactions (eg, by treatment with sulfamic acid, by reaction with thionyl chloride or chlorosulfonic acid, or by exposure to sulfur trioxide) are described in Samuel Shore and DR Berger in " Alcohol and Ether Alcohol Sulfates, "in Anionic Surfactants, Part 1, ed. Warner M. Linfield, New York: Marcel Dekker, Inc., 1976, pp. 135-149; and by Ben E. Edwards, "The Mechanisms of Sulfonation and Sulfation," in Anionic Surfactants, Part 1, ed. Warner M. Linfield, New York: Marcel Dekker, Inc., 1976, pp. 111-134, both of which are incorporated herein by reference.

In a further embodiment of the present invention, the ion sensitive polymer formulations described above are used as binding materials for products that may or may not be flushed. Being an effective binder in products that can be flushed across the United States. In order to prepare the ion-sensitive polymer formulations of the present invention, they must be stable and maintain their integrity in dry or relatively low concentrations of monovalent ions, but with water containing up to about 200 ppm of divalent ions, especially calcium and magnesium ions. Among them, it should be available. Preferably, the ion sensitive polymer formulation containing the acrylic acid copolymer of the present invention is insoluble in a salt solution containing at least about 0.3% by weight of one or more inorganic and / or organic salts containing monovalent ions. More preferably, the ion sensitive polymer formulation containing the acrylic acid copolymer of the present invention is insoluble in a salt solution containing from about 0.3% to about 5.0% by weight of one or more inorganic and / or organic salts containing monovalent ions. to be. Even more preferably, the ion sensitive polymer formulation containing the acrylic acid copolymer of the present invention is in a salt solution containing from about 1.0% to about 3.0% by weight of at least one inorganic and / or organic salt containing monovalent ions. Insoluble. Suitable monovalent ions include Na ⁺ ions, K ⁺ ions, Li ⁺ ions, NH ₄ ⁺ ions, low molecular weight quaternary ammonium compounds (eg having less than 5 carbon atoms on any side chain group) and these Combinations of but not limited to.

In another embodiment, the ion sensitive polymer formulations of the invention containing sulfonate anion modified acrylic acid copolymers are in a salt solution containing at least about 1% by weight of one or more inorganic and / or organic salts containing monovalent ions. Insoluble. More preferably, the ion sensitive polymer formulations containing the sulfonate anion modified acrylic acid terpolymers of the present invention contain from about 1% to about 5.0% by weight of one or more inorganic and / or organic salts containing monovalent ions. It is insoluble in the salt solution contained. Even more preferably, the ion sensitive polymer formulations containing the sulfonate anion modified acrylic acid terpolymers of the present invention contain from about 1% to about 3.0% by weight of at least one inorganic and / or organic salt containing monovalent ions. It is insoluble in salt solution containing%. Suitable monovalent ions include Na ⁺ ions, K ⁺ ions, Li ⁺ ions, NH ₄ ⁺ ions, low molecular weight quaternary ammonium compounds (eg having less than 5 carbon atoms on any side chain group) and these Combinations of but not limited to.

According to a recent study conducted by the American Chemical Society, water hardness varies significantly across the United States, with CaCO ₃ concentrations ranging from nearly zero for soft water to about 500 ppm CaCO ₃ (about 200 ppm Ca ²⁺ ) for very strong water. Range. In order to ensure dispersion of the polymer formulation throughout the country (and throughout the world), the ion-sensitive polymer formulation of the invention is preferably in water containing up to about 50 ppm Ca ²⁺ and / or Mg ²⁺ ions. Soluble. More preferably, the ion sensitive polymer formulations of the present invention are soluble in water containing up to about 100 ppm Ca ²⁺ and / or Mg ²⁺ ions. Even more preferably, the ion sensitive polymer formulations of the present invention are soluble in water containing up to about 150 ppm Ca ²⁺ and / or Mg ²⁺ ions. Even more preferably, the ion sensitive polymer formulations of the present invention are soluble in water containing up to about 200 ppm Ca ²⁺ and / or Mg ²⁺ ions.

A wide variety of polymer / surfactant systems can be used to provide the same functionality as ion-sensitive lion polymers and the ion-sensitive sulfonate anion-modified acrylic acid terpolymers of co-pending application 09 / 223,99 (sulphone groups or Need not be limited to carboxylic acid groups). Such other systems are described below.

Phosphorylated polymers containing phosphonic acid groups, thioffsulfonic acid groups or other organophosphorus groups, such as "soft" anions that can form mismatches with Ca ^{2 ++} can be used as the ion sensitive polymer of the present invention. have. This includes modified cellulose or cellulose derivatives and related gums (which become insoluble due to the presence of monovalent salts or other electrolytes). In one embodiment, soluble cellulose derivatives, such as CMC, are phosphorylated and insoluble, making them effective as ion-sensitive polymer formulations in solutions of high ionic concentration or moderate pH, but are dispersed in tap water. In other embodiments, aminophosphine groups that can be anionic or amphoteric are added to the polymer. Aminophosphine groups can be added via condensation of primary amines with hypophosphites. In addition, the reaction of amines with chloromethylphosphinic acid is described in Guenther W. Wasow in "Phosphorous-Containing Anionic Surfactants," Anionic Surfactants: Organic Chemistry, ed. Helmut W. Stache, New York: Marcel Dekker, 1996, pp. 589-590 can be used to produce useful anionic groups as described. The entire chapter of Wasow, including pages 551-629 of the book mentioned above, provides additional teaching relating to producing polymers with useful phosphorus groups, which are incorporated herein by reference.

Other methods of making phosphorylated cellulose fibers are well known. These methods can be applied to CMC, which can act as a binder. An exemplary method is described in US Pat. No. 3,739,782 (registered June 19, 1973 to Bernardin). Synthetic or natural polymers modified to have cellulose and other “soft” anionic groups may be useful as the ion sensitive polymer of the present invention.

In addition, natural polymers already provided with useful anionic groups may be useful in the present invention. Such polymers include agar and carrageenan with multiple sulphate groups. They can be further modified to have additional anionic groups if necessary (eg sulfonation, phosphorylation, etc.).

In addition, polymers having two or more different soft anionic groups, such as sulfone groups and phosphone groups, wherein the relative amounts of different anions can be adjusted to optimize the strength, ion sensitivity and dispersibility of the polymers. It is useful in the invention. It also includes zwitterionic and amphoteric compounds. In particular, multidentate electrolytes are readily soluble above or below the isoelectric point, but are insoluble at the isopotential point, providing the possibility of triggering mechanisms based on electrolyte concentration and pH. Examples of multidentate amphoteric electrolytes are polymers prepared directly from copolymers of methacrylic acid and allylamine, copolymers of methacrylic acid and 2-vinylpyridine, polysiloxane ionomers with suspended amphoteric groups and zwitterionic monovalent salts, eg See, eg, Salamone et al., All as summarized by Irja Piirma in Polymeric Surfactants, New York: Marcel Dekker, Inc., 1992, at pp. 251-254, including but not limited to ion pairs of comonomers (Salamone) and the like (IPC).

Proteins that can precipitate into salts (which can optionally be modified to have additional soft ionic groups) can be useful as the ion sensitive polymer of the present invention.

High concentrations of calcium ions (greater than 250 ppm or even lower than those that can be found in hard water) insolubilize the binder, but allow larger water to dilute the calcium ions to make the binder dispersible. Systems such as including algin derivatives or natural sulfonated polymers are useful in the present invention. Thus, although it is desirable for the ion sensitive binder of the present invention to be insoluble in a solution comprising monovalent metal ions above a critical concentration, in some embodiments useful ion sensitive binders are in a solution comprising divalent metal ions above a critical concentration. Insoluble but soluble when the divalent metal ion concentration drops to about 200 ppm or more specifically about 100 ppm, so that the fibrous substrate with the ion-sensitive polymer as a binder has good wet strength in solutions containing elevated concentrations of divalent metal ions. However, it becomes water-dispersible in hard or moderately strong water. Thus, the triggering mechanism results in a pre-soaked wipe that loses wet strength and can be flushed even in hard water, which may be due to dilution of monovalent or divalent metal ions, and especially alkali metal ions (preferably monovalent ions such as sodium). have. Natural polymers and gums that can be adapted for use as ion sensitive binders are described in R. R. L. Whistler and J. N. BeMiller in Industrial Gums, New York: Academic Press, Inc., 1973.

Algin (according to the reported embodiment in the use as a binder for pharmaceutical tablets—see Wiltler and BeMiller, page 62—it needs to be in the form of sodium alginate and calcium alginate for good dispersibility). ) Is insoluble as alginic acid, calcium alginate or generally most polyvalent metal salts, but is soluble as salts (p. 67) with sodium alginate or low molecular weight amines or quaternary ammonium compounds, which can be usefully used in the present invention. have. This material can be used especially when zinc is an insoluble metal ion.

Other useful polymers include carrageenan and iridopican, and both seaweed derivatives include ester sulfates.

Two natural polymers, including cellulose and synthetic polymers, may have anionic groups, such as sulfone groups, phosphone groups and carboxyl groups, and may form crosslinks with other molecules in the presence of ions of suitable type and concentration. When the ion concentration changes substantially, for example, when the cleaning product of the present invention is placed in the toilet body, the product weakens and decomposes.

Ion-sensitive polymers include those which are dispersed in a water soluble environment under defined conditions, but not in all water soluble environments. Examples include materials that are alkaline dispersible or brine insoluble. For example, Eastman AQ copolyester (Eastman Chemical Company, Kingsford, Tenn.) May be dispersed in distilled water but insoluble in saline solutions. They are designed for use in products such as diapers intended to absorb body fluids. Further information on these polymers is provided in the following patent document: European Patent Application No. 773,315-A1, "Nonwoven Web Comprising Water Soluble Polyamides and Articles Constructed Therefrom," published May 14, 1997 by S. U. Ahmed.

Useful multidentate electrolytes include polyacrylamide based copolymers that are extremely sensitive to sodium chloride concentration.

U. S. Patent No. 3,939, 836, the disclosure of which is incorporated herein by reference, shows good dry tensile strength to the fiber (when such fabric is in contact with a typical salt solution of body fluids such as blood, menstrual fluid or urine) Alkali salts of sulphated cellulose are described which provide a substantial portion but are readily dispersed in water). The resin has a degree of sulfate substitution of 0.10 to 0.45. Colloidal sulfate esters of cellulose in US Pat. No. 4,419,403 (incorporated herein by reference) are used as effective water dispersible binders, where the binder has a much higher degree of sulfate substitution than patent '836. The binder of patent '403 forms a gel in the presence of potassium ions. Other patents relating to dispersible polymers and wet wipes are described in U.S. Pat. Pat. Nos. 4,117,187; 5,417,977; 4,309,469; 5,317,063; 5,312,883; 5,384,189; 5,543,488; 5,571,876; 5,709,940; 5,718,790, the disclosures of which are incorporated herein by reference.

Cobinder Polymer

As described above, the polymer formulations of the present invention are formed from a single ion sensitive polymer or a combination of two or more different polymers, wherein the one or more polymers are ion sensitive polymers. The second polymer may be a cobinder polymer. The cobinder polymer is preferably dispersed mostly in the ion-sensitive polymer when combined with the ion-sensitive polymer, i.e. the ion-sensitive polymer is preferably in a continuous phase and the co-binder polymer is preferably in a discontinuous phase. -Type and amount. Preferably, the cobinder polymer can meet a number of additional criteria. For example, the cobinder polymer can have a glass transition temperature, ie, T _H , that is lower than the glass transition temperature of the ion sensitive polymer. In addition or alternatively, the cobinder polymer may be insoluble in water or may reduce the shear viscosity of the ion sensitive polymer. The cobinder is about 45% or less, specifically about 30% or less, more specifically about 20% or less, even more specifically 15% or less and most specifically about 10, relative to the solid quenching of the polymer that can be triggered It may be present at levels up to%, and exemplary ranges are from about 1% to about 45%, or from about 25% to about 35% and from about 1% to about 20% or from about 5% to about 25%. The amount of cobonder present is low enough that a possible cobinder forms a water-insoluble bond or film such that the co-bonder remains in a discontinuous layer that cannot produce crosslinks or insoluble bonds that endanger the dispersibility of the treated substrate. . In one embodiment, the ion sensitive formulation of the invention may comprise about 75% by weight acrylic acid terpolymer and about 25% by weight poly (ethylene-vinyl acetate) cobinder.

Preferably, but not necessarily, the cobinder polymer when combined with the ion sensitive polymer will reduce the shear viscosity of the ion sensitive polymer to such an extent that the combination of the ion sensitive polymer and the cobinder polymer can be sprayed. By spraying it is meant that the polymer can be applied to the nonwoven fibrous substrate by spraying and that the spraying of the polymer throughout the substrate and the penetration of the polymer into the substrate are such that the polymer formulation can be evenly applied to the substrate.

The cobinder polymer may be in the form of an emulsion latex. Surfactant systems used in such latex emulsions should not substantially compromise the dispersibility of the ion sensitive polymer.

In some embodiments, the combination of the ion sensitive polymer and the cobinder polymer reduces the stiffness of the product to which the combination is applied as compared to products containing only the ion sensitive polymer. When an ionic sensitive polymer, such as a sulfonate anion modified acrylic acid terpolymer, is applied to a nonwoven substrate such as an airlaid layer of wood pulp for the purpose of forming a wet wipe, the nonwoven sheet is either a dry product or a dry If slidability can impair operability, it may have an undesirable amount of slack that is detrimental to handling of the dry web during processing. By combining the ion sensitive polymer and the cobinder polymer, the stiffness of such a product can be reduced.

The cobinder polymers of the present invention may have an average molecular weight that varies with the end use of the polymer. Preferably, the cobinder has an average molecular weight in the range of about 500,000 to about 200,000,000. More preferably, the cobinder polymer has an average molecular weight of about 500,000 to about 10,000,000.

Cobonder polymers that can meet many or all of the above criteria are poly (ethylene-vinyl acetate), poly (styrene-butadiene), poly (styrene-acryl), vinyl acrylic terpolymers, neoprene, polyester lac Tes, acrylic acid emulsion lactes, polyvinyl chloride, ethylene-vinyl chloride copolymers, carboxylated vinyl acetate latex and the like (all of which contain non-crosslinking (e.g., N-methylol acrylamide or other crosslinkers) ), Crosslinking, or potentially crosslinking (i.e., prepared with the crosslinker present), but not substantially crosslinking in the final product).

Particularly preferred non-crosslinked poly (ethylene-vinyl acetate) is Dur-O-Set RB (available from National Starch and Chemical Co., Bridgewater, NJ). Particularly preferred uncrosslinked poly (styrene-butadiene) is Rovene 4817 (available from Mallard Creek Polymers, Charlotte, NC). Particularly preferred noncrosslinked poly (styrene-acrylic) is Rhoplex NM 1715K (available from Rohm and Haas, Philadelphia, PA).

When latex co-bonders, or potentially cross-linked co-bonders, are used, the latex binds to the fibrous substrate and should not form substantial insoluble bonds that compromise the dispersibility of the product. Thus, the latex may not contain a crosslinking agent such as NMA, or may contain no catalyst for crosslinking, or both. Alternatively, inhibitors may be added to interfere with the crosslinker or catalyst so that the crosslink is weakened even when the product is heated to the usual crosslink temperature. Such inhibitors may include free radical scavengers, methyl hydroquinone, t-butylcalcecol, pH adjusting agents such as potassium hydroxide, and the like. Some latex crosslinkers, such as N-methylol-acrylamide (NMA), may interfere with crosslinking at conventional crosslinking temperatures (eg, above about 130 ° C.), for example, at elevated pH above pH 8. have. Or alternatively, the product containing the latex co-binder may be at a temperature below the temperature at which crosslinking occurs such that the presence of the crosslinker does not cause crosslinking, or the degree of crosslinking is kept low enough so that the dispersion of the product does not endanger. Must be maintained at temperature. Alternatively, the amount of latex that can be crosslinked can be maintained below the critical level so that the product can be dispersible even if crosslinking occurs. For example, small amounts of crosslinkable latex dispersed as individual particles in the ion sensitive binder may allow dispersion even when fully crosslinked. For the following embodiments, the amount of latex may be less than about 20 weight percent, more specifically less than about 15 weight percent relative to the ion sensitive binder.

Whether crosslinkable or not, the latex compound need not be a cobinder. Useful noncrosslinker The SME microstructure of successful ion sensitive binder films in which latex emulsions have been dispersed has shown that the latex cobinder particles can be retained in part as a separate element in the ion sensitive binder and in part as a filler material. It is contemplated that other materials, including dispersed mineral or particulate fillers (containing optionally added surfactants / dispersants) in the ion sensitive binder, can play a similar role. For example, in one hypothesized embodiment, a free-flowing Ganzpearl PS-8F particle (Presperse, Inc., Piscataway, NJ, styrene / divinylbenzene copolymer having about 0.4 micro particles It may be dispersed in the ion sensitive polymer at a level of about 2 to 10% by weight to modify the mechanical, tactile and optical properties of the ion sensitive binder.Other filler-like approaches include metals, glass, carbon, minerals, quartz and / or ) Hollow particles with microparticles, microparticles or microbeads, such as acrylic or phenolic, and inert gaseous atmospheres sealed therein, such as EXPANCEL phenolic microparticles that substantially expand when heated. Small particles (Expancel, Sweden) or acrylic microparticles known as PM 6545 (from PQ Corporation, Pennsylvania) Includes the possible input) a blowing agent comprising a CO ₂ dissolved in the ion-sensitive binder can also provide a useful discontinuities as gas bubbles in the matrix of the ion-sensitive binder that allows the dispersed gas phase acts as the co-binder in the ion-sensitive binder Generally, any suitable material that cannot be mixed with the binder, in particular an adhesive-containing material, if no cobinder is provided in the state where substantially covalently linked fibers are provided in a manner that interferes with the water dispersibility of the product. Materials which have binding properties per se can be used as cobinders, however, those materials which provide further advantages, for example reduced spray viscosity, may be particularly preferred. Adhesive cohesive agents, such as latexes containing positive crosslinkers, have elevated temperatures. It is having been found to be particularly useful to provide excellent results across a wide range of processing conditions, including drying in.

As mentioned above, the Tg of the cobinder polymer may be lower than the Tg of the ion sensitive polymer, which is believed to improve the flexibility of the treated substrate, especially in the dried state. Table 1, shown below, compares the glass transition temperatures of some of the preferred polymers useful in the present invention.

TABLE 1 Glass transition temperatures of selected polymers

polymer Glass transition temperature -Tg Sulfonate Anion Modified Acrylic Acid Terpolymer (Dry) 55 ℃ Sulfonate Anion Modified Acrylic Acid Terpolymer (Wet) -22 ℃ Rhoplex NW 1715K (dry). -6 ℃ Rovene 4817 (dry) -4 ℃ Elite 33 (dry) 10 ℃ Elite 22 (dry) -15 ℃

In another embodiment, the ion sensitive polymer formulation of the present invention comprises about 55 to about 95 weight percent sulfonate anion modified acrylic acid terpolymer and about 5 to about 45 weight percent poly (ethylene-vinyl acetate). More preferably, the ion sensitive polymer formulation of the present invention comprises about 75% by weight of sulfonate anion modified acrylic acid terpolymer and about 25% by weight of poly (ethylene-vinyl acetate).

As mentioned above, useful cobinder polymers are Rovene. Series (Styrene Butadiene Latex, available from Mallard Creek Polymers, Charlotte, NC), Rhoplex Latex (Rom and Haas Company) and Elite Various commercial latex emulsions can be included, including those selected from latex (National Starch). Polymer emulsions or dispersions are generally small polymer particles, for example crosslinkable ethylene, dispersed in water, typically in spherical form and stabilized with surface active ingredients such as low molecular weight emulsifiers or high molecular weight protective colloids. Vinyl acetate copolymers. These liquid binders may be applied to airlaid webs or other substrates and then dried by methods known in the art for binder processing on nonwoven webs, including spray or foam application, flooded nip immersion, curtain coating, and the like. Generally, vinyl acetate copolymer latexes such as 76 RES 7800 (Union Oil Chemicals Divisions) and Resyn 25-1103, Resyn 25-1109, Resyn 25-1119, and Resyn 25-1189 (National Starch and Chemical Corporation), ethylene-vinyl acetate copolymer emulsions such as Airflex Ethylene-vinylacetate (Air Products and Chemicals Inc.), acrylic-vinyl acetate copolymer emulsion, for example Rhoplex AR-74 (Rom and Haas Company), Synthemul 97-726 (Reichhold Chemicals Inc.), Resyn 25-1140, 25-1141, 25-1142, and Resyn 6820 (National Starch and Chemical Corporation), vinyl acrylic terpolymer interpolymer latex, such as 76 RES 3103 (Union Oil Chemical Division), and Resyn 251110 (National Starch and Chemical Corporation), acrylic emulsion latex, eg Rhoplex B-15J, Rhoplex P-376, Rhoplex TR-407, Rhoplex E-940, Rhoplex TR934, Rhoplex TR-520, Rhoplex HA-24, and Rhoplex NW1825 (Rom and Haas Company), and Hycar 2600 X 322, Hycar 2671, Hycar 2679, Hycar 26120, and Hycar 2600 X347 (BF Goodrich Chemical Group), styrene-butadiene latex, for example 76 RES 4100 and 76 RES 8100 (available from Union Oil Chemical Division), Tylac Resin Emulsion 68-412, Tylac Resin emulsions 68-067, 68-319, 68-413, 68-500, 68-501, (available from Rayhold Chemical Inc.), and DL6672A, DL6663A, DL6638A, DL6626A, DL6620A, DL615A, DL617A, DL620A, DL640A , DL650A (commercially available from Dow Chemical Company); And rubber latexes such as neoprene (commercially available from Serva Biochemicals); Polyester latexes such as Eastman AQ 29D (commercially available from Eastman Chemical Company); Vinyl chloride latex, for example Geon 352 (commercially available from B. Goodrich Chemical Group); Ethylene-vinyl chloride copolymer emulsions such as Airflex Ethylene-vinyl chloride (commercially available from Air Products and Chemicals); Polyvinyl acetate copolymer emulsion, for example Vinac (Air products and chemicals); Carboxylated Vinyl Acetate Emulsion Resin, for example Synthemul Synthetic Resin Emulsions 40-502, 40-503, and 97-664 (Rayhold Chemical Inc) and Polyco A wide variety of latex compounds and other resins or emulsions are contemplated, including 2149, 2150, and 2171 (Roam and Haas Co.). In addition, silicone emulsions and binders may be considered.

The cobonded polymer may comprise a surface activated compound that enhances the wettability of the substrate after application of the binder mixture.

The wettability of dry substrates treated with ion sensitive polymer formulations can be problematic in certain embodiments, where the hydrophobic portion of the ion sensitive polymer formulation is selectively oriented towards the air layer upon drying so that the surfactant is applied when the wet composition is later applied. This is because hydrophobic surfaces that are difficult to soak can be created unless added to the wet composition. Surfactants or other surface active ingredients in the cobinder polymer may improve the wettability of the dried substrate treated with the ion sensitive polymer formulation. Surfactants in the cobinder polymer should not substantially interfere with the ion sensitive polymer formulation. Thus, the binder should be able to maintain good integrity and tactile properties in the pre-wet wipe in which the surfactant is present.

In one embodiment, the effective cobinder polymer comprises a portion of the ion sensitive polymer formulation that is sufficient to achieve the same desired tensile strength, except that it replaces a portion of the ion sensitive polymer formulation and does not contain the cobinder polymer. Allows certain strengths to be achieved in pre-wet wipes with one or more of low stiffness, good tactile properties (eg lubricity or smoothness) or reduced cost compared to pre-wet wipes.

Other Cobinder Polymers

Dry emulsion powder (DEP) binder (Wacker Polymer Systems, Burghausen, Germany), for example VINNEK The binder of the system can be applied in some embodiments of the present invention. These are free flowing binder powders formed from liquid emulsions that can be redispersed. Small polymer particles from the dispersion are provided in the protective matrix of the water soluble protective colloid in the form of powder particles. The surface of the powder particles is protected against solidification by a thin film of mineral crystals. As a result, the polymer particles that were in the liquid dispersion can be redispersed in water, or used in the form of free flowing dry powders that can be returned to the swelling, gooey particles by wet addition. These particles can be applied in a highloft nonwoven by depositing them with the fibers during the airlaid process, and then adding 10% to 30% moisture causes the particles to swell and adhere to the fibers. This is called the "chewing gum effect," which means that dry, non-sticky fibers in the web, such as wet chewing gum, become tacky. Excellent adhesion to polar and other surfaces is obtained. These binders can be used as free flowing particles formed from latex emulsions that have been treated with a drug to prevent agglomeration in the dry state. They may be carried out in air, deposited with the fibers during the airlaid process, or applied to the substrate by electrostatic methods, direct contact, gravity transport or other means. They can be applied separately from the binder, before or after the binder is dried. Contact with moisture—liquid or vapor—rehydrates the latex particles and causes them to swell and adhere to the fibers. Drying and heating to elevated temperatures (eg, above 160 ° C.) cause the binder particles to crosslink and become resistant to water, while drying at low temperatures (eg, below 110 ° C.) is presoaked. It can cause film formation and a certain moisture fiber bond without seriously reducing the water dispersion of the wipe. Thus, commercial products can be used without reducing the amount of crosslinker by controlling the curing of the cobinder polymer to provide some level of binding without significant crosslinking, for example by limiting drying time and temperature.

Dr. Klaus Kohlhammer in "New Airlaid Binders," Nonwovens Report International, September 1999, issue 342, pp. 20-22, 28-31, as opposed to applying the material to existing substrates, the dry emulsion binder powder can easily be incorporated into a nonwoven or airlaid web during formation of the web, thereby providing Allow for increased control over the batch. Thus, the nonwoven or airlaid webs contain a dry emulsion binder in advance therein and are wetted when an ionic sensitive polymer formulation solution is applied, at which time the dry emulsion powder becomes tacky and contributes to the binding of the substrate to be produced. Can be. Alternatively, the substrate can be treated with an ionic sensitive binder and dried and then the filtration method can trap the dry emulsion powder in the substrate, at which time the dry emulsion powder becomes tacky by the addition of the wet composition.

In another embodiment, the dry emulsion powder is prepared by applying the powder when the ion-sensitive polymer formulation solution is sprayed onto the web, or by adding and dispersing the dry emulsion powder particles into the ion-sensitive polymer formulation solution. Dispersed in, and then the mixture is applied into the web by spraying, foam application methods, or other techniques known in the art.

Binder Formulations and Fabrics Comprising the Same

The polymer formulation of the present invention can be used as a binder. The binder formulation of the present invention can be applied to any fibrous substrate. The binder is particularly suitable for use in waterborne products. Suitable fibrous substrates include, but are not limited to, nonwovens and woven fabrics. In many embodiments, especially among personal care products, the preferred substrate is a nonwoven fabric. The term "nonwoven fabric" as used herein has a structure (including paper) in which individual fibers or filaments are randomly arranged in a mat-like manner. Nonwoven fabrics may be made in a variety of ways, including but not limited to, air laid methods, wet methods, fluid bonding methods, staple fiber carding and bonding, and solution spinning.

The binder composition may be applied to the fibrous substrate by any known application method. Suitable methods for applying the binder material include, but are not limited to, printing, spraying, electrostatic spraying, coating, flooded nip, regulated press rolls, impregnation, or any other technique. The amount of binder composition may be metered and distributed uniformly in the fibrous substrate or may be unevenly distributed in the fibrous substrate. The binder composition may be distributed throughout the entire fibrous substrate or may be distributed in a small number of small spaced areas. In most embodiments, a uniform distribution of the binder composition is desired.

For ease of application to the fibrous substrate, the binder can be dissolved in water or in a non-aqueous solvent such as methanol, ethanol, acetone and the like, with water being the preferred solvent. The amount of binder dissolved in the solvent can vary depending on the polymer used and the fabric application. Preferably, the binder solution contains up to about 25% by weight binder composition solids. More preferably, the binder solution contains about 10 to 20 wt% binder composition solids, in particular about 12 wt% binder composition solids.

If necessary, plasticizers, perfumes, colorants, antifoams, fungicides, preservatives, surface active agents, thickeners, fillers, opacifiers, tackifiers, detackifiers and similar additives may be incorporated in the solution of the binder component.

When the binder composition is applied to the substrate, the substrate is dried by any conventional method. After drying, the sticky fibrous substrate has the ability to quickly "separate" while exhibiting improved tensile strength relative to the tensile strength of the untreated wet or dry substrate, or soft or hard water having a relatively high polyvalent ion concentration. Decomposes when placed and stirred. For example, the dry tensile strength of a fibrous substrate can be increased by at least 25% relative to the dry tensile strength of an untreated substrate that does not contain a binder. More specifically, the dry tensile strength of the fibrous substrate can be increased by at least 100% relative to the dry tensile strength of the untreated substrate containing no binder. More specifically, the dry tensile strength of the fibrous substrate can be increased by at least 500% relative to the dry tensile strength of the untreated substrate containing no binder.

A preferred feature of the present invention is that the improvement in tensile strength is affected when the amount of binder composition present "added" in the resulting fibrous substrate represents only a fraction of the weight of the total substrate. The amount of "addition" may vary depending on the particular application. However, the optimum amount of "addition" is integral during use and produces a fibrous substrate that disperses quickly when stirred in water. For example, the binder component is generally about 5 to about 65 weight percent of the total weight of the substrate. More specifically, the binder component is about 10 to about 35 weight percent of the total weight of the substrate. Even more specifically, the binder component is about 17 to about 22 weight percent of the total weight of the substrate.

The nonwoven fabric of the present invention has excellent tensile strength and ion triggerability. Preferably, the nonwoven fabric of the present invention is abrasion resistant and maintains significant tensile strength in aqueous solutions containing greater than about 0.3 wt.% NaCl or a mixture of monovalent ions for formulations with acrylic acid terpolymers, or For formulations with sulfonate anion modified acrylic acid terpolymers, significant tensile strength is maintained in aqueous solutions containing more than about 1% by weight of NaCl or a mixture of monovalent ions. However, nonwoven fabrics can be dispersed in hard water from very soft to moderate hard water. Due to this latter property, the nonwoven fabric of the present invention is used in disposable products, such as sanitary napkins, diapers, adult incontinence products and dry and pre-wet wipes (wet wipes) that can be discarded in a flush toilet after use anywhere in the world. Very suitable.

The fibers forming the fabric can be made from a variety of materials, including natural fibers, synthetic fibers, and combinations thereof. The choice of fiber depends, for example, on the intended end use of the finished fabric and the cost of the fiber. For example, suitable fibrous substrates include, but are not limited to, natural fibers such as cotton, linen, jute, hemp, wool, wood pulp, and the like. Similarly, regenerated cellulosic fibers (eg viscose rayon and copper ammonia rayon), modified cellulosic fibers or synthetic fibers such as cellulose acetate, eg polypropylene, polyethylene, polyolefins, polyesters, polyamides , Fibers derived from polyacrylic or the like can be similarly used alone or in combination with each other. If desired, blends of one or more of the above fibers can also be used. Among the wood pulp fibers, any known papermaking fiber can be used, including softwood and hardwood fibers. The fibers can be, for example, chemically made of fiber or mechanically made of fiber, bleached or unbleached, first used or recycled, in high yield or in low yield, and the like. Mercerized, chemically reinforced or crosslinked fibers may also be used.

Synthetic cellulosic fiber types include all strains of rayon and regenerated cellulose and other fibers from viscose or chemically modified cellulose, including solvent spun cellulose, eg, lyocells. Chemically treated natural cellulosic fibers, such as mercurized pulp, chemically reinforced or crosslinked fibers, or sulfonated fibers may be used. New fibers as well as recycled fibers can be used. Cellulose and other cellulosic derivatives produced by microorganisms can be used. As used herein, the term "cellulose-based" is meant to include any material with cellulose as its main component, especially at least 50% by weight of cellulose or cellulose derivatives. Thus, the term includes cotton, typical wood pulp, non-wood cellulosic fibers, cellulose acetate, cellulose triacetate, rayon, heat treated wood pulp, chemical wood pulp, exfoliated chemical wood pulp, countercurrent plant or bacterial cellulose. Fiber length is important in making the fabric of the present invention. In some embodiments, such as products that can be flushed, fiber length becomes more important. The minimum length of the fiber depends on the method chosen to form the fibrous substrate. For example, when fibrous substrates are formed by carding, the length of the fibers should generally be at least about 42 mm to ensure uniformity. When the fibrous substrate is formed by an air laid or wet method, the fiber length may preferably be about 0.2 to 6 mm. Although fibers having a length greater than 50 mm are within the scope of the present invention, when a significant amount of fibers having a length greater than about 15 mm are placed in a fabric that can be flushed, the fibers are dispersed and separated in water, but the length is It has been demonstrated that there is a tendency to form "ropes" of undesirable fibers when flushing from the toilet of a house. Fibers of various lengths may be applied in the present invention, but preferably the fibers have a length of less than about 15 mm so that the fibers readily disperse from each swarm that would have been in contact with water. In addition, fibers, in particular synthetic fibers, may be crimped.

The fabric of the present invention may be formed from a single layer or multiple layers. In the case of multiple layers, the layers are generally arranged in a parallel arrangement or surface to surface relationship, and all or part of the layers can be joined to adjacent layers. In addition, the nonwoven webs of the present invention may be formed from a plurality of separate nonwoven webs in which separate nonwoven webs may be formed from single or multiple layers. If the nonwoven web contains multiple layers, the overall thickness of the nonwoven web may depend on the application of the binder, or each individual layer may separately depend on the application of the binder, in combination with other layers in a parallel arrangement Form a finished nonwoven web.

In one embodiment, the fabric substrate of the present invention may be incorporated into cleansing and body fluid absorbent products, such as sanitary napkins, diapers, adult incontinence products, surgical bandages, tissues, wet wipes, and the like. These products may include absorbent cores containing one or more layers of absorbent fibrous material. In addition, they may include one or more body fluid permeable elements such as fibrous tissue, gauze, plastic net fabric, and the like. These are generally useful as packaging materials to keep the core components in one. In addition, the core may comprise a barrier means for blocking liquid impermeable components or core penetration and liquid flow on the exterior surface of the article. Preferably, the barrier is also water dispersible. Films of polymers having substantially the same composition as the above-mentioned water dispersible binders are particularly suitable for this purpose. According to the invention, the polymer composition is useful for forming each of the above mentioned product components comprising layers of absorbent cores, liquid permeable components, packaging materials and liquid impermeable components or barrier means.

The binder formulations of the present invention are particularly useful for binding fibers in airlaid nonwoven fabrics. These air materials are useful for body-side liners, body fluid dispensing materials, body fluid absorbing materials such as surge materials, absorbent wrap sheets and cover materials for various water dispersible personal care products. Airlaid materials are particularly useful for applications such as pre-wet wipes (wet wipes). The basis weight of the airlaid nonwoven fabric may range from about 20 to about 200 g / m ² (“gsm”) in staple fibers having a denier of about 0.5-10 and a length of about 6-15 mm. Surge or absorbent materials must have good elasticity and high loft in order for staple fibers with denier of about 6 or more to be used to make these products. Preferred final densities for surge or absorbent materials are from about 0.025 g / cm ³ (“g / cc”) to about 0.10 g / cc. The bodily fluid dispensing material may have a high density, preferably in the range of about 0.10 to about 0.20 g / cc when low denier fibers are used, most preferably the fibers have a denier of less than about 1.5. Wipes generally have a fiber density of about 0.025 g / cc to about 0.2 g / cc and a basis weight of about 20 gsm to about 150 gsm, specifically about 30 to about 90 gsm, most specifically about 60 gsm to about 65 may have gsm.

In addition, the nonwoven fabric of the present invention may be incorporated into body fluid absorbent products such as sanitary napkins, diapers, surgical bandages, tissues, and the like. In one embodiment, the binder does not dissolve when contacted with body fluids because the concentration of monovalent ions in the body fluids is above the concentration required for dissolution, ie, greater than 0.3% and / or greater than 1% by weight. Nonwoven fabrics retain their structure, flexibility and exhibit satisfactory strength for practical use. However, when polyvalent ions such as Ca ²⁺ and Mg ²⁺ are contacted with water containing a concentration of about 200 ppm or less, binders such as those containing sulfonate anion modified acrylic acid terpolymers are dispersed. Similarly, when polyvalent ions such as Ca ²⁺ and Mg ²⁺ are contacted with water containing a concentration of about 10 ppm or less, the binder containing the acrylic acid terpolymer is dispersed. Thereafter, the nonwoven fabric structure is easily broken and dispersed in water.

In one embodiment of the invention, the tensile strength in use of the nonwoven fabric forms a nonwoven fabric having a binding material comprising the ion sensitive polymer formulation of the present invention and then applies one or more monovalent and / or polybasic salts to the nonwoven fabric. Can be increased. The salt is applied to the nonwoven fabric by any method known to those skilled in the art, including but not limited to the application of solid powder onto the fabric and the spraying of the salt solution onto the fabric. Can be. The amount of salt can vary depending on the particular application. However, the amount of salt applied to the fabric is generally from about 0.1% to about 10% by weight salt solids, based on the total weight of the fabric. The salt containing fabrics of the present invention can be used in a variety of fabric applications, including but not limited to feminine pads, surgical bandages, and diapers.

Those skilled in the art will understand that the binder formulations and fibrous substrates of the present invention can be advantageously used in the manufacture of a wide variety of products, including but not limited to absorbent personal care products designed to contact body fluids. will be. Such products may comprise a single layer of fibrous substrate, as described above, or may include a combination of components. Although the binder formulations and fibrous substrates of the present invention are particularly suitable as personal care products, the binder formulations and fibrous substrates can be advantageously used in a wide variety of consumer products.

The combination of the acrylic acid terpolymer or sulfonate anion modified acrylic acid terpolymer and uncrosslinked poly (ethylene-vinyl acetate) of the present invention results in improved results compared to the use of terpolymer alone. For example, when the ion sensitive polymer formulation of the present invention is used as a binder composition for wet wipes, the wet wipes have improved wettability in the first insult without losing dispersibility, so that the wipe basesheet Easily wet with wet wipe solution at commercial rates. In addition, the ion sensitive polymer formulations of the present invention can reduce the stiffness of the dry basesheets, can improve the operability of drying and other brittle sheets during further conversion of the product, ) The degree of spraying of the ion sensitive binder can be reduced, thereby improving the distribution and penetration of the binder in the basesheet.

Unlike other binder systems known in the art, the ion sensitive polymer formulations of the present invention can be activated as a binder without the need for elevated temperatures. Drying or moisture removal is useful in achieving good distribution of the binder in the fibrous web, but the elevated temperature itself is not critical, as the binder may undergo crosslinking or other chemical reactions with high activation energy to act as a binder. It is not required. Rather, interaction with soluble activating compounds, generally salts, is sufficient to cause the binder to be activated (insoluble) or "salt precipitate". Thus, if necessary, the drying step should be avoided or replaced by a cold moisture removal operation such as room temperature drying or freeze drying. Elevated temperatures generally aid in drying, but drying may occur below the temperature normally required to induce crosslinking reactions. Thus, the peak temperature at which the substrate is exposed or the substrate is elevated may be below any of the following temperatures: 180 ° C., 160 ° C., 140 ° C., 120 ° C., 110 ° C., 105 ° C., 100 ° C., 90 ° C., 75 ° C., and 60 ° C. Exemplary ranges of peak web temperatures are from about 50 ° C to about 110 ° C or from about 70 ° C to about 140 ° C. Of course, higher temperatures may be used, but are not necessary in most embodiments. Cobonder polymer systems, such as commercial latex emulsions, may also include crosslinkers suitable for reactions at temperatures above 160 ° C., however, maintaining a low peak temperature may be beneficial to prevent the occurrence of excessive strength in the cobinder polymer. Otherwise, it will interfere with the water dispersibility of the wet wipes.

Wet wipes Wet compositions and wet wipes containing them

One particularly interesting embodiment of the present invention is the preparation of wipes or wet wipes previously wetted from the ion sensitive binder compositions and fibrous materials described above. In the case of wipes, the fibrous material may be in the form of a woven or nonwoven fabric. However, nonwoven fabrics are more preferred. Preferably, the nonwoven fabric is made from relatively short fibers, for example wood pulp fibers. The minimum length of the fiber depends on the method chosen for nonwoven fabric formation. When the nonwoven fabric is formed by the wet or dry method, the fiber length is preferably about 0.1 mm to 15 mm. Preferably, the nonwoven fabric of the present invention has a relatively low wet adhesive strength when not bonded with an adhesive or binder material. When such nonwoven fabrics are bonded together in a binder composition, they lose their bond strength in tap water and sewage water and will be easily broken by movement through the agitation and sewer pipes provided by flushing.

The finished wipe may be packaged individually, preferably in a nested state, in a moisture resistant package, or in a container containing any desired number of sheets in a waterproof package containing the wet composition applied to the wipe. Can be. The finished wipe may also be packaged in a roll of sheets that can be separated in a moisture resistant container containing any desired number of sheets on a roll with the wet composition applied to the wipe. The roll may be coreless, hollow or hollow. Coreless rolls with or without hollow centers are listed in SRP Industries, Inc., Jose, Calif., And US Pat. No. 4,667,890 (Gietman, May 26, 1987). Can be produced with a known tireless roll winder comprising the device disclosed in Cold tireless rolls can provide more products for a given volume and can be adapted to a wide variety of dispensers.

By weight of the dry fabric, the wipe is preferably from about 10% to about 400% wet composition, more preferably from about 100% to about 300% wet composition, and even more preferably from about 180% to about 240 % Of the wetting composition. Wipes retain their desired characteristics over the periods involved in warehouses, transportation, retail display and consumer storage. Thus, lifespan can range from two months to two years.

Various forms of impermeable packaging and storage means for containing wet packaged materials, such as wipes and towels, are known in the art. Any of these may be used to package pre-wet wipes of the present invention.

Preferably, the pre-wet wipes of the present invention are wetted with a water soluble wetting composition having at least one of the following properties:

(1) is compatible with the ion sensitive binder composition described above of the present invention;

(2) pre-soaked wipes to maintain their wet strength during conversion, storage and use (including trials), while maintaining dispersibility in the toilet;

(3) does not cause skin irritation;

(4) reduces the stickiness of the wipe and provides unique tactile properties such as skin activity and "feel like lotion";

(5) Act as a vehicle to deliver “wet cleansing” and other skin health benefits.

The wetting composition cannot act as a solvent for the binder and generally contains no solvent other than water, and especially no organic solvent, but depending on the orientation and salt concentration of the wetting composition, such as polysorbate 20 (<1 %) Fragrance solubilizer may be present. Preferably, the wet composition contains less than about 10% by weight organic solvent, such as propylene glycol or other glycols, polyhydroxy alcohols, and the like, based on the total weight of the wet composition. More preferably, the wet composition contains less than about 4 weight percent organic solvent. Even more preferably, the wet composition contains less than about 1 weight percent organic solvent. The wet composition may be substantially free of organic solvents.

One aspect of the present invention is a wet composition comprising an activating compound that maintains the strength of the water dispersible binder until the activating compound is diluted with water to lower the strength of the water dispersible binder. The water dispersible binder may be any ion sensitive binder composition of the present invention or any other ion sensitive binder composition. The activating compound in the wetting composition may be a salt such as sodium chloride or any other compound that provides strength during use and storage to the water dispersible binder composition, which is diluted in water when the binder polymer is triggered in a weakened state to disperse the substrate. You can do that. Preferably, the wet composition contains about 10% by weight of the activating compound based on the total weight of the wet composition. Specifically, the wet composition may contain about 0.3% to about 5% by weight of the activating compound. Even more specifically, the wet composition may contain about 2% to about 4% by weight of the activating compound.

The wetting composition of the present invention may further comprise various additives that are compatible with the activating compound and the water dispersible binder so that the strength and dispersing function of the wipe are not compromised. Suitable additives in the wetting composition include the following additives, skin protection additives, odor control agents, detackifiers, particulate matter, antimicrobial agents, preservatives, detergents, surfactants and some silicones to reduce the tackiness of the binder, skin Emollients, surface feel enhancers for enhanced tactile sensation (eg, smoothness) on the skin, fragrances, fragrance solubilizers, opacifiers, fluorescent brighteners, UV absorbers, pharmaceuticals and pH regulators such as malic acid or potassium hydroxide It is not limited.

Skin protection additive

As used herein, the term "skin protection additive" refers to an additive that provides the user with one or more advantages, such as a reduction in the likelihood of skin damage caused by diaper rash and / or other fecal enzymes. These enzymes, especially trypsin, chymotrypsin and elastase, are proteolytic enzymes produced in the gastrointestinal tract for digesting food. In infants, for example, feces tend to be thin and contain bacteria and small amounts of undegraded digestive enzymes, among other substances. If these enzymes remain in contact with the skin for any significant amount of time, they have been found to cause unpleasant inflammation per se and can make the skin susceptible to infection by microorganisms. As an alternative, skin protection additives include, but are not limited to, enzyme inhibitors and scavengers described below. The wet composition may contain less than about 5 weight percent skin protection additive based on the total weight of the wet composition. More specifically, the wetting composition may comprise about 0.01% to about 2% by weight of a skin protection additive. More specifically, the wet composition may contain from about 0.01% to about 0.05% by weight of a skin protection additive.

Various skin protection additives may be added to or included in the wetting compositions and pre-soaked wipes of the present invention. In one embodiment of the invention, skin protective additives in the form of particles are added to function as fecal enzyme inhibitors to provide potential advantages in reducing diaper rash and skin damage caused by fecal enzymes. US Pat. No. 6,051,749 (Schulz et al., April 18, 2000), which is hereby incorporated by reference in its entirety, is an organophilic in a fabric or nonwoven web believed to be useful for inhibiting fecal enzymes. Describes clay Such materials can be used in the present invention, including reaction products of long-chain organic quaternary ammonium compounds with one or more of the following clays, montmorillonite, bentonite, baydelirite, hectoride, saponite and stebencite.

Other known enzyme inhibitors and scavengers (those that inhibit trypsin and other digestive or fecal enzymes and inhibitors of urease) can be used as skin protection additives in the wetting compositions of the invention. For example, enzyme inhibitors and antimicrobial agents can be used to prevent odor formation in body fluids. For example, urease inhibitors, which are said to play a role in odor absorption, are described in T. Trinh in World Patent Application No. 98/26808, "Absorbent Articles with Odor Control System," published Jun. 25, 1998, the entirety of which is incorporated herein by reference. Such inhibitors may be incorporated into the wet compositions and pre-wet wipes of the present invention and include transition metal ions and their soluble salts, such as silver, copper, zinc, iron and aluminum salts. In addition, anions such as borate and phytate can provide urease inhibition. Potentially valuable compounds are silver chlorate, silver nitrate, mercury acetate, mercury chloride, mercury nitrate, copper metaborate, copper bromate, copper bromide, copper chloride, copper dichromate, copper nitrate, copper salicylate, copper sulfide, zinc acetate Zinc borate, zinc phytate, zinc bromide, zinc bromide, zinc chlorate, zinc chloride, zinc sulfate, cadmium acetate, cadmium borate, cadmium bromide, cadmium chlorate, cadmium chloride, cadmium formate, cadmium iodide, cadmium iodide, peroxide Cadmium manganese, cadmium nitrate, cadmium sulfate and gold chloride.

Other salts described as having urease inhibitory properties include iron and aluminum salts, in particular nitrate and bismuth salts. Other urease inhibitors are described in Trinin, including hydroxamic acid and its derivatives; Thiourea; Hydroxylamine; Phytate salt; Plant extracts of various species, including various tannins, for example derivatives thereof such as carob tandine and chlorogenic acid derivatives; Natural acids such as ascorbic acid, citric acid and salts thereof; Phenyl phosphor diamidate / diamino phosphoric acid phenyl ester; Metal aryl phosphoramidate complexes including substituted porodiamidate compounds; Phosphoramidate without substitution on nitrogen; Boric acid and / or salts thereof, in particular comprising borax and / or organic boric acid compounds; Compounds disclosed in European Patent Application No. 408,199; Sodium, copper, manganese and / or zinc dithiocarbamate; Quinones; phenol; Thioram; Substituted rhodanine acetic acid; Alkylated benzoquinones; Formarnidine disulfide; 1: 3-dikenone malic anhydride; Succiamide; Phthalic anhydride; Fehenic acid; N, N-dihalo-2-imidazolidinone; N-halo2-oxazolidinone; Thio- and / or acyl-phosphorylamide and / or substituted derivatives thereof, thiopyridine-N-oxide, thiopyridine and thiopyrimidine; Oxidized sulfur derivatives of diarinophosphinyl compounds; Cyclotriphosphatriene derivatives; Ortho-diaminoporfinyl derivatives of oxime; Bromo-nitro compounds; S-aryl and / or alkyl diaminophosphothiolates; Diaminophosphinyl derivatives; Mono- and / or polyphosphorodiamides; 5-substituted-benzoxathiol-2-ones; N (diaminophosphinyl) arylcarboxamide; Alkoxy-1,2-benzothiazine compound and the like.

If the additive is compatible with the ion sensitive binder compositions that bind them, in particular the ion sensitive binder compositions of the present invention (i.e. they do not cause a substantial loss of strength in the wet state of the wetted wipes prior to dilution in water, but Many skin protection additives can be incorporated into the wetting compositions and pre-soaked wipes of the present invention, which include sunscreens and UV absorbers, acne treatments, pharmaceuticals, baking soda (their encapsulated form) Vitamins such as vitamins A or E and derivatives thereof, hazelnut extracts and vegetable drugs such as aloe vera, allantoin, emollients, disinfectants, anti-wrinkle agents or hydroxy acids for sun protection, sunscreen, Sunburn accelerators, skin lighteners, deodorants and antiperspirants, ceramides, astrates for skin benefits and other uses Lintants, wetting agents, nail polish removers, insect repellents, antioxidants, fungicides, anti-inflammatory agents and the like.

Materials useful for skin protection and other benefits are described in McCutcheon's 1999, Vol. 2: Functional Materials, MC Publishing Company, Glen Rock, N.J. Many useful botanicals for skin care are provided by Active Organics, Lewisville, Tex.

Odor control additives

Odor control additives suitable for use in the wet compositions and pre-wet wipes of the present invention include zinc salts; Talc powder; Encapsulated aroma (including microcapsules, macrocapsules, aromas encapsulated in liposomes, membrane vesicles or microemulsions); Chelates such as ethyllandidiamine tetra-acetic acid; Zeolites; Activated silica, activated carbon granules or fibers; Activated silica particles; Polycarboxylic acids such as citric acid; Cyclodextrins and cyclodextrin derivatives; Chitosan or chitin and derivatives thereof; Oxidizing agents; Antimicrobial agents including silver loaded zeolites (for example sold under the trade name HEALTHSHEIDL ™ by BF Technologies, Beverly, Mass.); Triclosan; Diatomaceous earth; And mixtures thereof. In addition to odor control from the body or body waste, an odor control scheme may be used to block or control any odor of the treated substrate. Preferably, the wet composition contains less than about 5 weight percent odor control additive based on the total weight of the wet composition. More preferably, the wet composition contains about 0.01% to about 2% by weight odor control additive. Even more preferably, the wet composition contains from about 0.03% to about 1% by weight odor control additive.

In one embodiment of the invention, the wet composition and / or pre-wet wipe comprises an induced cyclodextrin, for example hydroxylpropyl beta-cyclodextrin in a solution that remains after wiping and provides an odor absorbing layer. In other embodiments, the odor source is removed or neutralized by the application of an odor control additive, which is often exemplified by the action of chelates that bind metal groups necessary for the action of many proteases and other enzymes that produce odors.

The principle of applying chitosan or chitin derivatives to nonwoven webs and cellulosic fibers is described in S. Lee et al. in "Antimicrobial and Blood Repellent Finishes for Cotton and Nonwoven Fabrics Based on Chitosan and Fluoropolymers," Textile Research Journal, 69 (2); 104-112, February 1999.

Detackifier

Elevated salt concentrations may reduce the tack of the ion sensitive binder, but other methods of reducing the tack are often preferred. Thus, the detackifier may be used in the wet composition to reduce this tack when the tackiness of the ion sensitive binder is present. Suitable detackifiers include any material known in the art to reduce the tack between two adjacent fibrous sheets treated with an adhesive like polymer or any material that can reduce the sticky feel of the adhesive like polymer on the skin. do. The detackifier may be applied as a solid particle, suspension or slurry of particles in dry form. Deposition can occur by spraying, coating, electrostatic deposition, impregnation, filtration (i.e., the pressure difference causes the particle loaded gas layer to pass through the substrate, depositing particles by filtration mechanisms), and the like. It may be applied uniformly over the layer or may be applied in a patterned manner (eg, a repeating or random pattern) on part or surfaces of the substrate surface. Detackifiers may be present throughout the substrate thickness, but may be concentrated on one or both of the surfaces and may be present on substantially only one or both surfaces of the substrate.

Specific detackifiers include talc powder, calcium carbonate, mica; Starch such as corn starch; Calendula powder; Mineral fillers such as titanium dioxide; Silica powder; Alumina; Common metal oxides; Baking powder; Diatomaceous earth and the like. In addition, polymers and other additives with low surface energy can be used, including a wide variety of fluorinated polymers, silicone additives, polyolefins and the like, including compounds having alkyl side chain groups such as those having 16 or more carbon atoms known in the art of papermaking. Thermoplastics, waxes, debonders and the like can be used. In addition to the compounds used as release agents for the manufacture of shaped articles and candles, dry lubricants and fluorinated release agents can also be considered.

In one embodiment, the detackifier is a PTFE telomer (KRYTOX) used in PTFE release agent dry lubricant MS-122DF. Polytetrafluoroethylene (PTFE) (Miller-Stephenson, Danbury, Conn.), Such as DF), is included as a spray product. For example, the PTFE particles can be applied by spraying on one side of the substrate prior to winding up the wipes previously wetted. In one embodiment, the detackifier is applied to only one side of the substrate prior to being wound into the roll.

The wet composition preferably contains less than about 25 weight percent detackifier, based on the total weight of the wet composition. More preferably, the wet composition contains from about 0.01% to about 10% by weight of detackifier, more specifically up to about 5% of detackifier. Even more specifically, the wet composition contains about 0.05% to about 2% by weight of detackifier.

In addition to acting as a detackifier, starch compounds can also improve the strength properties of pre-wet wipes. For example, when ungelled starch particles, such as hydrophilic tapioca starch, are present at a concentration of at least about 1% by weight relative to the weight of the wet composition, the wipes pre-soaked at salt concentrations lower than possible when no starch is present It is possible to maintain the same strength. Thus, for example, the desired strength can be achieved with 2% salt in the wet composition in the presence of salt compared to the salt concentration of 4% required when no starch is present. Starch may be added by adding starch in a suspension of laponite to enhance the dispersion of starch in the wet composition.

Particulate

The wet composition of the present invention may be further modified by adding solid particles or particulates. Suitable particles include, but are not limited to, mica, silica, alumina, calcium carbonate, cannoline, talc and zeolites. Particles can be treated with stearic acid or other additives as needed to increase the attraction of particles or binding of the particles to the binder system. In addition, two-component particulate systems commonly used as retention aids in the papermaking industry can be used. Such bicomponent particulate systems generally comprise a water soluble cationic polymer for connecting the particles to colloidal particulates such as silica particles and fibers of the web to be formed. The presence of the particles in the wetting composition may include (1) an increase in the opacity of the pre-wet wipe; (2) deformation or deterioration of the rheology of the wet wipes; (3) improvement of the tactile properties of the wipe; (4) It may be responsible for one or more useful functions such as delivering a desired drug to the skin by a particulate carrier such as a porous carrier or microcapsules. Preferably, the wet composition contains less than about 25 weight percent particles based on the total weight of the wet composition. More specifically, the wet composition may contain from about 0.05% to about 10% by weight of particulates. Even more specifically, the wet composition may contain from about 0.1% to about 5% by weight of particulates.

Microcapsules and Other Delivery Vehicles

In addition, the microcapsules and other delivery vehicles are moisturizing compositions of the present invention to provide skin protectants, drugs, comfort promoters such as eucalyptus, perfumes, skin protectants, odor control additives, vitamins, powders and other additives to the user's skin. Can be used. Specifically, the wet composition may contain up to about 25% by weight microcapsules or other delivery vehicle based on the total weight of the wet composition. More specifically, the wet composition may contain about 0.05% to about 10% by weight microcapsules or other delivery vehicle. Even more specifically, the wet composition may contain from about 0.2% to about 5% by weight microcapsules or other delivery vehicle.

Microcapsules and other delivery vehicles are known in the art. For example, POLY-PORE E200 (Chemdal Corp., Arlington Heights, Ill.) Is a delivery agent that contains a soft hollow sphere containing an additive 10 times the weight of the delivery vehicle. POLY-PORE Known additives reported to be used with E200 include, but are not limited to, benzoyl peroxide, salicylic acid, retinol, retinyl palmitate, octyl methoxycinnamate, tocopherol, silicone compounds (DC 435) and mineral oils. . Another useful delivery vehicle is POLY-PORE Sponge-like material sold as L200, which has been reported to be used with silicone (DC 435) and mineral oils. Other known delivery systems include cyclodextrins and derivatives thereof, liposomes, polymer sponges, and spray dried starches.

The additives present in the microcapsules are isolated from the environment and other drugs in the wetting composition, and when the wipe contacts the skin, the microcapsules are destroyed to deliver the load to the skin or other surface.

Preservatives and Antimicrobials

In addition, the wetting compositions of the invention may include preservatives and / or antimicrobial agents. Many preservatives and / or antimicrobials, such as Mackstat H 66 (available from the McIntyre Group, Chicago, Ill.), Have excellent results in inhibiting bacterial and fungal growth. I found that. Other suitable preservatives and antimicrobial agents include DMDM Hydantoin (e.g., Glydant Plus ™, Lonza, Inc., Fairlon, NJ), iodopropyl butylcarbamate, Ketone (Kathon) (Rom and Haas, Philadelphia, PA), methylparabine, propylparabine, 2-bromo-2-nitropropane-1,3-diol, benzoic acid, and the like. Preferably, the wet composition contains less than about 2 weight percent based on the activity of the preservative and / or antimicrobial agent, based on the total weight of the wet composition. More preferably, the wet composition contains from about 0.01% to about 1% by weight preservative and / or antimicrobial agent. Even more preferably, the wetting composition comprises from about 0.01% to about 0.5% by weight of preservative and / or antimicrobial agent.

Wetting Agents and Cleaners

Various wetting agents and / or cleaning agents may be used in the wetting compositions of the present invention. Suitable wetting agents and / or cleaning agents include, but are not limited to, surfactants and nonionic, amphoteric and anionic surfactants, especially surfactants based on amino acids. Amino acid based surfactant systems, such as those derived from L-glutamic acid and other natural fatty acid amino acids, provide pH compatibility and good detergency to human skin, while being relatively stable and improved hand and wetting compared to other anionic surfactants. Provide the nature. One action of the surfactant is to improve the wettability of the dry substrate containing the wetting composition. Another action of the surfactant is to disperse bathroom contamination when the wet wipes are in contact with the soiled area and also to increase their absorption into the substrate. In addition, surfactants may be useful in removing makeup, general personal cleansing, hard surface cleaning, odor control, and the like.

One commercial example of an amino acid based surfactant is an acyl glutamate sold under the trade name Amisoft (Ajinomoto Corp., Tokyo, Japan). Preferably, the wet composition contains about 3% by weight wetting agent and / or detergent based on the total weight of the wet composition. More preferably, the wetting composition contains from about 0.01% to about 2% by weight wetting agent and / or cleaning agent. Even more preferably, the wetting composition contains from about 0.1% to about 0.5% by weight wetting agent and / or cleaning agent.

While amino acid based surfactants are particularly useful in the wet compositions of the present invention, a wide variety of surfactants can be used in the present invention. Suitable nonionic surfactants include, but are not limited to, condensation products of hydrophobic (lipophilic) polyoxyalkylene bases and ethylene oxide formed by condensation of propylene oxide with propylene glycol. The hydrophobic portions of these compounds preferably have a molecular weight that is high enough to render them water insoluble. The addition of polyoxyethylene groups to this hydrophobic portion increases the water solubility of the molecule as a whole, and the liquid properties of the product retain the polyoxyethylene content below about 50% of the total weight of the condensation reaction product. Examples of this type of compound include commercially available Pluronic surfactants (BASF Wyandotte Crop.), In particular polyoxypropylene ethers, having a molecular weight of about 1500-3000, and the content of polyoxyethylene has a molecular weight About 35-55% of Pluronic L-62.

Other useful nonionic surfactants include, but are not limited to, condensation products of C ₈ -C ₂₂ alkyl alcohols containing 2-50 moles of ethylene oxide per mole alcohol. Examples of this type of compound include condensation products of 3-50 moles of ethylene oxide and C ₁₁ -C ₁₅ secondary alkyl alcohols per mole of alcohol, which is poly-tergent of Olin Chemicals. Tergent) SLF series or Union Carbide Tergitol (TERGITOL ), Ie tergitol It can be purchased as 25-L-7, which is formed by the condensation reaction of about 7 moles of ethylene oxide with a C ₁₂ -C ₁₅ alkanol.

Other nonionic surfactants that can be used in the wetting compositions of the present invention include ethylene oxide esters of C ₆ -C ₁₂ alkyl phenols, such as (nonylphenoxy) polyoxyethylene ethers. Particularly useful are esters prepared by the condensation reaction of about 8-12 moles of ethylene oxide with nonylphenol, ie IGEPAL CO series (GAF Corp.).

In addition, nonionic surface active agents include, but are not limited to, alkyl polyglycosides (APGs) derived as condensation products of dextrose (D-glucose) and straight or branched chain alcohols. The glycoside portion of the surfactant provides hydrophilicity with high hydroxyl group density, which increases water solubility. In addition, the inherent stability of the acetal linkages of glycosides provides chemical stability in alkaline systems. In addition, unlike some nonionic active surface agents, alkyl polyglycosides do not have a cloud point and allow them to be formulated without nostalgic substances, which are extremely irritating and easily biodegradable nonionic surfactants. Surfactants of this class are commercially available from Horizon Chemical under the trade names APG-300, APG-350 and APG-500.

Silicones are another class of wetting agents that can be purchased in pure form or as microemulsions, macroemulsions, and the like. One exemplary group of nonionic surfactants is silicone-glycol copolymers. These surfactants can be prepared by adding poly (lower) alkyleneoxy chains to the free hydroxyl groups of dimethylpolysiloxaneanol, and from Dow Corning Corp., Dow Corning 190 and 193 surfactants (CTFA name: Dimethicone copolyol). In the presence or absence of any volatile silicone used as the solvent, these surfactants act to control the foam produced by other surfactants and impart gloss to metal, ceramic, and glass surfaces.

Anionic surfactants can also be used in the wetting compositions of the present invention. Anionic surfactants useful because of their high detergency include water soluble high fatty acid alkali metal soaps, such as anionic synthetic detergent salts having alkyl substituents having 8 to 22 carbon atoms, such as sodium myristate and sodium palmitate. Preferred classes of anionic surfactants are water soluble sulfates and sulfonated anionic alkali and alkaline earth metal synthetic detergent salts containing hydrophobic higher alkyl groups (typically containing about 8 to 22 carbon atoms), for example For example, salts of higher alkyl mono or polynuclear aryl sulfonates having about 1 to 16 carbon atoms in the alkyl group, examples of which can be obtained as the Bio-Soft series, ie Bio-Soft D-40 It can be obtained as (Stepan Chemcial Co.).

Other useful classes of anionic surfactants include alkali metal salts of alkyl naphthalene sulfonic acids (methyl naphthalene sodium sulfonate, Petro AA, Petrochemical Corporation); Sulfated higher fatty acid monoglycerides such as sodium salts of sulfated monoglycerides of cocoa oil fatty acids and potassium salts of sulfated monoglycerides of tallow fatty acids; Alkali metal salts of sulfated fatty alcohols containing about 10 to 18 carbon atoms (eg, sodium lauryl sulfate and sodium stearyl sulfate); Sodium C ₁₄ -C ₁₆ -alphaolefin sulfonates such as the Bio-Terge series (Stephan Chemical Corporation); Alkali metal salts of sulfated ethyleneoxy fatty alcohols (sodium or ammonium sulfate of condensation products of about 3 moles of ethylene oxide with C ₁₂ -C ₁₅ n-alkanols, ie Neodol ethoxysulfate, cell chemical Shell Chemical Co .; alkali metal salts of higher fatty esters of low molecular weight alkylol sulfonic acids, such as fatty acid esters of sodium salts of isotionic acid, fatty ethanolamide sulfates; fatty acid amides of amino alkyl sulfonic acids. , Lauric amide of taurine, and many other anionic organic surface active materials, such as, but not limited to, sodium xylene sulfonate, sodium naphthalene sulfonate, sodium toluene sulfonate, and mixtures thereof .

A further useful class of anionic surfactants includes 8- (4-n-alkyl-2-cyclohexenyl) -oxanonic acid, wherein the cyclohexenyl ring is substituted with additional carboxylic acid groups. These compounds or their potassium salts can be purchased as phosphate 1550 or H-240 from Westvaco Corporation. In general, these anionic surface active materials can be used in the form of their alkali metal salts, ammonium or alkaline earth metal salts.

Macroemulsion and Microemulsion of Silicon Particles

The wetting composition may further comprise a water soluble microemulsion of silicon particles. For example, US Pat. No. 6,037,407 ("Process for the Preparation of Aqueous Emulsions of Silicone Oils and / or Gums and / or Resins", dated Mar. 14, 2000) discloses organopolysiloxanes in water-soluble microemulsions. Doing. Preferably, the wet composition contains less than about 5 weight percent microemulsion of silicon particles based on the total weight of the wet composition. More preferably, the wet composition contains about 0.02% to about 3% by weight of microemulsion of silicon particles. Even more preferably, the wet composition contains about 0.02% to about 0.5% by weight of microemulsion of silicon particles.

Silicone emulsions may generally be applied to the wipes previously wetted by any known coating method. For example, the wipes previously wetted may be wetted with a water-soluble composition containing a water-dispersible or water-miscible silicone based component compatible with the activating compound in the wet composition. In addition, the wipe may comprise a nonwoven web of fibers containing a water dispersible binder, where the web is moistened with a lotion comprising a silico succinate. Silicone based sulfosuccinates provide gentle and effective cleaning without high concentrations of surfactants. In addition, silicosuccinates based on solubilization provide a solubilizing action, which prevents precipitation of oil-soluble components such as fragrance components, vitamin extracts, plant extracts and essential oils.

In one embodiment of the present invention, the wet composition comprises a silicone copolyol sulfosuccinate, for example disodium dimethicone copolyol sulfosuccinate and diammonium dimethiconecopolyolsulfosuccinate. Preferably, the wet composition comprises less than about 2 weight percent silicone based sulfosuccinate, more preferably from about 0.05 weight percent to about 0.30 weight percent silicone based sulfosuccinate.

In another example of an article comprising a silicone emulsion, Dow Corning 9506 powder may also be present in the wetting composition. Dow Corning 9506 powder is believed to contain dimethicone / vinyldimethicone crosslinked polymers, which are spherical powders and are mentioned as useful in controlling skin oils ("New Chemical Perspectives," Soap and Cosmetics, Vol. 76). , No. 3, March 2000, p. 12). Accordingly, water dispersible wipes that deliver effective powders in controlling skin oils are also within the scope of the present invention. The production principle of silicone emulsions is described in WO 97/10100 (published on March 20, 1997).

Emollients

In addition, the wetting compositions of the present invention contain one or more emollients. Suitable emollients are PEG 75 Lanolin, Methyl Gluset 20 Benzoate, C ₁₂ -C ₁₅ Alkyl Benzoate, Ethoxylated Cetyl Stearyl Alcohol (Lambent Wax WS-L, Ramvent WD-F, Cetiol (Cetiol) HE (Henkel Corp., Glucam P20 (Amerchol, Polyox WSR N-10 (Union Carbide), Polyox WSR N-3000 (Union Carbide), Ruby Luviquat (BASF), Finsolv SLB101 (Finetex Corp.), mink oil, allatoin, stearyl alcohol, Estol 1517 (Unichema) and pinsolve SLB 201 (Pinetex Corporation), but not limited thereto.

In addition, emollients may be applied to the surface of the product before or after soaking with the wetting composition. Such emollients are insoluble in the wetting compositions and may be immobilized except when exposed to some force. For example, petrolatum based emollients can be applied to one surface in some pattern, and then the other surface is wetted to saturate the wipe. Such a product can provide one cleaning surface and the skin treatment surface opposite.

The emollient compositions in such and other products of the present invention may include one or more liquid hydrocarbons, including polysiloxanes, described in US Pat. No. 5,891,126 (registered April 6, 1999 to Osborn III et al.) Plastic or liquid emollients such as, for example, petrolatum), mineral oils, vegetable and animal fats (eg, lanolin, phospholipids and derivatives thereof) and / or silicone materials such as one or more alkyl substituted polysiloxane polymers, and the like. It may include. Optionally, hydrophilic surfactants can be combined with plastic emollients to improve the wettability of the coated surface. In some embodiments of the present invention, it is contemplated that the liquid hydrocarbon emollient and / or alkyl substituted polysiloxane polymer may be blended or combined with one or more fatty acid ester emollients derived from fatty acids or fatty alcohols.

In one embodiment of the invention, the emollient material is in the form of an emollient blend. Preferably, the emollient blend is combined with at least one liquid hydrocarbon (eg petroleum jelly), mineral oil, vegetable and animal fats (eg lanolin, phosphoric acid and derivatives thereof) and at least one alkyl substituted polysiloxane polymer. Combinations of the same silicone materials. More preferably, the emollient blend comprises a combination of liquid hydrocarbons (eg petrolatum) with dimethicone or dimethicone and other ilkyl substituted polysiloxane polymers. In some embodiments of the invention, the blend of liquid hydrocarbon emollients and / or alkyl substituted polysiloxane polymers may be blended with one or more fatty acid ester emollients from fatty acids or fatty alcohols. In addition, PEG-7 glyceryl cocoate (Standamul HE (commercially available as Henkel Corporation, Hoboken, NJ)) can be considered.

Water-soluble self-emulsifying emollient oils useful in the wetting compositions of the present invention are polyoxyalkoxylated lanolin and polyoxyalkoxylated fatty alcohols (Smith et al., US Patent No. 4,690,821, registered September 9, 1987). Disclosed in the call). The polyoxyalkoxy chain preferably comprises mixed propyleneoxy and ethyleneoxy units. Lanolin derivatives typically include about 20-70 lower alkoxy units, while C ₁₂ -C ₂₀ -fatty alcohols are derivatized to about 8-15 lower alkyl units. One such useful lanolin derivative is Lanexol AWS (PPG-12-PEG-50, Croda, Inc., New York City, NY). Useful poly (15-20) C ₂ -C ₃ -alkoxylates are PPG-5-Ceteth-20 known as Procetyl AWS (Croda Inc).

According to one embodiment of the invention, the emollient material reduces the undesirable tactile properties (if present) of the wetting composition. For example, emollient materials, including dimethicone, can reduce the level of tack that can be caused by ion sensitive binders or other components in the wetting composition, acting as a detackifier.

Preferably, the wet composition contains less than about 25% by weight emollient based on the total weight of the wet composition. More specifically, the wet composition may comprise less than about 5% by weight emollient, more specifically less than about 2% by weight emollient. More preferably, the wet composition may contain about 0.01% to about 8% by weight emollient. Even more preferably, the wetting composition may comprise from about 0.2% to about 2% by weight emollient.

In one embodiment, the wet compositions and / or pre-wet wipes of the present invention comprise one or more skin softener oils and one or more skin dispersed in an aqueous layer containing one or more polyhydric alcohol emollients and one or more organic water soluble detergents. Oil-in-water emulsion comprising an oil layer containing a softener wax stabilizer (US Patent No. 4,559,157, registered with Zara Smith et al. 12/17/1985, incorporated herein by reference in its entirety) Disclosed herein).

Surface tactile modifiers

Surface feel modifiers are used to enhance the skin's feel (eg lubricity) during use of the product. Suitable surface tactile modifiers include commercial release agents; And softeners such as, but not limited to, softeners used in the manufacturing arts, including quaternary ammonium compounds with fatty acid side chains, silicones, waxes, and the like. Exemplary quaternary ammonium compounds having utility as emollients are disclosed in U.S. Patent Nos. 3,554,862, filed on January 12, 1971 to Hervey et al .; US Patent No. 4,144,122, registered March 13, 1979 to Emanuelsson et al .; Nov. 12, 1996; US Pat. No. 5,573,637, registered with Zarlo Ampulski et al .; And US Patent No. 4,476,323, filed J. October 9, 1984 to Hellsten et al., The entire contents of which are incorporated herein by reference. Preferably, the wet composition contains less than about 2 weight percent surface active modifier based on the total weight of the wet composition. More preferably, the wet composition contains from about 0.01% to about 1% by weight surface tactile modifier. Even more preferably, the wet composition contains from about 0.01% to about 0.05% by weight surface tactile modifier.

direction

Various directions can be used in the wetting compositions of the present invention. Preferably, the wet composition comprises less than about 2 weight percent of aromatics based on the total weight of the wet composition. More preferably, the wet composition contains from about 0.01% to about 1% by weight of fragrance. Even more preferably, the wet composition contains from about 0.01% to about 0.05% by weight of fragrance.

Aroma solubilizer

In addition, various fragrance solubilizers can be used in the wetting compositions of the present invention. Suitable aromatic solubilizers include polysorbate 20, propylene glycol, ethanol, isopropanol, diethylene glycol monoethyl ether, dipropylene glycol, diethyl phthalate, triethyl citrate, Ameroxol OE-2 (amerchol) Corporation (Amerchol Corp.), Brij 78 and Brij 98 (ICI surfactant), Arlassolve 200 (ICI surfactant), Calfax 16L-35 (Pilot Chemical Co. ), Capmul POE-S (Abitec Corp.), Finsolv SUBSTANTIAL (Finetex), and the like. Preferably, the wet composition contains less than about 2% by weight fragrance solubilizer, based on the total weight of the wet composition. More preferably, the wet composition contains about 0.1% to about 1% by weight fragrance solubilizer. Even more preferably, the wet composition contains from about 0.01% to about 0.05% by weight fragrance solubilizer.

Opaque agent

Suitable opacifying agents are titanium dioxide or other minerals or pigments, REACTOPAQUE Synthetic opacity agents such as, but not limited to, particles (commercially available from Sequo Chemicals, Inc., Chester, South Carolina). Preferably, the wet composition contains less than about 2 weight of opaque agent based on the total weight of the wet composition. More preferably, the wet composition contains from about 0.01% to about 1% by weight opaque agent. Even more preferably, the wet composition contains from about 0.01% to about 0.05% by weight of the opaque agent.

pH regulator

Suitable pH adjusting agents for use in the wetting compositions of the present invention include, but are not limited to, malic acid, citric acid, hydrochloric acid, acetic acid, sodium hydroxide, potassium hydroxide, and the like. Appropriate pH ranges minimize the amount of skin inflammation caused by the wetting composition on the skin. Preferably, the pH range of the wet composition is about 3.5 to about 6.5. More preferably, the pH range of the wet composition is about 4 to about 6. Preferably, the wet composition contains less than about 2 weight percent pH adjuster based on the total weight of the wet composition. More preferably, the wet composition contains about 0.01% to about 1% by weight of pH adjuster. Even more preferably, the wet composition contains from about 0.01% to about 0.05% by weight pH adjuster.

Although a variety of wet compositions from one or more of the components described above can be used in the wet wipes of the present invention, in one embodiment, the wet composition comprises the following components in a predetermined weight percent of the wet composition as shown in Table 2 below. It contains.

TABLE 2 Wet Composition Components

Wetting Composition Ingredients: weight %: Deionized water About 86 to about 98 Activating compound About 1 to about 6 Preservative About 2 or less Surfactants About 2 or less Silicone emulsion About 1 or less Emollients About 1 or less direction About 0.3 or less Aroma solubilizer About 0.5 or less pH regulator About 0.2 or less

In another embodiment of the present invention, the wet composition contains the following components in a predetermined weight percent of the wet composition, as shown in Table 3 below.

TABLE 3 Wetting Composition Components

Group of Wetting Composition Components: Specific Wetting Composition Ingredients: Compound name: weight%: Vehicle Deionized water About 86 to about 98 Activating compound Sodium Chloride (Milport Ent., Milwaukee, WI) About 1 to about 6 Preservative Glycerin, IPBC and DMDM Hydantoin Maxstat H-66 (McIntyre Group, Chicago, Illinois) About 2 or less Surfactants Acyl glutamate CS22 (Ajinomoto, Tokyo, Japan) About 2 or less Silicone Emulsion Dimethiconol and TEA dodecyl benzene sulfonate DC1785 (Dow Corning, Midland, Michigan) About 1 or less Emollients PEG-75 Lanolin Solulan L-575 (amercall in Middlesex, New Jersey) About 1 or less direction direction Dragoco 0/708768 (Dragoco, Roseville, Minnesota) About 0.3 or less Aroma solubilizer Polysorbate 20 Glensurf L20 (Glenn Corp., St. Paul, Minn.) About 0.5 or less pH regulator Malic acid, pH 5 (Haarman & Reimer, Tetreboro, NJ) About 0.2 or less

In another embodiment of the present invention, the wet composition contains the following components in a predetermined weight percent of the wet composition, as shown in Table 4 below.

Table 4 Exemplary Wetting Compositions

Group of Wetting Composition Components: Specific Wetting Composition Compound name: weight%: Vehicle Deionized water Approximately 93 Activating compound Sodium chloride About 4 Preservative Glycerin, IPBC and DMDM Hydantoin Maxstart H-66 About 1 Surfactants Acyl glutamate CS22 / ECS 229 About 1 Silicone emulsion Dimethiconol and TEA dodecylbenzenesulfonate DC1784 / DC1785 About 0.5 Emollients PEG-75 Lanolin Soluran L-575 About 0.25 direction direction To Dragoco 0/708768 About 0.05 Aroma solubilizer Polysorbate 20 Glensurf L20 About 0.25 pH regulator Malic acid to pH 5 About 0.07

It should be noted that the wetting compositions of the present invention described above may be used with any one of the above described ion sensitive binders. In addition, the wet compositions of the present invention described above can be used with any other binding composition, including conventional binder compositions, or with any known fibrous or absorbent substrate (whether dispersible).

Strength characteristics

Unless otherwise specified, tensile tests are performed according to the following protocol. Testing of the dry product should be performed under Tapi conditions (50% relative humidity, 73 ° F.) in a manner similar to ASTM-1117-80, section 7. Tensile testing is performed with a constant crosshead speed tensile tester, such as the Twine 1256-100 tensile tester with RSA-2 10-kg load gauge. Samples were cut to 3 inches wide and 6 inches long and raised between jaws of 4 inch long gauge. Crosshead speed was 12 inches per minute. Peak load (relative to tensile strength) and elongation at peak load were measured. For the transverse (CD) tensile test, the samples were cut transversely. For longitudinal (MD) tensile test, samples were cut longitudinally.

Tensile tests in the dry state were reported for the web obtained prior to applying the wetting composition. The longitudinal dry tensile strength was abbreviated as "MDDT" and the transverse dry tensile strength as "CDDT". Results can be reported in kg / 3-in or converted to g / in or g / 2.54 cm.

Based on the dry weight of the sample cut to the appropriate size, excess wet solution (4% saline solution without other additives, unless otherwise indicated) was added to reach a solution addition of 250-400%. The solution was then uniformly dispersed in the sample to achieve a final 200% solution addition, and the wetted sample was then transferred to an Atlas Lab Launcher (Atlas Elite Device, Chicago, USA) to gently remove excess solution. Quickly passed through Atlas Electric Devices Company, III.No. 10404 LW-1, no load). Several iterations or passages may be required to reach the addition target according to the sample. The finished presoaked sample was then placed in a plastic bag to prevent drying before testing.

The water was equilibrated by stirring in a sealed plastic bag overnight, and the transverse wet tensile test (CDWT) or the longitudinal wet tensile test (MDWT) was performed as described above using pre-soaked samples.

For testing related to the reduction in strength in the resulting pre-soaked web after exposure to fresh solution, a volume of vessel with a depth sufficient to hold 200 mm x 120 mm and 1000 ml was filled with 700 ml of the selected immersion solution. Samples up to 108 inches ² were immersed in 700 ml immersion solution, depending on the sample size. Equilibrated overnight soaked samples were soaked in immersion solution and allowed to immerse calmly for the designated time (typically 1 hour). When the immersion time is complete, the sample is carefully collected from the immersion solution, allowed to drain, and then tested as described above (ie, the sample is quickly placed in the tensile tester and tested without passing through the impeller). . In the case of highly dispersible materials, samples are often not recovered from the immersion solution without separation. The immersed tensile value of such a sample is reported as zero for that solution.

For deionized immersed cross section wet tensile test, S-CDWT, samples were tested after immersion in deionized water for 1 hour. For water-immersed cross-sectional wet tensile test, S-CDWT-M (M represents divalent metal ion), water containing 2: ppm of 200 ppm Ca ²⁺ / Mg ²⁺ prepared from potassium chloride and magnesium chloride The sample was immersed in and then immersed for 1 hour before testing. Hard water immersed cross-sectional wet tensile test, for MS-CDWT-M, samples were immersed in water containing 2: ppm of 50 ppm Ca ²⁺ / Mg ²⁺ at 2: 1 ratio and tested after soaking for 1 hour. Tests performed with other time increments or immersion solutions should be marked to avoid confusion with S-CDWT or S-CDWT-M tests.

In one embodiment of the invention, the wet wipe comprises any of the wet compositions of Table 3 described above and about 80% by weight of bleached kraft fiber and 20% by weight of the ion sensitive binder composition of the invention described above. It is prepared using an airlaid fibrous material comprising a composition, where the weight percent is based on the total weight of the dry nonwoven fabric. In a further embodiment of the invention, the wet wipe comprises 10 of the wet composition of Table 3 described above and a copolymer comprising substantially 90% by weight of softwood fibers and an acrylic acid terpolymer or an acrylic acid monomer. It is prepared using a weight percent ion sensitive binder composition, wherein the weight percent is based on the total weight of the dry nonwoven fabric. The amount of wet composition added to the nonwoven fabric relative to the weight percentage of dry nonwoven fabric in these embodiments is preferably from about 180% to about 240% by weight.

Preferably, the wet wipes of the present invention are immersed (MS-CDWT-M) for 1 hour in water at a concentration of about 50 ppm Ca ²⁺ and / or Mg ²⁺ ions, followed by in-use wet tensile strength of at least 100 g / in. (CDWT) and a tensile strength of less than about 30 g / in. More preferably, the wet wipe is immersed (MS-CDWT-M) for 1 hour in water at a concentration of about 50 ppm Ca ²⁺ and / or Mg ²⁺ ions, followed by in-use wet tensile strength (CDWT) of at least 300 g / in. ) And a tensile strength of less than about 30 g / in. In another embodiment, the wet wipe is immersed (S-CDWT-M) for 1 hour in water at a concentration of about 200 ppm Ca ²⁺ and / or Mg ²⁺ ions, followed by in-use wet tensile strength (CDWT) of at least 200 g / in. ) And a tensile strength of less than about 20 g / in. Even more preferably, the wet wipe is immersed (S-CDWT-M) for 1 hour in water at a concentration of Ca ²⁺ and / or Mg ²⁺ ion of about 200 ppm, followed by in-use wet tensile strength of 300 g / in ( CDWT) and a tensile strength of less than about 20 g / in.

Preferably, the wet wipe treated with the binder material of the present invention comprising an acrylic acid terpolymer is immersed in a 10% to 400% wet wipe solution containing a monovalent ion (NaCl) concentration of at least 0.3% by weight. Samples of 1 inch wide transverse surface have a tensile strength of less than about 30 g / in after being immersed in in-use wet tensile strength for at least 100 g / in and deionized water for about 1 hour. More preferably, the wet wipes treated with the binder material of the present invention comprising an acrylic acid terpolymer may be immersed in a 10% to 400% wet wipe solution containing at least 0.3% by weight monovalent ion (NaCl) concentration. A sample of 1 inch wide longitudinal surface has a tensile strength of less than about 30 g / in after being immersed for about 1 hour in wet wet strength and deionized water of at least 200 g / in.

In another embodiment, the wet wipe treated with the binder material of the present invention comprising a sulfonate anion modified acrylic acid terpolymer is preferably 10% to 400% by weight containing a monovalent ion (NaCl) concentration of at least 1% by weight. Approximately 1 ppm in water with an in-use wet tensile strength and concentration of Ca ²⁺ and / or Mg ²⁺ ions of at least 200 g / in for samples of 1 inch wide transverse surface when immersed in% wet wipe solution After soaking for a time, it has a tensile strength of less than about 30 g / in. Even more preferably, the wet wipe treated with the binder material of the present invention comprising a sulfonate anion modified acrylic acid terpolymer is preferably 10% to 400 containing a monovalent ion (NaCl) concentration of at least 1% by weight. About one inch wide cross-section samples, when immersed in a wt% wet wipe solution, in water with an in-use wet tensile strength of at least 200 g / in and a concentration of Ca ²⁺ and / or Mg ²⁺ ions in about 200 ppm After soaking for 1 hour, it has a tensile strength of less than about 30 g / in.

Articles having a basis weight or wet strength higher than the wet wipes that can be flushed may have a relatively high wet tensile strength. For example, a product such as a pre-soaked towel or hard surface cleaning wipes has a basis weight greater than 70 gsm, such as 80 gsm to 150 gsm. Such products have a CDWT of 500 g / in or more, an S-CDWT value of about 150 g / in or less, more specifically about 100 g / in or less, even more specifically, having a similar range possible in the case of S-CDWT-M Have an S-CDWT of about 50 g / in or less.

Dispersion

Preliminary work to measure the dispersion of a web that has been dried or pre-soaked often depends on systems in which the web is exposed to shear forces in water, such as measuring the time the web decomposes during stirring by a mechanical mixer. Continuous exposure to shear forces provides an unrealistic and overly optimistic test for products that are designed to be weakly sheared and flushed in the toilet extremely short. If the product passes through the neck of the toilet and reaches the decay bath, the shear rate may be negligible. In addition, the product may not be sufficiently wetted by water from the toilet body when flushed, and may not have enough time for the wet composition of the product to be replaced by water in the toilet body when instantaneous shearing force is applied. . Thus, a preliminary measurement of the degree of dispersion suggests that the product can be dispersed in practice, suggesting that the product is not very well suited for corruption systems.

For a practical assessment of dispersion, it is believed that a relatively static means is needed to better mimic the low shear forces experienced when the actual product is fully wetted with water in the toilet. Thus, test methods for dispersibility have been developed that do not rely on shear forces and provide an improved method for evaluating the suitability of a product for a decay system. In this method, the tensile strength of the product is measured in its original form, in wet form (described above with the CDWT assay) and after immersion in the second solution for 1 hour (S-CDWT or S-CDWT-M test). . The second solution can be either deionized water to determine the "deionized dispersion" value or hard water to determine the "hard water dispersion" value (according to the S-CDWT-M test). In either case, the degree of dispersion is defined as (1. 1 cross-sectional wet tensile strength / first wet cross-sectional tensile strength in the second solution) * 100%. Thus, after 1 hour immersion in hard water, if the pre-soaked wipe loses its CD wet tensile strength by 75%, the hard water dispersion is (1-0.25) * 100% = 75%. The article of the invention may have a deionized dispersion of at least 80%, more specifically at least 90%, more specifically at least 95%, and may also have a deionized dispersion of about 100%. The article of the invention may have a hard water dispersion of at least 70%, more specifically at least 80%, more specifically at least about 90%, and may also have a deionized dispersion of about 100%.

How to Make Wet Wipes

The pre-wet wipes of the present invention can be made in a number of ways. In one embodiment, the ion sensitive polymer composition is applied to the fibrous substrate as part of an aqueous solution or suspension, where subsequent drying is required to remove water and promote bonding of the fibers. In particular, upon drying, the binder migrates to the intersection of the fibers and is activated as a binder in this area, providing satisfactory strength to the substrate. For example, the following steps can be applied:

1. Providing a strongly unbound absorbent substrate (eg, unbound arate, tissue web, carded web, baffle pulp, etc.).

2. Applying the ion sensitive polymer composition to the substrate, generally in the form of an accessor, suspension or foam.

3. Applying the cobinder polymer to the substrate.

4. Drying the substrate to promote binding of the substrate.

The substrate may be dried such that the peak substrate temperature does not exceed 160 ° C, or 140 ° C, or 120 ° C, 110 ° C, or 100 ° C. In one embodiment, the substrate temperature does not exceed 80 ° C or 60 ° C.

5. Applying the wetting composition to the substrate.

6. Arranging the wet substrate in roll form or stack and packaging the product.

Application of the co-binder composition may be carried out simultaneously with the binder composition by premixing with the binder composition, or the co-bond polymer may be added before or after the binder is applied. The other steps are preferably performed in the order indicated above.

Application of the ion sensitive polymer composition to the substrate can be accomplished by spraying means; Foam applications; Impregnation in solution bath; Curtain coating; Metering by coating and coiling rods; Passage of the substrate through the flooded nip; Contact with a pre-weighed soak roll coated with a binder composition; Compressing the substrate against a deformable carrier containing an ion-sensitive polymer composition such as a sponge or felt to affect delivery to the substrate; Printing or flexographic printing such as gravure, inkjet; And any other method known in the art.

In the use of a foam to apply the binder or co-binder polymer, the mixture is generally foamed with a foaming agent, applied uniformly over the substrate, and then vacuumed to bleed through the substrate. US Patent No. 4,018,647 ("Process for the Impregnation of a Wet Fiber Web with a Heat Sensitized Foamed LatexBinder", April 19, 1999) Any known foam application method can be used, including the method of. Wittsma may be thermally sensitized by the addition of a heat sensitive agent, such as functional siloxane compounds, including siloxane oxyalkylene block copolymers and organopolysiloxanes. Applicable thermal agents and their use as latex sensitizers are described in US Pat. Nos. 3,255,140, 3,255,141, 3,483,240 and 3,484,394, all of which are incorporated herein by reference. The use of thermal sensitizers is said to produce a very soft and fabric-like product compared to previous methods of applying a foamed latex binder.

The amount of thermal agent that should be added depends, inter alia, on the type of latex used, the desired flocculation temperature, the machine speed and temperature in the drying section of the machine, and generally calculated from the dry weight of the latex as dry material. About 3% by weight. However, more or less than that may be used. The heat sensitive agent may be added in such an amount so that the latex agglomerates well below the boiling point of water, for example in the range of 35 ° C. to 95 ° C., or at a temperature of about 35 ° C. to 65 ° C.

Without wishing to be bound by theory, the drying step after application of the binder solution and before application of the wet composition facilitates efficient use of the binder by increasing the binding force of the fibrous substrate by allowing the binder to reach the fiber turning point as the moisture flies away. do. In other methods, however, the drying step described above is omitted, and after the ion sensitive polymer composition is applied to the substrate, the wet composition is applied without significant intermediate drying steps. In one variant of this method. The ion sensitive polymer composition selectively adheres to the fibers, allowing excess water to be removed in any compaction step without significant loss of binder from the substrate. In other variations, no significant amount of water removal occurs prior to application of the wetting composition. In another method, the ion sensitive polymer composition and the wetting composition are applied simultaneously, optionally adding salts or other activating compounds subsequently to activate or further activate the binder.

The present invention will be further illustrated by the following examples, but these should not be construed as in any way limiting the scope of the invention. Conversely, after reading the technology herein, various other embodiments, modifications, and equivalents thereof will be made available to those skilled in the art without departing from the spirit of the invention and / or the scope of the appended claims. It will be clearly understood that it is a means of suggesting itself.

As used herein, the "thickness" of the web is one of the acrylic plastic discs connected to the spindle of the Mitutoyo Digimatic indicator (Mitsyo Corporation, 3-19, Shiba 5-chome, Shiba, 108, Tokyo, Japan). Measured at 3, this places a net load of 0.05 psi on the sample to be measured. The Mitsyo Digimatik indicator is set to zero scale when the disc stays on a flat surface. When a sample having a size larger than the acrylic disk is placed under the disk, the thickness reading can be obtained from the digital reading of the indicator. The water dispersible substrate of the present invention may have any suitable thickness, such as about 0.1 mm to 5 mm. In the case of a wet wipe, the thickness may range from 0.2 mm to about 1 mm, more specifically from about 0.3 mm to about 0.7 mm. The thickness can be adjusted, for example, by applying compression during or after the web formation, applying the binder or wetting composition and then compressing, or adjusting the winding tension when forming the roll well.

The use of the platen of the present invention to measure thickness provides an average thickness at a visually visible level. The local thickness can vary, especially when the product is embossed or otherwise given a three-dimensional texture.

Example 1

Preparation of Sulfonate Anion Modified Acrylic Acid Terpolymer

43.3 g (0.60 mol) of acrylic acid, 10.7 g (0.052 mol) of AMPS, 35.2 g (0.27 mol) of butyl acrylate and 20 g (0.11 mol) of 2-ethylhexyl acrylate in 55 g of acetone / water (70 / In a mixture of 30). Initiator, 0.51 g (3.1 * 10 mol) of 2,2-azobisisobutyronitrile (AIBN) was dissolved in 20 ml of acetone. The monomer solution was deoxygenated by boiling N ₂ through the solution for 20 minutes. 120 g of acetone water (70/30) mixture was added to a 1000 ml three neck round bottom flask equipped with a condenser, two addition funnels and a magnetic stirrer. The solvent was heated to moderate reflux under nitrogen. The monomer and initiator were added simultaneously over 2 hours from the addition funnel. The polymerization was allowed to occur for an additional 2 hours and at the end of the reaction, the addition funnel and condenser were replaced with a distillation head mechanical stirrer to remove acetone. While maintaining a constant N ₂ stream during distillation, the temperature was increased slightly from about 65 ° C. to about 90 ° C. When distillation was complete, 400 g deionized water was added to reduce the viscosity of the polymer solution. A cloudy but homogeneous solution was obtained.

A total of nine polymers (Samples 1-9) were synthesized using the method described above. 2.1 g (0.052 mol) of NaOH in 20 ml of water was added at room temperature to neutralize the AMPS component in the sample. The compositions of Samples 1-9 are summarized in Table 5 below. All percentages are given in mol%.

TABLE 5 Sulfonate Anion Modified Acrylic Acid Terpolymer

Example 2

Preparation of Acrylic Acid Terpolymer

Acrylic acid terpolymers were prepared using the polymerization process outlined in Example 2 of US Pat. No. 5,312,883. The following monomers were used: The polymer was neutralized with 50 g (0.69 mol) of acrylic acid, 25 g (0.20 mol) of butyl acrylate and 25 g (0.14 mol) of 2-ethylhexyl acrylate, 0.1 mol of sodium hydroxide.

Example 3

Preparation of Ion Sensitive Polymer Formulations

The polymers prepared in Table 5, Sample 9 and Example 2 above were combined with Dur-O-Set RB to form the ion sensitive polymer formulations of the present invention. Polymer formulations were prepared as shown in Table 6 below.

Table 6 Ion Sensitive Polymer Formulations

Example 4

Solubility of Ion Sensitive Polymer Formulations

The sensitivity of the polymer formulation of Example 3 to divalent cations present in hard water was measured. Samples 1-10 of Example 3 were placed in a number of CaCl ₂ solutions containing Ca ²⁺ at concentrations varying from <10-200 ppm. After soaking for 1 hour, the solubility of each polymer was recorded. Solubility results are shown in Table 7 below.

Table 7 Solubility Results

In each case, the film form from the blend containing NaAMPS is more soluble than the film containing the acrylic acid terpolymer, especially as the calcium ion concentration increases.

Example 5

Adhesion testing of polymer formulations with or without crosslinking

For medium test scale tests, airlaid based sheet based pulp (CF 405 or NB 416 pulp from Weyerhaeuser) was used combined with 2-5% of bico fibers. Vico fibers are either Type-255 (activated by KoSa Fiber, Salisbury, NC) with activated polyethylene sheets and polyester cores or Danaklon fibers with polyethylene sheets and polypropylene cores ( FiberVisions, Bard, Denmark). The two types of bico fibers were 2-3 denier and cut to 6 mm length. The binder formulation was applied by spraying 12-15% by weight solution on both sides of the substrate sheet. The strength of the base sheet was reported under various conditions after subtracting the base strength of the web due to the Vico fibers. Table 8 reports the strength (CDWT) of the base sheets containing different formulations in 0.4 wt.% Of NaCl, as well as the strength (S-CDWT) after immersion in distilled water for one hour:

Table 8 Tensile Strength

BW: basis weight

CDWT: Transverse longitudinal wet tensile strength

S-CDWT: CDWT after immersion in deionized water for 1 hour

All of the above codes are better wetted in the first insult compared to the binder formulation containing 100% acrylic acid terpolymer. In addition, binder formulations containing EVA spray better than 100% acrylic acid terpolymers, resulting in improved binder distribution and penetration on the substrate. Importantly, these agents, ie samples 5, 11 and 12, which cannot be crosslinked, have an S-CDWT of less than 30 g / in.

Example 6

A binder formulation having the composition shown in Table 9 below was prepared. A binder formulation of 12 wt% solids was sprayed on both sides of the airlaid web. Airlaid web is based on pulp (CF405 from Warhauser). Table 9 shows the strength (CDWT) of the substrate sheet in 0.9% NaCl solution and the strength after immersion in deionized water for 1 hour (S-CDWT). The impact on strength after aging the sample in the salt solution over a period of up to 16 weeks is shown below. Preservatives, such as Mackstat H66, are added to prevent mycelial growth on the substrate sheet when aged in a salt solution.

Table 9 Tensile Strength of Base Sheet

The results in Table 9 show that the web does not lose its original properties even after excessive aging in the salt solution in use when Dur-O-Set RB was used as EVA. If a crosslinker is present in the EVA, low dispersion occurs after aging the sample for several weeks.

Example 7

Figure 1 also shows the strength properties of NaAMPS modified terpolymers that can be dispersed in hard water (up to 200 ppm Ca ²⁺ / Mg ²⁺ solution). 75 wt% NaAMPS modified acrylic acid terpolymer (SSB) and 25 wt% EVA (Dur-O-Set RB) substrate sheets exhibited good strength in use (1.5% or 4.0% NaCl solution) and were dispersed in very strong water. SSB-4 was dispersed within 10 minutes in hard water. SSB-5 was dispersed within 3 hours in hard water. NaAMPS-SSB is more viscous than Lion-SSB.

The tensile results of Examples 5-7 were obtained with an MTS tensile test fixture, TestTS ™ 3.10 for Windows Software, MTS 500 / S unit (MTS Systems, Research Park, North Carolina). Instead of a typical 3-inch strip for testing, a 1-inch wide strip cut to 6 inches long was used. The gauge length between the rubber coated jaws of the test apparatus was 3 inches. The test was performed at a crosshead speed of 12 in / min. MTS instruments with improved test procedures generally use a 3-inch wide sample and a Thing-Albert tester to give results comparable to the tensile test protocol described above.

Example 8

The addition of the cobinder polymer into the ion sensitive polymer reduces the shear viscosity of the polymer blend as compared to the shear viscosity of the ion sensitive polymer alone. Table 10 illustrates the effect of adding various cobinder polymers to the acrylic acid terpolymer (SSB-2) according to the present invention.

TABLE 10 Effect of adding various cobinder polymers into SSB-2

Polymer blends Viscosity @ 100sec ^-1 18 wt% SSB-2 solids Too high to measure:> 100,000 cps 15% by weight sodium polyacrylate solids (MW = 250,000, 50% neutralization) 10,000 cps 12 wt% pure SSB-2 80 cps 12 weight percent blend of 80 weight parts SSB-2 and 20 weight parts Rhoplex NW 1715K 25 cps 12 weight percent blend of 80 weight parts SSB-2 and 20 weight parts Rovene 28 cps 12 weight percent blend of 80 weight parts SSB-2 and 20 weight parts Dur-O-Set RB 20 cps

Table 10 shows Rhoplex NW 1715K, Rovene 4817 and Dur-O-Set It is shown that the addition of RB reduces the shear viscosity of the SSB-2 acrylic acid terpolymer alone. The decrease in viscosity is not simply due to dilution of SSB-2, but because the addition of sodium polyacrylate caused a significant increase in shear viscosity of SSB-2.

Example 9

Rhoplex NW 1715K, Rovene 4817 and Dur-O-Set A dry solid bar was prepared from RB. A rod was prepared by pouring a significant amount of polymer into a rectangular silicone mold of an open rectangular silicone mold 1 cm wide, 4 cm long and 3 mm deep. The polymer in the mold was then heated to 60 ° C. overnight. Thereafter, the dry polymer in the mold was placed in a vessel containing 30 ml of deionized water at about 23 ° C., and allowed to stand for 1 hour. None of the rods were dispersed in deionized water.

Since, Rhoplex rod samples NW 1715K, Rovene 4817 and Dur-O-Set Prepared from sulfonate anion modified acrylic acid terpolymer (NaAMPS + SSB) blended separately with RB. The polymer blend was prepared from 75 wt% sulfonate anion modified acrylic acid terpolymer and 25 wt% cobinder polymer. Bar samples were prepared in the same manner as described above. The rod sample was then added to deionized water. Each rod sample was prepared from the following polymer blends, namely NaAMPS + SSB / Rhoplex NW 1715K, NaAMPS + SSB / Rovene 4817 and NaAMPS + SSB / Dur-O-Set RB dispersed in deionized water within 1 hour.

Example 10

Substrates in the form of airlaid webs were prepared on a commercial airlaid machine 66.5 inches wide. A substrate having a basis weight of about 60 gsm was prepared using a DanWeb airlaid molding machine with two molding machine heads. Wehrhauser CF405 bleached softwood kraft fiber in pulp sheet foam was used and fiberized in a hammer mill and then formed into an airlaid web on a wire traveling at a speed of 200 to 300 feet / minute. A heated compaction roller is used to increase the density of the newly formed web and transfer it to the second wire, where the second heating compaction roll adds an estimated 5% moisture level just before the web further increases the density of the web. The web was soaked using an automated water sprayer to apply. The web was then transferred to an oven wire, sprayed on top using an ion sensitive polymer formulation on the exposed surface of the web, and 10% ion sensitive polymer formulation solids applied to the dry fiber weight of the web.

The ion sensitive polymer formulation mixture comprises water as a carrier with 12% binder solids, wherein the binder is 75% SSB-4 as the ion sensitive polymer formulation and 25% Rhoplex NW-1715K latex emulsion (Roam and Haas Corporation) was contained as the cobinder polymer.

Spray the Quick Veejet One of a series of nozzles was applied using nozzle No. 730077 (Spraying Systems Co., Wheaton, Ill.) Operating at 95 psi. The spray boom on the web provided 13, such as a nozzle of 8 inches, center 5.5 inches, from tip to wire. This arrangement provides 100% overlap of the spray cone for the ion sensitive polymer formulation of this test.

After the web was applied, it was transferred into an oven with airflow at about 225 ° C. The web is then transferred to the bottom of the other oven wire and then onto another spray boom, where more ionic sensitive polymer formulation solution is applied to the bottom of the web to add an additional 10% by weight of solids to the dry fiber weight of the web. Was applied. The web was then penetrated into two successive drying units where flow through drying occurred using air at about 225 ° C. The pressure difference across the web was about 10 inches of water height. From the first to the third, the three drying sections were about 9, 10 and 6 feet in length, respectively.

The thickness of the web after drying was 1.14 mm (this value can vary depending on the fiber, basis weight, etc., as other physical properties reported herein). The longitudinal dry tensile (MDDT) strength of the web was measured at 4.59 kg / 3 in. The transverse dry tensile (CDDT) strength of the web was measured to be 3.82 kg / 3 in. And CD strength of 8.98%.

The dried and treated web was then cut to 60 inches wide, wound, cut into 4 inches wide rolls, and then made into a tireless roll suitable for treatment with the wet composition and use as a pre-soaked bathroom wipe. The wet composition was evenly sprayed on one side of the 4 inch wide web before winding the web to a size suitable for use. The wet composition was 4 wt% NaCl in deionized water.

The transverse wet tension (CDWT) at 4 wt% saline was measured at 0.76 kg / 3 in. The immersed CDWT strength was virtually zero, like the immersed CD tension, meaning that the sheet was completely dispersible.

Example 11

The sheet formed was the same as the sheet of Example 10 except that the fibers in the airlaid web were 75% softwood kraft and 25% PET fibers. The thickness of the web after drying was 1.35 mm. The lateral dry tensile (MDDT) strength of the web was measured at 3.87 kg / 3 in. The lateral dry tensile (CDDT) strength of the web had a CD tension of 11.31% and was determined to be 2.84 kg / 3 in. The longitudinal wet tension (CDWT) at 4% saline was determined to be 0.82 kg / 3 in. The immersed CDWT strength was virtually zero as in the immersed CD tension.

Example 12

Rovene latex emulsion was used as the cobinder polymer and a further example was performed according to Example 10 except that the basis weight and fiber composition were changed as shown in Table 11. The immersed CDWT results were all zero, indicating a complete loss of tensile strength. Other results are shown in Table 11, where pulp / PET represents the ratio of softwood to synthetic fibers in the substrate, BW is the basis weight in gsm, TH is the thickness in mm, and S-CDWT-M is 2 1 hour immersion CD wet tensile test on samples immersed in water containing: 1 ratio of 200 ppm Ca ²⁺ / Mg ²⁺ .

TABLE 11 Measurement of Examples 3A-3F

The non-zero S-CDWT-M value (wet tensile immersed in hard water) was not zero in both experiments with 25% PET fiber, suggesting that large amounts of synthetic fiber may begin to impair water dispersibility. .

Example 13

Modified elites where the cobinder polymer is substantially free of crosslinkers (Elite Wet wipes were prepared in the same manner as in Example 10 except that it was a latex emulsion (manufactured by National Starch). The basis weight of the web is 61.35, the thickness is 1.21mm, the MDDT is 5.09kg / 3-in, the MD tension is 7.89%, the CDDT is 3.90kg / 3-in, the CD tension is 9.50%, and the CDWT is 0.78kg in 4% saline. / 3-in, CDWT tensile strength was 32.96%, residual strength after 1 hour in deionized water (S-CDWT) and hard water (S-CDWT-M) was 0kg / 3-in.

Example 14

Particulate addition

A pre-wet wipe comprising the base sheet of Example 10 was prepared using a wet composition comprising a particulate slurry. Particulates were selected from the following products sold by Presperse, Inc. (Pitskataway, NJ).

TABLE 12 Preferred Inc. Fine Particles Selected for Use in Pre-Wet Wet Wipes

product name Composition Characteristic MCP-45 Mica and Polymethyl Methacrylate Fine powder, plate coated with microparticles, 13-17 micron Cicada SL-012 98% Mica, 2% Meticon Fine white powder, hydrophobic surface, 2-10 micron Rose Talc talc White powder, 10-12 micron Permethyl 104A Iso-octahexacontane (polyisobutene) Cashmere K-II Mica (97%), Silica Beads (3%), 0.3 Micron Fine white powder, plate coated with microparticles, 10-14 micron Synthetic FNK-100 Synthetic Fluoropogite Fine powder, 10-15 micron Gang's pearl GMX-0610 Methyl Methacrylate Higher Polymer Spherical powder, 4.5-8.5 micron Gang's pearl GS-0605 Styrene / Divinylbenzene Copolymer White powder, 4.5-8.5 micron Gang's pearl PS-8F Styrene / Divinylbenzene Copolymer 0.4 micron Speron N-2000 Amorphous silica White powder, 2-15 micron, less oil absorption Speron L-1500 Amorphous silica White powder, 3-15 micron, many oil absorption

For each particle type in Table 12, batches of five 1000-grams of wet composition were prepared using particle concentrations of 0.5%, 1%, 2%, 5% and 10% by weight. Each batch was prepared by adding the appropriate amount of deionized and filtered water to a 1.15-liter beaker (in five batches, the amounts of water were 926.3g, 921,3g, 911g, 881g and 831g, respectively). The contents in the vessel were agitated with a 2.5-inch magnetic stir bar and placed on a Thermomolyne Cimarec 2 stirrer to set the stirring speed to the maximum to provide a strong central vortex in each of the five vessels. Each batch consisted of 4 weight percent sodium chloride added in water with 40 g of salt; 1 wt% (10 g) Amisoft ECS22-P acylglutamate surfactant (Ajinomoto, Tokyo, Japan); 0.5% by weight (5 g) of DC silicone emulsion (Dow Corning) added in brine and surfactant; 1 wt% (10 g) of Macstat H 66 preservative (McIntyre Group, Chicago, Illinois; and first mixed into 0.25 wt% (2.5 g) of Polysorbate 20, followed by 0.05 wt% (0.5 g) of aroma mixed into a solution comprising, and each powder amount (0.5 to 10 wt% or 5 g to 100 g) .The powder was added into the solution with stirring and allowed to wet, Suspended over a period of about 30 minutes after the addition of the powder Some manual stirring was required to facilitate the mixing of some powders As soon as the powder was dispersed in the liquid, malic acid prepared at a concentration of 50% by weight in water was added. The pH was adjusted to 5.0 by addition, pH was measured using a Cole Parmer Model 59002-00 pH / mV / ° C meter with model 59002-72KK8 electrodes.

Each particulate suspension was then added to a dry airlaid basesheet treated with NaAMPS binder and co-binder polymer according to Example 13. The level of addition applied by spray on one side of the web was 200%. The wet web was then sealed in plastic and left overnight. Testing of pre-wet wipes treated with a particulate suspension, such as a wet composition, revealed that the particulates generally remained in the wet wipes without the need for additional thickening agents or polymeric preservative aids. For example, squeezing a pre-soaked wipe produced a mostly clear liquid that was substantially free of apparent particulates, as opposed to the milky suspension used to wet the wipe. In general, no visible residue remained on the hand using the wipe. In addition, particulates have generally been improved in impermeability and have been shown to provide a slight improvement in tactile properties (reduced stickiness, improved rheological touch).

Example 15

The role of the ungelled starch particles in the wetting composition of the present invention has been studied as a means of reducing the stickiness of the wipes previously wetted and improving the surface feel. Five wet compositions containing tapioca starch were prepared according to the formulation of Table 13. The softwood airlaid web according to Example 10 was moistened with a wet composition with an addition level of 300% (QS means "sufficient amount" to achieve the desired pH).

TABLE 13Formulations for Five Wet Compositions Containing Starch

Water layer A B C D E Water (tap) 76.9 71.9 68.9 66.9 96.45 Laponite XLS 2 2 2 2 Phospholipid CDM 0.5 Malic acid (50% solution), pH 4 7 7 7 7 Tapioca 28-1810 10 15 18 20 DC 1784 One One One One To Dragoco 0/708768 0.1 0.1 0.1 0.1 0.05 Max Stat H 66 0.5 0.5 0.5 0.5 0.5 Sodium chloride 1.5 1.5 1.5 1.5 1.5 McCalm 2C One One One One One Malic acid (50% solution), pH 4 QS QS QS QS QS

Pre-soaked wipes containing starch exhibited reduced stickiness when handled by human hands compared to pre-wetted wipes containing no starch. In addition, the wipe containing starch felt more soft.

Example 16

Additional pre-wet wipes were prepared using the wet compositions shown in Table 14, one of which contained starch as an additive and the other containing plant components as an additive. The wet composition was added in an airlaid fibrous substrate containing an ion sensitive binder. The wet composition was added at addition levels of 300% and 200% by weight, respectively.

Table 14 Formulations for Two Wet Compositions

code Starch Plant composition Formulation # One 2 Raw material Water layer Water (tap) 61.4 95.45 Laponite XLS 2 Phospholipid CDM 0.5 Malic acid (50% solution), pH 4 7 Tapioca 28-1810 25 DC 1784 One 0.5 To Dragoco 0/708768 0.1 0.05 Maxstart H 66 One 0.5 Sodium chloride 1.5 1.5 McCalm 2C One Malic acid (50% solution), pH 4 QS QS CS-22 0.5 Bite G 0.5 Location hazel 0.5 100 100 Final pH Addition solution 300% 200%

Example 17

Binder details

At the mole% and mole molecular weights shown in Table 15, various ion sensitive binders containing acrylic acid (AA), butacrylic acid (BA), 2-ethylhexyl-acrylic acid and AMPS were prepared.

Table 15 Ion-Sensitive Binders Containing AMPS

These binders were prepared according to the method of Example 1, but scaled up to a batch process capable of producing hundreds of gallons per batch.

Example 18

Typical wetting solution

A wet composition was prepared by mixing the following ingredients in accordance with the following specific weight percent: 92.88 wt% deionized water, 4 wt% NaCl, 1 wt% Maxstat H-66 preservative (McIntire Group, Chicago, Illinois) ), 1% by weight of CS22 acyl glutamate anionic surfactant (Amisoft Corporation, Tokyo, Japan), 0.5% by weight of DC 1785 silicone emulsion (Dow Corning), 0.25% by weight of Soluran L-575 (PEG-75 lanolin) , Available from Amercho, a subsidiary of Union Carbide), 0.05% by weight of Dragoco direction 0/708768 (Dragoco SA, Cuautitlan, Mexico DF), 0.25% by weight Polysorbate 20 and about 0.07% by weight of 50% by weight malic acid solution (pH 5.0).

Example 19

Treated substrate

Airlaid substrates were prepared using the apparatus described in Example 10. The basis weight was 65 gsm and the fibers were 100% Wehrhauser CF405 bleached softwood kraft pulp. The binder solution contained 12.8 wt% binder solids, 75 wt% of which is SSB code H of Table 15, and 25 wt% of Dur-O-Set RB latex co-binder (National Starch). The binder solution was sprayed onto the web using a dryer with an air temperature of 215 ° C. in all three oven sections as described in Example 1.

Example 20

Treated substrate

An airlaid substrate was prepared according to Example 10 except that the basis weight was 63 gsm and the oven temperature was 227 ° C. Reel speed was 197 fpm. The thickness of the dried web was 1.30 mm.

MDDT was 5.55kg / 3-in, CCDT was 4.83kg / 3-in, CDWT (in 4% NaCl solution) was 1.07kg / 3-in, and S-CDWT was S-CDWT-M (1 hour immersion test) As in 0kg / 3-in.

A portion of the dry web was cut off to a width of 4.25-inch and treated with a wet composition of 225% addition level containing no surfactant and containing 4% NaCl in deionized water. The wetted web was punched using a porous-knife operating at 0.070 inches deep, punched at 4.5 inch intervals. The perforated web was rolled into a tireless roll with 100 perforated sheets per roll (approximately 37.5 feet per roll) and placed in a white plastic cartridge for later use in a pre-wet wipe dispenser.

Example 21

A portion of the dried and treated web of Example 20 was moistened using the wet composition of Example 18 and converted to perforated roll form for use as a pre-wet wipe dispensed from a bathroom dispenser.

Comparative Example 22

A typical, sticky airlaid substrate having a basis weight of 60.1 gsm was produced using the method described in Example 10. Dur-O-Set E-646 (National Starch) was used with wood pulp (CF405). The substrate was wetted with 4% NaCl solution and tested using the described method. The binder was a fully self-crosslinking Dur-O-Set E-646 compound; No salt sensitive binder was applied. Binder solid weight was 17% of substrate weight. The dry thickness of the web was 1.4 mm, the CDWT value was 1.3 kg / 3-in, the S-CDWT was 1.2 kg and the S_CSWT-M was 1.15 kg, indicating that the web maintained almost all its strength after immersion, Crosslinked latex provided most of the tensile strength of the web, suggesting that the latex bond was not substantially weakened in water.

Example 23

Various binder / co-binder combinations were prepared using the salt-sensitive binders of Table 15 and co-bonds as shown in Table 16, which do not crosslink themselves, as described below.

Table 16 Latex Co-Bonder Not Self-crosslinking

Cobinder ID Cobinder Manufacturer One Dur-O-Set RB National Starch 2 Rhoplex NW-1715K Rome and Haas 3 Rovene 4817 Malad Creek

Using the method described in Example 10, airlaid substrates were prepared from bleached kraft fibers. Substrates were wetted with 4% NaCl solution and tested using the described method. All substrates contained wood pulp (CF405) and binder. The results are shown in Table 17, where the binder mixture consistently contained 75% salt sensitive binder selected from Table 15 and 25% co-binder selected from Table 16. Binder / Co-Binder columns refer to the binder and co-binder listed in Tables 15 and 16, respectively. For example, "A / l" refers to a mixture of SSB code A of Table 15 and co-binders of Table 16.

Table 17 Tensile Data for Various Binder Systems

As shown in Table 17, almost all of the substrates lost a tensile strength of 80% or more after immersion in deionized water for 1 hour (S-CDWT). The substrate lost strength of 60% or more after immersion in 200 ppm of divalent cation solution (S-CDWT-M) for 1 hour. In particular, for the tests shown in Table 17, the samples lost their strength completely within 1 hour in a 200 ppm solution when the salt-sensitive binder had a molecular weight of less than 1.2 million. After 3 hours immersion in 200 ppm divalent cation solution, high molecular weight SSBs generally lost most of their strength but still retained tensile strength as a non-agent.

As a comparison, Comparative Example 22 lost less than 15% of its strength after immersion in deionized water or 200 ppm of divalent ion solution for 1 hour. All substrates of Table 17 lost more tensile strength than Comparative Example 22 upon immersion.

Example 24

The different cobinders of Table 16 were blended with the salt sensitive binder code F of Table 15. The binder blend was then applied using the method described in Example 10 to produce the airlaid substrates described in Table 18. In each case, 20% binder solids were applied to the substrate in a blend of 75% SSB / 25% cobinder.

Table 18 Tensile data for various cobinder systems

Under similar test conditions, all three cobinders are run comparable. All substrates lost their tensile strength (S-CDWT-M) in 200 ppm of divalent cations regardless of the cobinder type.

Example 25

The peel force required to release the product from the outer layer of the tireless roll of pre-wet wipes suitable for use as a wet toilet paper product was measured. The product was prepared according to Example 10 using a wet composition addition level of 200%. Cut dry web to 4.25 inches wide and wet composition at 200% addition level containing 4% NaCl in deionized water with surfactants, silicones and lanolin described in Table 19 for wet compositions Q, R and S Treated with. The wet web was punched with a porous knife to punch every 4.5 inches. The perforated web was rolled into a tireless roll with 100 porous sheets per roll (about 37.5 feet per roll) and sealed in a plastic cartridge for subsequent use in a dispenser for pre-wet wipes.

Table 19 Other Additives in Three Wet Compositions

solution Silicone emulsion lanolin Acyl Glutamate Surfactant Q 0.50% 0.25% CS22 R 1.00% 0.25% ECS 22P S 1.00% 0% ECS 22P

The roll was placed freely in a plastic tube with a round ribbed bottom that held the roll in place with minimal friction when the roll was pulled up vertically towards the end of the roll. Adjacent layers were attached to each other to require a constant force to separate the layers. As partly evidenced by the angle between the web and the roll upon separation, the required peel force was less than the weight of the roll and appeared to substantially exceed the frictional resistance provided by the tub as the roll rotates. In the absence of peeling force, the angle between the web pulled up upon separation and the line perpendicular to the roll will be 90 degrees, but when the wet roll is unwound with a salt-sensitive binder, the angle is substantially less than 90 degrees to separate the web. Provide peel force.

Peel force was measured using an MTS Sintech 1 / G tester equipped with TestWorks 3.10 software. All tests were performed in a suitable laboratory under Tappi standard conditions. A 4.5 inch wide clamp with a rubber surface holds the end of the roll, and if the web does not have peeling force to cover part of the roll and move it away from the vertical, the end of the roll will remain vertical when it is released from the roll. Place the roll directly under the clamp. The clamp was coupled to a crosshead that pulled the tissue at a rate of 100 cm / min. Peel force was measured with a 50 N load meter. The average load for pulling 18 sheets from the roll was recorded averaging three tests on four separate sheets and two tests on five separate sheets, respectively. Only the first 18 sheets of roll were used in the measurement. The average peel force (total average obtained from a total of 36 sheets) for two rolls for each condition is reported in Table 20 below.

TABLE 20 Peel force to release web from wound wet rolls (gram)

Peel force for rolls having a width of 7 to 15 cm (roll width tested in Table 20 is 10.8 cm) is preferably less than 500 g, more specifically less than 300 g, more specifically less than about 200 g, even more specifically Is less than about 160 g, most specifically less than about 120 g, with an exemplary range of about 50 g to about 350 g, or about 80 g to about 200 g. More generally, the peel force per 4 inch width of the wet roll can be any range of values mentioned above.

Example 26

Additional samples were prepared according to Example 24 above, except for 15 wt% fiber blend consisting of 6 mm corrugated PET fibers (KoSa). The different cobinders of Table 16 were blended with the salt sensitive binder code F of Table 15. The binder blend was then applied using the method described in Example 10 to produce an airlaid substrate having the properties described in Table 21. In each case, 20% binder solids were applied to the substrate in a blend of 75% SSB / 25% cobinder. The properties of these substrates were measured after wetting with 4% NaCl solution. All three of these co-binders perform as comparable. Regardless of the cobinder type, all substrates lost their tensile strength in 200 ppm divalent cation solution. Compared to the comparative results of Example 24, the incorporation of synthetic fibers imparts a slight or no increase in strength (CDWT) and a low increase in dry bulk.

Table 21 Data on substrates containing PET fibers and various cobinders

Example 27

A further example was performed according to example 26, while increasing the amount of synthetic fibers added to the fiber blend. Either 6 mm pleated PET fibers (KoSa) or 6 mm, pleated 2.4 dtex Lyocell fibers were used as shown in Table 22 below. The binder blend was a constant blend of 75% SSB and 25% cobinder.

Table 22 Data on substrates containing PET fibers and various cobinders

Non-zero immersed CDWT in 200 ppm divalent cation was not zero for a test combination containing 25% synthetic fiber (PET or Lyocell), suggesting that high amounts may begin to drop water dispersion.

Example 28

The substrates shown in Table 23 were all prepared according to the method of Example 10 and according to the method described in Example 23. All substrates in Table 23 were formed from airlaid pulp (CF405). All binder blends were 75% SSB and 25% cobinder. The thickness of the sheet was adjusted by adjusting the level of web compression by the two compression rolls before the primary spray application of the binder. SSB codes O and Q of Table 15 were used.

Table 23 Data on substrates containing PET fibers and various cobinders

Compression of the dry web before binder application appears to be able to significantly increase the final sheet web strength without compromising the degree of dispersion. This unexpected level of strength increase enables even wet tension to be achieved in various combinations, including a reduction in basis weight and / or a reduction in% binder in the sheet.

Example 29

All substrates were prepared according to the method described in Example 27. All substrates consisted of the fiber blends described in Table 24 containing Dur-O-Set RB acting as a binder and co-binder in 20% of the sheets. Synthetic fibers were pleated and either 6 mm PET (KoSa) or 6 or 8 mm Lyocell (Accordis) with 1.7 or 2.4 dtex.

TABLE 24 Data on Substrates Containing Various Fibers and Binders

The examples in Table 24 suggest that the synthetic fiber length, SSB molecular weight and web compression during the combination can affect the degree of dispersion of the product as indicated by the S-CDWT-M value. All substrates composed of 6 mm or 8 mm synthetic fibers could be dispersed in low molecular weight SSB. As the molecular weight increased, 8 mm Lyocell substrate began to maintain some of its strength after immersion in divalent cation solution for 1 hour. However, this substrate was dispersed in DI water. In addition, increasing the density of the dry web prior to binder application can affect the dispersion of synthetic fibers containing substrates (codes 3015 and 3016). Both codes 3015 and 3016 were completely dispersed in DI water. Sheet dispersion can be adjusted by selecting low molecular weight SSBs as well as densifying synthetic fibers and dry webs.

Example 30

The substrates described in Table 25 were prepared, wetted with 4% NaCl solution and tested according to the method described in Example 29. Each substrate consisted of 20% binder containing the fiber blends described in Table 25 and the SSB / co-binder blends described. Dur-O-Set RB was the cobinder used in all the samples listed in Table 25. All cords used 100% softwood fibers except the last cord 2813 (consisting of 15% PET fiber, a 6mm corrugated fiber purchased from Kosa). The basis weight was generally kept constant at about 60 gsm. The thickness of the airlaid web was adjusted by adjusting the web compression level by two compression rolls prior to the primary spray application of the binder. The dry SD lecture of the selected substrates in Table 25 was measured using a handle-o-meter and recorded as lecture.

Table 25 Data for Substrates Containing Various Binder Blends

When the percentage of salt sensitive binder in the blend is reduced from 100% to 55%, there is only a minor decrease in CDWT in a constant dry bulk. In the composition of 65% salt sensitive binder in the binder blend, the substrate begins to retain a significant amount of its wet strength after immersion in 200 ppm of divalent cation solution for 1 hour. After increasing the density of the web before reducing the first binder and reducing the% of the salt-sensitive binder to 65% or less, after 1 hour of soaking in DI or 200 ppm of divalent cation solution compared to the same composition in high dry bulk Maintain a large amount of strength. These examples suggest that increasing the binder content with or without further densification of the web may begin to impair the dispersion of the substrate.

In addition, the results in Table 25 show that a significant CDWT increases when the thickness of the dry web is compressed before binder application. Codes 3007 to 3010 show that CDWT increases with decreasing dry bulk content at constant binder conditions without loss of substrate dispersion. Based on the handle-O-measurement results (lecture intensity), the CD yield of the substrate appears to decrease as the percentage of salt sensitive binder in the blend decreases.

Example 31

The substrates described in Table 26 were prepared following the methods described in Examples 10 and 23. Each substrate contained pulp (CF405) and 20% binder. The binder contained the SSB / cobinder blends given in Table 26. Dur-O-Set RB was a cobinder. The substrate was converted to roll form and wetted with solution Q (solution D) in Table 19. Determination of the peel force required to dislodge the product from the outer layer of the tireless roll of the wipe previously wetted was performed according to the method described in Example 25. The results of these tests are reported in Table 26 below.

TABLE 26 Peel force results for tireless rolls

In this case, the percent reduction of the salt sensitive binder in the blend reduced the peel force.

Example 32

In accordance with the information in Table 27 below, samples were prepared as in Example 10 using SSB binders (see Table 15) and Dur-O-Set RB co-bonders (co-bonders in Table 16) of 75/25. The tensile results in Table 27 show good dispersion throughout the range of product conditions.

Table 27 Tensile Results for Range of Binder and Substrate Sheet Properties

The samples reported in Table 27 specify part of the range of binder content, basis weight and web thickness from which dispersible substrates can be made.

Example 33

Samples were generally prepared as in Example 10 using a blend of 75/25 SSB binder (see Table 15) and co-binder (see Table 16) as shown in Table 28. All substrates contain 6 mm pleated, 2.4 dtex Lyocell (Accordis) in 85% softwood pulp (CF405) and 15% fiber blend. All substrates consist of 19% binder and 81% binder blend.

Table 28 Tension Results for Binder and Substrate Sheet Property Ranges

In Table 28, all samples lost more than 75% of their wet strength after immersion (S-CDWT) for 1 hour in 200 ppm divalent ionic solution. The main difference between these samples is the SSB composition as shown in Table 15. The salt sensitive binders L and E have the same composition but different molecular weights compared to the salt sensitive binders W and AB (Table 15). Salt sensitive binders W and AB have the same composition but different molecular weights. W / 1- and AB / 2-treated substrates appear to be less dispersed than L / 1- and E / 2-treated substrates independently of the cobinder. Reduction of the salt sensitive binder molecular weight can be used to make the substrate more dispersed as shown in Substrate AB / 1. Alternatively, variations in the salt sensitive binder composition can be used to make the substrate more dispersed as indicated by L / 1 and E / 2. Thus, blends that can be completely dispersed can be prepared by modifying the molecular composition of the salt-sensitive binder or its molecular weight. Alternatively, blends that can be fully dispersed, such as shown by substrates AB / 2 and AB / 1, can be prepared by selecting other cobinder compounds that are more compatible with the salt sensitive binder.

Example 34

A latex emulsion containing about 6% NMA crosslinker, AirFlex 105 (Air Products, Allentown, Pennsylvania) was mixed at a ratio of SSB code H in Table 15, 75 parts SSB, and 25 parts latex solid, It was cast out of eight rods with a volume of 1 cm × 4 cm × 3 mm as described in Example 9. Four bars were prepared by drying in air at 60 ° C. and the other four bars were dried at 167 ° C. for 3 hours. Thereafter, two bars from each set were placed in 30 ml of 4% NaCl solution and allowed to stand for 1 hour, after which the solubility was measured with a hydrometer. The rods from both sets (2 dry conditions) were essentially totally insoluble in the saline solution. The remaining rods from each set were placed in 30 ml of hard water at about 23 ° C. containing 200 ppm of calcium and magnesium ions in a 2: 1 ratio. The two rods, dried at 167 ° C. and placed in hard water, were essentially totally insoluble (0% solubility). The two rods dried at 60 ° C. and placed in hard water were 54% and 53% solubility, respectively, with unexpectedly low solubility, considering that the latex should not be substantially crosslinked to dry at this temperature. However, when the latex is mixed with SSB, some agglomeration occurs, which suggests a problem of possible compatibility between the two mixtures, so that the solubility may be impaired or some aggregated particles may not pass through the filter paper. In addition, some of the NMA crosslinkers in Airflex latex have been able to promote crosslinking or gelling of the blends. More suitable latex emulsions provide higher solubility, but also relatively low co-bonders in crosslinkers (eg, less than 6%, specifically less than 2%, more specifically less than 1%, and most specifically 0.3% by weight of solids). Below) may be useful to maintain high solubility of the dry polymer blend.

1 shows tensile results for treated airlaid basesheets where the test was performed in different saline solutions or hard water. The airlaid substrate sheet was prepared according to Example 10 and provided a 20% addition level of the salt sensitive binder composition named Code X, Code Y and Code Z. Code X is 60% acrylic acid, 10.5% 2-ethylhexyl acrylate, 24.5% butyl acrylate and 5% polymerized according to Example 1 having a molecular weight of 1.3 million, corresponding to code B of Table 15 A binder polymer comprising NaAMPS. Code Y is similar but has a molecular weight of about 550,000, which corresponds to code D of Table 15. Code Z is similar but has 62% acrylic acid and 8.5% 2-ethylhexyl acrylate as monomer, having a molecular weight of about 1.2 million corresponding to code G of Table 15. All binders were blended with the Dur-O-Set RB co-binder in a 75:25 ratio. The treated web was dried as in Example 10 and then wetted with 4% or 1.5% NaCl solution. Wet tensile tests were performed according to the CDWT protocol with exceptions as described in Example 5 (eg, using a 1-inch wide strip and MTS tensile tester).

A CD tensile test immersed was performed on a sample prepared with 4% solution. The four columns shown for each code (some of which are not visible due to zero values) correspond to the results obtained from four different tests. The first two columns are the CDWT values for one web of either 4% or 1.5% NaCl solution. The third and fourth columns are the S-CDWT-M (hard water soak) results at 1 and 3 hours for each web soaked with 4% solution.

The results show good wet strength in both 1.5% NaCl and 4% NaCl, good strength loss (100% hard water dispersion) for webs treated with code Y, good strength loss for code Z and still for code X Indicates residual strength present. The comparison of Code X and Code Y suggests that a decrease in molecular weight can promote the degree of dispersion of the salt sensitive binder.

FIG. 2 shows how wet tensile strength (reported in CDWT expressed in grams per 2.54 cm over immersion time) when 68 gsm of softwood airlaid containing an ion sensitive binder is immersed in a solution containing calcium ions. Show if it can change. The wet web was made up of 20% by weight binder containing 85% of SSB-3b acrylic acid based terpolymers from Lion (Tokyo, Japan) and 15% of Dur-O-Set RB (National Starch) co-binder. Prepared. After drying, the web was moistened with a solution containing 0.9% NaCl, 0.5% phospholipid CDW (Mona) and 0.5% Maxstat H-66, which was about 400 g / in (or g / 2.54 cm) wet. Strength is shown. Solution addition was 250% based on the dry weight of the web. The treated web was then immersed in NaCl free water containing 0, 13, 29 and 109 ppm levels of calcium ions, giving four curves for time versus wet tensile strength shown in FIG. At 109 ppm calcium ions there is essentially no loss of strength. An intensity exceeding 100 g / in is maintained in 29 ppm of calcium ions. Even small amounts of calcium ions in water appear to interfere with the dispersion of the web treated with Lion SSB-3b.

FIG. 3 compares two data of the Lion SSB-3b product (labeled code 3300) in FIG. 2 and sulfonated salt sensitive binder blended with Dur-O-Set RB polymer at a ratio of 75/25. The data set labeled Code 2102 refers to a 65 gsm web containing sulfonated salt sensitive binder corresponding to SSB Code H of Table 15. The web was wetted with the solution described in Table 4. Solution addition was 225% based on the dry weight of the web. This binder formulation, when immersed in hard water, exhibits a rapid decrease in phosphorus strength—and thus excellent triggering properties—even at calcium ion concentrations of 257 ppm. Accordingly, the sulfonated salt sensitive binders of the present invention show a dramatic increase in their ability to disperse in hard water compared to conventional acrylic acid based terpolymers.

Tension results for the data in FIGS. 2 and 3 were obtained using an MTS tensile test fixture, MTS 500 / S unit (MTS Systems, Research Park, North Carolina) using Testworks ™ 3.10 for Windows software. Instead of a typical 3-inch strip for testing, a strip cut to 6 inches long by 1-inch wide was used. The gauge length between the rubber coated jaws of the test apparatus was 3 inches. The test was performed at the designated crosshead speed of 12 in / min.

It is to be understood that the above description is directed to certain disclosed embodiments of the invention, and that many modifications or variations are possible within these embodiments without departing from the spirit and scope of the invention as set forth in the appended claims.

Claims (188)

A polymer composition having a wet strength in a neutral salt solution containing at least 1% by weight of a salt comprising at least one monovalent ion, which may be dispersed in hard or soft water, and comprising a salt-sensitive binder and a cobinder. A polymer composition comprising a salt-sensitive binder and a cobinder, insoluble in water that does not contain a sufficient amount of a first salt and soluble in water that contains a second salt that is different from the first salt in a solubilizing amount. An ion sensitive polymer composition comprising an ion sensitive polymer and a cobinder polymer dispersed in the ion sensitive polymer. 4. The polymer composition of claim 3, wherein each of said polymers has a Tg and the Tg of said cobinder polymer is less than the Tg of said ion sensitive polymer. The polymer composition of claim 3, wherein the cobinder polymer is of any type and is present in an amount capable of dispersing the polymer composition. 4. The polymer composition of claim 3, wherein the ion sensitive polymer is a ternary interpolymer prepared from monomers capable of free radical polymerization into ternary interpolymers, wherein the monomers are selected from acrylic acid monomers and alkyl acrylate monomers. The polymer composition of claim 3, wherein the acrylic acid monomer is selected from acrylic acid and methacrylic acid. The polymer composition of claim 6, wherein the alkyl acrylate monomer is selected from acrylic esters and methacrylic esters having 1 to 18 carbon atoms or cycloalkyl groups having 3 to 18 carbon atoms. The polymer composition of claim 6 wherein said acrylic ester monomer is selected from acrylamide and methacrylamide based monomers. The method of claim 6, wherein the acrylic ester monomer is selected from acylamide, N, N-dimethyl acrylamide, N-ethyl acrylamide, N-isopropyl acrylamide and hydroxymethyl acrylamide; N-vinylpyrrolidinone; N-vinylformamide; A polymer composition selected from hydroxyalkyl acrylates and hydroxyalkyl methacrylates. The polymer composition of claim 6 wherein the acrylic ester monomer is selected from hydroxyethyl methacrylate and hydroxyethyl acrylate. 4. The polymer composition of claim 3, wherein the ion sensitive polymer is a ternary interpolymer comprising acrylic acid, butyl acrylate and 2-ethylhexyl acrylate. The polymer composition of claim 3, wherein the cobinder polymer is noncrosslinkable. 4. The polymer composition of claim 3, wherein said cobinder polymer is not water soluble. 4. The polymer composition of claim 3 wherein the cobinder polymer is selected from noncrosslinkable poly (ethylene-vinyl acetate), noncrosslinkable poly (styrene-butadiene) and noncrosslinkable poly (styrene-acrylic). 4. The polymer composition of claim 3, wherein the cobinder polymer is in emulsion form. The polymer composition of claim 3, wherein the cobinder polymer has a molecular weight of about 500,00 to about 200,000,000. 4. The polymer composition of claim 3, wherein the ion sensitive polymer is present in an amount of about 65 to about 75 weight percent, and the cobinder polymer is present in an amount of about 25 to about 35 weight percent. 4. The ion-sensitive polymer of claim 3, wherein the ion-sensitive polymer is insoluble in a neutral salt solution containing at least about 1% by weight of a salt containing at least one monovalent ion and is soluble in water containing at least about 200 ppm of at least one polyvalent ion. Composition. The ion sensitive polymer composition of claim 19 which is soluble in water containing from about 15 ppm to about 200 ppm of at least one polyvalent ion. 20. The ion sensitive polymer composition of claim 19, wherein the ion sensitive polymer composition is soluble in water containing from about 15 ppm to about 150 ppm of at least one polyvalent ion. 20. The ion-sensitive polymer composition of claim 19, wherein the ion sensitive polymer composition is soluble in water containing from about 15 ppm to about 100 ppm of at least one polyvalent ion. 20. The ion-sensitive polymer composition of claim 19, wherein the ion sensitive polymer composition is soluble in water containing from about 15 ppm to about 50 ppm of one or more polyvalent ions. 20. The ion-sensitive polymer composition of claim 19, wherein the ion sensitive polymer composition is soluble in water containing less than about 10 ppm of one or more polyvalent ions. 20. The ion sensitive polymer composition of claim 19, wherein the ion sensitive polymer composition is insoluble in a neutral salt solution containing about 1 to about 5 weight percent salt. 20. The ion sensitive polymer composition of claim 19, wherein the ion sensitive polymer composition is insoluble in a neutral salt solution containing about 1 to about 3 weight percent salt. 20. The ion-sensitive polymer composition of claim 19, wherein said polyvalent ions comprise Ca ²⁺ ions, Mg ²⁺ ions, Zn ²⁺ ions, or a combination thereof. The ion sensitive polymer composition of claim 19, wherein the monovalent ions comprise Na ⁺ ions, Li ⁺ ions, K ⁺ ions, NH ₄ ⁺ ions, or a combination thereof. The ion sensitive polymer composition of claim 3 wherein the ion sensitive polymer comprises a sulfonate anion modified acrylic acid terpolymer. The method of claim 29 wherein the sulfonate anion modified acrylic acid terpolymer is acrylic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid and alkaline earth metals and their organic amine salts, butyl acrylate and 2 An ion-sensitive polymer composition selected from ethylhexyl acrylate. 30. The method of claim 29, wherein the sulfonate anion modified acrylic acid terpolymer is at least about 35 mole percent and less than 80 mole percent acrylic acid, greater than 0 mole percent and up to about 20 mole percent 2-acrylamido-2- From methyl-1-propanesulfonic acid and alkaline earth metals and their organic amine salts, greater than 0 mol% up to about 65 mol% butyl acrylate and greater than 0 mol% up to about 45 mol% up to 2-ethylhexyl acrylate The ion sensitive polymer composition being selected. The method of claim 29, wherein the sulfonate anion-modified acrylic acid terpolymer is at least about 50 mol% and less than 67 mol% acrylic acid, greater than 0 mol% and less than about 10 mol% 2-acrylamido-2- Selected from methyl-1-propanesulfonic acid and alkaline earth metals and their organic amine salts, from about 15 mol% to about 28 mol% butyl acrylate and from about 7 mol% to about 15 mol% 2-ethylhexyl acrylate Phosphorus ion sensitive polymer composition. The method of claim 29, wherein the sulfonate anion modified acrylic acid terpolymer is at least about 57 mol% and less than 66 mol% acrylic acid, from about 1 mol% to about 6 mol% 2-acrylamido-2-methyl -1-propanesulfonic acid and alkaline earth metals and their organic amine salts, from about 15 mol% to about 28 mol% butyl acrylate and from about 7 mol% to about 13 mol% 2-ethylhexyl acrylate Ion Sensitive Polymer Compositions. A sulfonate anion-modified acrylic acid copolymer and a latex, insoluble in a salt solution containing at least about 1% by weight of a salt containing at least one monovalent cation and containing 50 ppm of calcium and magnesium ions in a 2: 1 ratio An ion-sensitive polymer composition soluble in water. 35. The ion sensitive polymer composition of claim 34 wherein said latex is noncrosslinkable. 35. The ion sensitive polymer composition of claim 34 wherein less than 50% of the latex is crosslinked. 35. The ion sensitive polymer composition of claim 34 wherein less than 20% of the latex is crosslinked. 35. The ion sensitive polymer composition of claim 34 wherein said latex comprises a noncrosslinkable poly (ethylene-vinyl acetate). A sulfonate anion-modified acrylic acid copolymer and latex, insoluble in a salt solution containing at least about 1% by weight of a salt containing at least one monovalent cation, containing 100 ppm of calcium and magnesium ions in a 2: 1 ratio An ion sensitive polymer composition soluble in water. A sulfonate anion-modified acrylic acid copolymer and latex, insoluble in a salt solution containing at least about 1% by weight of a salt containing at least one monovalent cation, containing 150 ppm of calcium and magnesium ions in a 2: 1 ratio An ion-sensitive polymer composition soluble in water. A sulfonate anion-modified acrylic acid copolymer and latex, insoluble in a salt solution containing at least about 1% by weight of a salt containing at least one monovalent cation, containing 200 ppm of calcium and magnesium ions in a 2: 1 ratio An ion-sensitive polymer composition soluble in water. 40. The ion-sensitive polymer composition of claim 39, wherein the ion sensitive polymer composition is soluble in water containing from about 15 ppm to about 100 ppm of at least one polyvalent cation. 35. The ion-sensitive polymer composition of claim 34, wherein the ion sensitive polymer composition is soluble in water containing less than about 10 ppm of at least one polyvalent cation. 35. The ion sensitive polymer composition of claim 34, wherein the ion sensitive polymer composition is insoluble in a salt solution containing from about 1% to about 5% by weight salt. 35. The ion sensitive polymer composition of claim 34, wherein the ion sensitive polymer composition is insoluble in a salt solution containing from about 3% to about 5% by weight salt. 35. The ion sensitive polymer composition of claim 34, wherein the ion sensitive polymer composition is insoluble in a salt solution containing about 4% by weight sodium chloride. 35. The ion sensitive polymer composition of claim 34, wherein the ion sensitive polymer composition is insoluble in a salt solution in the pH range of about 3 to about 8. 35. The ion sensitive polymer composition of claim 34, wherein the ion sensitive polymer composition is insoluble in a salt solution in the pH range of about 4 to about 7. 35. The ion sensitive polymer composition of claim 34, wherein the ion sensitive polymer composition is insoluble in a salt solution at pH 5. 35. The ion sensitive polymer composition of claim 34, wherein the salt solution has a pH of about 3.5 to about 7. 35. The ion sensitive polymer composition of claim 34, wherein said salt solution has a pH of 4.2 to 6.1. 35. The ion-sensitive polymer composition of claim 34, wherein said polymer is insoluble in a salt solution containing from about 1% to about 3.0% by weight salt. The ion-sensitive polymer composition of claim 34, wherein the copolymer is prepared by sulfonation of a polymer having a molecular weight greater than about 100,000. 35. The ion-sensitive polymer composition of claim 34, wherein the copolymer is prepared by polymerization of a monomer comprising a sulfonate containing monomer. 35. The ion sensitive polymer composition of claim 34 wherein said copolymer is a ternary interpolymer. The method of claim 34, wherein the sulfonate-containing monomer is acrylamido propanesulfonic acid, 2-methyl-2-propene sulfonic acid, vinyl sulfonic acid, styrene sulfonic acid, 2-sulfopropyl methacrylate and 3-sulfopropyl. Ion-sensitive polymer compositions selected from acrylates and organic or inorganic salts thereof. Salts containing latex and sulfonate anion-modified acrylic acid copolymers prepared noncrosslinked without addition of crosslinkers or dried without substantial crosslinking and containing at least 1% by weight of salts containing at least one monovalent cation An ion-sensitive polymer composition insoluble in solution and soluble in water containing at least 50 ppm of divalent cations. 58. The ion sensitive polymer composition of claim 57 wherein said latex is a noncrosslinkable poly (ethylene-vinyl acetate). 59. The ion sensitive polymer composition of claim 57 wherein the divalent cation comprises Ca ²⁺ ions, Mg ²⁺ ions, Zn ²⁺ ions or a combination thereof. The ion sensitive polymer composition of claim 57, wherein the divalent cation comprises Ca ²⁺ ions and Mg ²⁺ ions in a 2: 1 ratio and wherein the monovalent cation is Na ⁺ . The ion-sensitive polymer composition of claim 57, wherein the monovalent cation comprises Na ⁺ ions, Li ⁺ ions, K ⁺ ions, NH ₄ ⁺ ions, or a combination thereof. 58. The ion sensitive polymer composition of claim 57 wherein the acrylic acid copolymer is a ternary interpolymer prepared from acrylic acid, methacrylic acid or combinations thereof and at least one alkyl acrylate. 63. The method of claim 62 wherein the sulfonate anion modified acrylic acid terpolymer is selected from acrylic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid and alkali metals and organic amine salts thereof, butyl acrylate, and Ion-sensitive polymer composition prepared from 2-ethylhexyl acrylate. 63. The ion sensitive polymer composition of claim 62, wherein the sulfonate anion modified acrylic acid terpolymer is made from acrylic acid, AMPS or NaAMPS, butyl acrylate and 2-ethylhexyl acrylate. 63. The method of claim 62, wherein the sulfonate anion modified acrylic acid terpolymer is at least about 57 mole percent and less than 66 mole percent acrylic acid, from about 1 mole percent to about 6 mole percent AMPS or NaAMPS, from about 15 mole percent Ion-sensitive polymer composition prepared from about 28 mole% butyl acrylate and about 7 mole% to about 13 mole% 2-ethylhexyl acrylate 58. The ion sensitive polymer composition of claim 57 which is an acrylic acid terpolymer. 67. The ion-sensitive polymer composition of claim 66, wherein the acrylic acid terpolymer comprises acrylic acid, methacrylic acid or a combination thereof and at least one alkyl acrylate. 67. The ion sensitive polymer composition of claim 66 wherein the acrylic acid terpolymer is made from acrylic acid, butyl acrylate and 2-ethylhexyl acrylate. 67. The method of claim 66, wherein the acrylic acid terpolymer is at least about 35 mole percent and less than 80 mole percent acrylic acid, greater than 0 mole percent and up to about 65 mole percent butyl acrylate and greater than 0 mole percent and about 45 mole percent An ion-sensitive polymer composition comprising the following 2-ethylhexyl acrylate. 67. The method of claim 66, wherein the acrylic acid terpolymer is at least 50 mol% and less than 67 mol% acrylic acid, from about 15 mol% to about 28 mol% butyl acrylate and from about 7 mol% to about 15 mol% 2 An ion-sensitive polymer composition comprising ethylhexyl acrylate. 67. The method of claim 66, wherein the acrylic acid terpolymer is at least about 57 mole percent and less than 66 mole percent acrylic acid, from about 15 mole percent to about 28 mole percent butyl acrylate and from about 7 mole percent to about 13 mole percent Ion-sensitive polymer composition comprising 2-ethylhexyl acrylate. 59. The ion sensitive polymer composition of claim 57 comprising about 65 to 75 weight percent of the sulfonate anion modified acrylic acid copolymer. 59. The ion sensitive polymer composition of claim 57 comprising about 25 to 35 weight percent of the latex. 59. The ion sensitive polymer composition of claim 57 comprising about 55 to 99 weight percent of the sulfonate anion modified acrylic acid copolymer and about 1 to 45 weight percent of the latex. 58. A binder composition for bonding a fibrous material to a unitary web comprising the ion sensitive polymer composition of claim 57. 58. A binder material comprising the ion sensitive polymer composition of claim 57 and Fibrous material Non-woven comprising a. At least one polyvalent ion, insoluble in a neutral salt solution comprising at least about 0.3% by weight of a salt comprising at least one monovalent ion and an acrylic acid terpolymer interpolymer and non-crosslinkable poly (ethylene-vinyl acetate) Ion-sensitive polymer composition soluble in water containing less than about 10 ppm. 78. The ion sensitive polymer composition of claim 77 insoluble in a neutral solution of monovalent salt containing from about 0.3 to about 5.0 weight percent salt. 78. The ion sensitive polymer composition of claim 77 wherein said polymer is insoluble in a neutral solution of monovalent salt containing from about 0.5 to about 3.0 weight percent salt. 78. The ion sensitive polymer composition of claim 77 wherein the polyvalent ion comprises Ca ²⁺ ions, Mg ²⁺ ions, Zn ²⁺ ions, or a combination thereof. 78. The ion-sensitive polymer composition of claim 77, wherein said monovalent ions comprise Na ⁺ ions, Li ⁺ ions, K ⁺ ions, NH ₄ ⁺ ions, or a combination thereof. 78. The ion-sensitive polymer composition of claim 77, wherein the acrylic acid terpolymer comprises acrylic acid, methacrylic acid or a combination thereof and at least one alkyl acrylate. 78. The ion sensitive polymer composition of claim 77 wherein said acrylic acid terpolymer is made from acrylic acid, butyl acrylate and 2-ethylhexyl acrylate. 78. The method of claim 77, wherein the acrylic acid terpolymer is at least about 35 mole percent and less than 80 mole percent acrylic acid, greater than 0 mole percent and up to about 65 mole percent butyl acrylate and greater than 0 mole percent and about 45 mole percent An ion-sensitive polymer composition comprising the following 2-ethylhexyl acrylate. 78. The method of claim 77, wherein the acrylic acid terpolymer is at least about 50 mole percent and less than 67 mole percent acrylic acid, about 15 mole percent to about 28 mole percent butyl acrylate and about 7 mole percent to about 15 mole percent Ion-sensitive polymer composition comprising 2-ethylhexyl acrylate. 78. The method of claim 77, wherein the acrylic acid terpolymer is at least about 57 mole percent and less than 66 mole percent acrylic acid, about 15 mole percent to about 28 mole percent butyl acrylate and about 7 mole percent to about 13 mole percent Ion-sensitive polymer composition comprising 2-ethylhexyl acrylate. The ion sensitive polymer composition of claim 76 comprising from about 65 to about 75 weight percent acrylic acid terpolymer. 78. The ion sensitive polymer composition of claim 77 comprising about 25 to about 35 weight percent uncrosslinkable poly (ethylene-vinyl acetate). 78. The ion sensitive polymer composition of claim 77 comprising about 1 to about 45 weight percent uncrosslinkable poly (ethylene-vinyl acetate). 78. The method of claim 77, wherein the acrylic acid terpolymer is at least about 57 mole percent and less than 66 mole percent acrylic acid, about 15 mole percent to about 28 mole percent butyl acrylate and about 7 mole percent to about 15 mole percent An ion-sensitive polymer composition comprising 2-ethylhexyl acrylate, present in an amount of about 65 to about 75, and wherein the non-crosslinkable poly (ethylene-vinyl acetate) is present in an amount of about 25 to about 35% by weight. . 78. A binder composition for bonding a fibrous material to an integrated web comprising the ion sensitive polymer composition of claim 77. 78. A binder material comprising the ion sensitive polymer composition of claim 77 and Fibrous material Non-woven comprising a. A salt comprising a first polymer prepared from acrylic acid, butyl acrylate and 2-ethylhexyl acrylate, and a second polymer comprising non-crosslinkable poly (ethylene-vinyl acetate) and comprising at least one monovalent ion. An ion-sensitive polymer composition insoluble in a neutral salt solution containing at least about 0.3% by weight and soluble in water containing less than about 10 ppm of one or more polyvalent ions. 95. The method of claim 93, wherein the first polymer is at least about 35 mole percent and less than 80 mole percent acrylic acid, greater than 0 mole percent up to about 65 mole percent butyl acrylate and greater than 0 mole percent up to about 45 mole percent Ion-sensitive polymer composition comprising 2-ethylhexyl acrylate. 95. The method of claim 93, wherein the first polymer is at least about 50 mol% and less than 67 mol% acrylic acid, about 15 mol% to about 28 mol% butyl acrylate and about 7 mol% to about 15 mol% 2- An ion sensitive polymer composition comprising ethylhexyl acrylate. 95. The composition of claim 93, wherein the first polymer is at least about 57 mol% and less than 66 mol% acrylic acid, about 15 mol% to about 28 mol% butyl acrylate and about 7 mol% to about 13 mol% 2- An ion sensitive polymer composition comprising ethylhexyl acrylate. 95. The ion sensitive polymer composition of claim 93, wherein the second polymer comprises about 25 to about 35 weight percent of noncrosslinkable poly (ethylene-vinyl acetate). 95. The ion sensitive polymer composition of claim 93, wherein the second polymer comprises about 1 to about 45 weight percent of noncrosslinkable poly (ethylene-vinyl acetate). 95. The method of claim 93, wherein the acrylic acid terpolymer is at least about 57 mole percent and less than 66 mole percent acrylic acid, about 15 mole percent to about 28 mole percent butyl acrylate and about 7 mole percent to about 13 mole percent An ionic sensitive polymer comprising 2-ethylhexyl acrylate, wherein the first polymer is present in an amount of about 65 to about 75 mole percent and the second polymer is present in an amount of about 25 to about 35 weight percent Composition. 95. A binder composition for bonding a fibrous material to an integrated web, comprising the ion sensitive polymer composition of claim 93. A binder material comprising the ion sensitive polymer composition of claim 93 and Fibrous material Nonwovens, including At least one salt insoluble in a neutral salt solution containing at least about 0.3% by weight of a salt comprising at least one monovalent ion, comprising mixing an acrylic acid terpolymer and a noncrosslinkable poly (ethylene-vinyl acetate) A method of making an ion sensitive polymer composition that is soluble in water containing less than about 10 ppm of polyvalent ions. 102. The method of claim 102, wherein the acrylic acid terpolymer comprises acrylic acid, methacrylic acid, or a combination thereof, and at least one alkyl acrylate. 107. The method of claim 102, wherein the acrylic acid terpolymer is made from acrylic acid, butyl acrylate and 2-ethylhexyl acrylate. 103. The method of claim 102, wherein the acrylic acid terpolymer is at least about 35 mole percent and less than 80 mole percent acrylic acid, greater than 0 mole percent and up to about 65 mole percent butyl acrylate and greater than 0 mole percent and about 45 mole percent A method comprising the following 2-ethylhexyl acrylate. 102. The method of claim 102, wherein the acrylic acid terpolymer is at least about 50 mole percent and less than 67 mole percent acrylic acid, from about 15 mole percent to about 28 mole percent butyl acrylate and from about 7 mole percent to about 15 mole percent And 2-ethylhexyl acrylate. 103. The method of claim 102, wherein the acrylic acid terpolymer is at least about 57 mole percent and less than 66 mole percent acrylic acid, about 15 mole percent to about 28 mole percent butyl acrylate and about 7 mole percent to about 13 mole percent And 2-ethylhexyl acrylate. 103. The method of claim 102, wherein the weight percent of the acrylic acid terpolymer is about 65 to about 75. 107. The method of claim 102, wherein the noncrosslinkable poly (ethylene-vinyl acetate) is present in about 25 to about 35 weight percent. 107. The method of claim 102, wherein the noncrosslinkable poly (ethylene-vinyl acetate) is present in an amount of about 1 to about 45 weight percent. 103. The method of claim 102, wherein the acrylic acid terpolymer is at least about 57 mole percent and less than 66 mole percent acrylic acid, about 15 mole percent to about 28 mole percent butyl acrylate and about 7 mole percent to about 13 mole percent And 2-ethylhexyl acrylate, present in an amount of about 65 to 75% by weight, and wherein the non-crosslinkable poly (ethylene-vinyl acetate) is present in about 25 to about 35% by weight. A fibrous substrate comprising a fibrous material and a binder composition for bonding the fibrous material to a unitary web, the binder composition comprising an acrylic acid terpolymer and a noncrosslinkable poly (ethylene-vinyl acetate) A fibrous substrate insoluble in a neutral salt solution containing about 0.3% by weight or more of a salt containing the above monovalent ions and soluble in water containing less than about 10 ppm of one or more polyvalent ions. 124. The fibrous substrate of claim 112, wherein the binder composition is soluble in a neutral solution of monovalent salt containing from about 0.3 to about 5.0 weight percent salt. 112. A water dispersible product comprising the fibrous substrate of claim 112. A method of making an ion sensitive polymer composition, comprising dispersing a cobinder polymer in an ion sensitive polymer. 116. The method of claim 115, wherein said polymer composition is insoluble in a neutral salt solution containing at least about 1% by weight of a salt comprising at least one monovalent ion, and in water containing at least about 200 ppm of at least one polyvalent ion. How to be soluble. 116. The method of claim 115, wherein each polymer has a Tg and the Tg of the cobinder polymer is less than the Tg of the ion sensitive polymer. 116. The method of claim 115, wherein the cobinder polymer is of any type and present in an amount capable of dispersing the polymer composition. 116. The method of claim 115, wherein the cobinder polymer is noncrosslinkable. 116. The method of claim 115, wherein the cobinder polymer is not water soluble. 116. The method of claim 115, wherein the cobinder polymer is selected from noncrosslinkable poly (ethylene-vinyl acetate), noncrosslinkable poly (styrene-butadiene), and noncrosslinkable poly (styrene-acrylic). 116. The method of claim 115, wherein the cobinder has a molecular weight of about 500,00 to about 200,000,000. 116. The method of claim 115, wherein the ion sensitive polymer is present in an amount of about 55 to about 99 weight percent and the cobinder polymer is present in an amount of about 1 to about 45 weight percent. 116. The method of claim 115, wherein the ion sensitive polymer is selected from an acrylic acid terpolymer, a sulfonate anion modified acrylic acid terpolymer. 116. The method of claim 115, wherein the ion sensitive polymer is a sulfonate anion modified acrylic acid terpolymer. 126. The method of claim 125, wherein the sulfonate anion modified acrylic acid terpolymer is selected from the group consisting of acrylic acid, methacrylic acid, or a combination thereof; 2-acrylamido-2-methyl-1-propanesulfonic acid and alkaline earth metals and organic amine salts thereof; And one or more alkyl acrylates. 126. The method of claim 125, wherein the sulfonate anion modified acrylic acid terpolymer is made from acrylic acid, AMPS or NaAMPS, butyl acrylate and 2-ethylhexyl acrylate. 116. The method of claim 115, wherein the cobinder polymer is made from noncrosslinkable poly (ethylene-vinyl acetate), noncrosslinkable poly (styrene-butadiene), and noncrosslinkable poly (styrene-acrylic). 116. The method of claim 115, wherein the cobinder polymer is a noncrosslinkable poly (ethylene-vinyl acetate). First and non-crosslinkable poly (ethylene) prepared from acrylic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid and alkaline earth metals and their organic amine salts, butyl acrylate and 2-ethylhexyl acrylate -Vinyl acetate), a non-crosslinkable poly (styrene-butadiene), and a second polymer selected from noncrosslinkable poly (styrene-acrylic) and contain at least about 1% by weight of a salt comprising at least one monovalent ion An ion-sensitive polymer composition that is insoluble in a neutral salt solution and is soluble in water containing at least about 200 ppm of one or more polyvalent ions. 130. A binder composition for bonding a fibrous material to a unitary web, comprising the ion sensitive polymer composition of claim 130. Fibrous material and 130. A binder material comprising the ion sensitive polymer composition of claim 130. Non-woven comprising a. From a first polymer prepared from acrylic acid, butyl acrylate and 2-ethylhexyl acrylate and uncrosslinked poly (ethylene-vinyl acetate), uncrosslinked poly (styrene-butadiene) and uncrosslinked poly (styrene-acrylic) Ions which are selected in the neutral salt solution containing at least about 1% by weight of a salt comprising a second polymer and containing at least one salt containing at least one monovalent ion and are soluble in water containing at least about 200 ppm of at least one polyvalent ion. Sensitive Polymer Composition. 133. A binder composition for bonding a fibrous material to a unitary web, comprising the ion sensitive polymer composition of claim 133. Fibrous material and 134. A binder material comprising the ion sensitive polymer composition of claim 133 Non-woven comprising a. From a first polymer prepared from acrylic acid, butyl acrylate and 2-ethylhexyl acrylate and uncrosslinked poly (ethylene-vinyl acetate), uncrosslinked poly (styrene-butadiene) and uncrosslinked poly (styrene-acrylic) Soluble in water and insoluble in neutral salt solutions containing at least about 1% by weight of salts comprising at least one monovalent ion and mixing up to about 200 ppm of at least one polyvalent ion comprising mixing the selected second polymer. A method of making a phosphorus ion sensitive polymer composition. A fibrous substrate comprising a fibrous material and a binder composition for bonding the fibrous material to a unitary web, the binder composition comprising an ion sensitive polymer and a cobinder polymer dispersed in the ion sensitive polymer and at least one monovalent ion A fibrous substrate insoluble in a neutral salt solution containing at least about 1% by weight of a salt containing and soluble in water containing at least about 200 ppm of at least one polyvalent ion. 138. The fibrous substrate of claim 137, wherein said binder composition is insoluble in a neutral solution of monovalent salt containing from about 1 to about 5.0 weight percent salt. A fibrous substrate comprising a fibrous material and a binder composition for bonding the fibrous material to the integral web, the binder composition comprising at least about 1% by weight of a salt comprising an ion sensitive polymer and containing at least one monovalent ion A fibrous substrate insoluble in a neutral salt solution containing and soluble in water containing about 200 ppm or less of one or more polyvalent ions. 139. The fibrous substrate of claim 139, wherein the binder composition further comprises a cobinder polymer. 139. The fibrous substrate of claim 139, wherein the cobinder polymer is dispersed in a dye-sensitive polymer. A fibrous substrate comprising a fibrous material and a binder composition for bonding the fibrous material to the integral web, the binder composition comprising a sulfonate anion modified acrylic acid terpolymer and a noncrosslinkable poly (ethylene-vinyl acetate) A fibrous substrate comprising at least about 1% by weight of a salt containing at least one monovalent ion and insoluble in a neutral salt solution and soluble in water containing at least about 200 ppm of at least one polyvalent ion. 142. The fibrous substrate of claim 142, wherein the binder composition is soluble in water containing from about 15 ppm to about 200 ppm of one or more polyvalent ions. 142. The fibrous substrate of claim 142, wherein the binder composition is soluble in water containing from about 15 ppm to about 150 ppm of one or more polyvalent ions. 142. The fibrous substrate of claim 142, wherein the binder composition is soluble in water containing from about 15 ppm to about 100 ppm of one or more polyvalent ions. 142. The fibrous substrate of claim 142, wherein the binder composition is soluble in water containing from about 15 ppm to about 50 ppm of one or more polyvalent ions. 142. The fibrous substrate of claim 142, wherein the binder composition is soluble in water containing less than about 10 ppm of one or more polyvalent ions. 142. The fibrous substrate of claim 142, wherein the binder composition is insoluble in a neutral salt solution containing about 1 to about 5 weight percent salt. 142. The fibrous substrate of claim 142, wherein the binder composition is insoluble in a neutral salt solution containing about 1 to about 3 weight percent salt. 142. The fibrous substrate of claim 142, wherein the multivalent ions comprise Ca ²⁺ ions, Mg ²⁺ ions, Zn ²⁺ ions, or a combination thereof. 142. The fibrous substrate of claim 142, wherein the monovalent ions comprise Na ⁺ ions, Li ⁺ ions, K ⁺ ions, NH ₄ ⁺ ions, or a combination thereof. 142. The fibrous substrate of claim 142, wherein the acrylic acid terpolymer comprises at least one of acrylic acid and methacrylic acid and at least one alkyl acrylate. 142. The method of claim 142, wherein the sulfonate anion modified acrylic acid terpolymer is acrylic acid; 2-acrylamido-2-methyl-1-propanesulfonic acid and alkaline earth metals and organic amine salts thereof; Butyl acrylate; And at least four monomers selected from 2-ethylhexyl acrylate. 142. The fibrous substrate of claim 142, wherein the sulfonate anion modified acrylic acid terpolymer is made from four or more monomers selected from acrylic acid, AMPS, NaAMPS, butyl acrylate, and 2-ethylhexyl acrylate. 142. The method of claim 142, wherein the sulfonate anion modified acrylic acid terpolymer is at least about 35 mole percent and less than 80 mole percent acrylic acid, greater than 0 mole percent and up to about 20 mole percent 2-acrylamido-2- Methyl-1-propanesulfonic acid and alkaline earth metals and their organic amine salts, greater than 0 mol% up to about 65 mol% butyl acrylate and greater than 0 mol% up to about 45 mol% up to 2-ethylhexyl acrylate Fibrous base material to contain. 142. The method of claim 142, wherein the sulfonate anion modified acrylic acid terpolymer is at least about 50 mol% and less than 67 mol% acrylic acid, greater than 0 mol% and up to about 10 mol% 2-acrylamido-2- Methyl-1-propanesulfonic acid and alkaline earth metals and their organic amine salts, from about 15 mol% to about 28 mol% butyl acrylate and from about 7 mol% to about 15 mol% 2-ethylhexyl acrylate Fibrous base material. 142. The method of claim 142, wherein the sulfonate anion modified acrylic acid terpolymer is at least about 57 mole percent and less than 66 mole percent acrylic acid, from about 1 mole percent to about 6 mole percent 2-acrylamido-2-methyl 1-propanesulfonic acid and alkaline earth metals and organic amine salts thereof, from about 15 mol% to about 28 mol% butyl acrylate and from about 7 mol% to about 13 mol% 2-ethylhexyl acrylate Phosphorus fibrous base material. 142. The fibrous substrate of claim 142, wherein the binder composition comprises about 65 to about 75 weight percent sulfonate anion modified acrylic acid terpolymer. 142. The fibrous substrate of claim 142, wherein the binder composition comprises about 55 to about 99 weight percent of noncrosslinkable poly (ethylene-vinyl acetate). 142. The fibrous substrate of claim 142, wherein the binder composition comprises about 25 to about 35 weight percent of non-crosslinkable poly (ethylene-vinyl acetate). 142. The method of claim 142, wherein the sulfonate anion modified acrylic acid terpolymer is at least about 57 mole percent and less than 66 mole percent acrylic acid, from about 1 mole percent to about 6 mole percent AMPS or NaAMPS, from about 15 mole percent to About 28 mole percent butyl acrylate, about 7 mole percent to about 13 mole percent 2-ethylhexyl acrylate, wherein the binder composition comprises about 65 to 75 wt% of sulfonate anion modified acrylic acid terpolymer And about 25 to 35 weight percent uncrosslinked poly (ethylene-vinyl acetate). 142. The fibrous substrate of claim 142, wherein the fibrous material comprises at least one layer of woven, nonwoven, knitted fabric, or combinations thereof. 142. The fibrous substrate of claim 142, wherein the fibrous material comprises at least one layer of nonwoven. 142. The fibrous substrate of claim 142, wherein the fibrous material includes fibers having a length of about 15 mm or less. 142. The fibrous substrate of claim 142, wherein the fibrous material comprises natural fibers, synthetic fibers, or a combination thereof. 142. The fibrous material of claim 142, wherein the fibrous material comprises at least one fiber comprising cotton, linen, jute, hemp, wool, wool pulp, viscose rayon, copper ammonium rayon, cellulose acetate, polyester, polyamide, and polyacrylic. The fibrous base material to be. 142. The fibrous substrate of claim 142, wherein the fibrous material comprises wood pulp. A fibrous substrate comprising a fibrous material and a binder composition for bonding the fibrous material to a unitary web, the binder composition comprising acrylic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid and alkaline earth metals and these A first polymer prepared from at least four monomers selected from organic amine salts, butyl acrylate, and 2-ethylhexyl acrylate, and a second polymer comprising a non-crosslinkable poly (ethylene-vinyl acetate) A fibrous substrate insoluble in a neutral salt solution containing at least about 1% by weight of a salt containing at least one monovalent ion and soluble in water containing at least about 200 ppm of at least one polyvalent ion. 168. The composition of claim 168, wherein the first polymer is at least about 35 mole percent and less than 80 mole percent acrylic acid, greater than 0 mole percent and up to about 20 mole percent 2-acrylamido-2-methyl-1-propanesulfonic acid And alkaline earth metals and organic amine salts thereof, greater than 0 mol% and up to about 65 mol% butyl acrylate and greater than 0 mol% and up to about 45 mol% up to 2-ethylhexyl acrylate. 168. The composition of claim 168, wherein the first polymer is at least about 50 mol% and less than 67 mol% acrylic acid, greater than 0 mol% and up to about 10 mol% 2-acrylamido-2-methyl-1-propanesulfonic acid And alkaline earth metals and organic amine salts thereof, from about 15 mol% to about 28 mol% butyl acrylate and from about 7 mol% to about 15 mol% 2-ethylhexyl acrylate. 168. The composition of claim 168, wherein the first polymer is at least about 57 mole percent and less than 66 mole percent acrylic acid, from about 1 mole percent to about 6 mole percent 2-acrylamido-2-methyl-1-propanesulfonic acid and A fibrous substrate comprising alkaline earth metals and organic amine salts thereof, from about 15 mol% to about 28 mol% butyl acrylate and from about 7 mol% to about 13 mol% 2-ethylhexyl acrylate. 168. The fibrous substrate of claim 168, wherein the first polymer is present in an amount from about 65 to about 75 weight percent. 168. The fibrous substrate of claim 168, wherein the second polymer is present in an amount from about 1 to 45 weight percent. 168. The fibrous substrate of claim 168, wherein the binder composition comprises about 25 to about 35 weight percent of noncrosslinkable poly (ethylene-vinyl acetate). 168. The method of claim 168, wherein the first polymer is at least about 57 mole percent and less than 66 mole percent acrylic acid, about 1 mole percent to about 6 mole percent AMPS or NaAMPS, about 15 mole percent to about 28 mole percent butyl acrylic Rate, from about 7 mol% to about 13 mol% 2-ethylhexyl acrylate, wherein the binder composition comprises about 65 to 75 wt% of the first polymer and about 25 to 35 wt% of the second polymer Fibrous base material. 161. The fibrous substrate of claim 160, wherein said binder composition is insoluble in a neutral solution of monovalent salt containing from about 1 to about 5.0 weight percent salt. 168. The fibrous substrate of claim 168, wherein the fibrous material comprises at least one layer of woven, nonwoven, knitted fabric, or combinations thereof. 168. The fibrous substrate of claim 168, wherein the fibrous material comprises at least one layer of nonwoven fabric. 168. The fibrous substrate of claim 168, wherein the fibrous material comprises fibers having a length of about 15 mm or less. 168. The fibrous substrate of claim 168, wherein the fibrous material comprises natural fibers, synthetic fibers, or a combination thereof. 168. The fiber according to claim 168, wherein the fibrous material comprises cotton, linen, jute, hemp, wool, wool, wood pulp, viscose rayon, copper ammonium rayon, cellulose acetate, polyester, polyamide and polyacrylic Fibrous substrate comprising a. 168. The fibrous substrate of claim 168, wherein the fibrous material comprises wood pulp. 168. A water dispersible product comprising the fibrous substrate of claim 168. A fibrous substrate comprising a fibrous material and a binder composition for bonding the fibrous material to a unitary web, wherein the binder composition is a non-crosslinkable and first polymer made from acrylic acid, butyl acrylate and 2-ethylhexyl acrylate Insoluble in a neutral salt solution comprising a second polymer selected from poly (ethylene-vinyl acetate) and non-crosslinkable poly (styrene-acrylic) and containing at least about 1% by weight of a salt containing at least one monovalent ion; A fibrous substrate soluble in water containing up to about 200 ppm or more of polyvalent ions or more. 188. A water dispersible fibrous product comprising the fibrous substrate of claim 184. A method of making a fibrous substrate comprising adding a binder composition to a fibrous material for bonding the fibrous material to a unitary web, the binder composition comprising an ion sensitive polymer and a cobinder polymer dispersed in the ion sensitive polymer; Wherein the solution is insoluble in a neutral salt solution containing at least about 1% by weight of a salt comprising at least one monovalent ion and is soluble in water containing at least about 200 ppm of at least one polyvalent ion. 186. The method of claim 186, wherein the binder composition is applied to the fibrous material in foam form and drawn to the fibrous material through reduced air pressure. 186. The wetted roll of claim 186 wherein the binder composition is sprayed, foamed, immersed in a binder composition bath, curtain coating, passage of the fibrous material into a submerged nip, coated wet roll rolled coated binder composition. A method applied to a fibrous material in liquid form by one of contact with, compressing and printing the fibrous material against a deformable carrier carrying the binder composition.